Environmental Protection Agency Pt. 63, App. A

APPENDIX A TO PART 63—TEST METHODS posed as an alternative test method to meet an applicable requirement or in the absence METHOD 301—FIELD VALIDATION OF POLLUT- of a validated method. Additionally, the val- ANT MEASUREMENT METHODS FROM VARIOUS idation procedures of Method 301 are appro- WASTE MEDIA priate for demonstration of the suitability of alternative test methods under 40 CFR parts USING METHOD 301 59, 60, and 61. If, under 40 CFR part 63 or 60, 1.0 What is the purpose of Method 301? you choose to propose a validation method other than Method 301, you must submit and 2.0 What approval must I have to use Method obtain the Administrator’s approval for the 301? candidate validation method. 3.0 What does Method 301 include? 2.0 What approval must I have to use Method 301? 4.0 How do I perform Method 301? If you want to use a candidate test method REFERENCE MATERIALS to meet requirements in a subpart of 40 CFR part 59, 60, 61, 63, or 65, you must also request 5.0 What reference materials must I use? approval to use the candidate test method according to the procedures in Section 16 of SAMPLING PROCEDURES this method and the appropriate section of 6.0 What sampling procedures must I use? the part (§ 59.104, § 59.406, § 60.8(b), § 61.13(h)(1)(ii), § 63.7(f), or § 65.158(a)(2)(iii)). 7.0 How do I ensure sample stability? You must receive the Administrator’s written approval to use the candidate test meth- DETERMINATION OF BIAS AND PRECISION od before you use the candidate test method to meet the applicable federal requirements. 8.0 What are the requirements for bias? In some cases, the Administrator may decide 9.0 What are the requirements for precision? to waive the requirement to use Method 301 for a candidate test method to be used to 10.0 What calculations must I perform for meet a requirement under 40 CFR part 59, 60, isotopic spiking? 61, 63, or 65 in absence of a validated test method. Section 17 of this method describes 11.0 What calculations must I perform for the requirements for obtaining a waiver. comparison with a validated method? 3.0 What does Method 301 include? 12.0 What calculations must I perform for analyte spiking? 3.1 Procedures. Method 301 includes minimum procedures to determine and docu- 13.0 How do I conduct tests at similar sources? ment systematic error (bias) and random error (precision) of measured concentrations OPTIONAL REQUIREMENTS from exhaust gases, wastewater, sludge, and other media. Bias is established by com- 14.0 How do I use and conduct ruggedness paring the results of sampling and analysis testing? against a reference value. Bias may be ad- 15.0 How do I determine the Limit of Detection justed on a source-specific basis using a cor- for the candidate test method? rection factor and data obtained during the validation test. Precision may be determined OTHER REQUIREMENTS AND INFORMATION using a paired sampling system or quadruplicate sampling system for isotopic spiking. 16.0 How do I apply for approval to use a A quadruplicate sampling system is required candidate test method? when establishing precision for analyte spiking or when comparing a candidate test 17.0 How do I request a waiver? method to a validated method. If such proce- 18.0 Where can I find additional information? dures have not been established and verified for the candidate test method, Method 301 19.0 Tables. contains procedures for ensuring sample stability by developing sample storage proce- USING METHOD 301 dures and limitations and then testing them. Method 301 also includes procedures for rug- 1.0 What is the purpose of Method 301? gedness testing and determining detection Method 301 provides a set of procedures for limits. The procedures for ruggedness testing the owner or operator of an affected source and determining detection limits are re- to validate a candidate test method as an al- quired for candidate test methods that are to ternative to a required test method based on be applied to multiple sources and optional established precision and bias criteria. These for candidate test methods that are to be ap- validation procedures are applicable under 40 plied at a single source. CFR part 63 or 65 when a test method is pro- 3.2 Definitions.

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Affected source means an affected source as dures in Sections 5.1 through 5.4 of this defined in the relevant part and subpart method. under Title 40 (e.g., 40 CFR parts 59, 60, 61, 63, 5.1 Exhaust Gas Test Concentration. You and 65). must obtain a known concentration of each Candidate test method means the sampling analyte from an independent source such as and analytical methodology selected for field a specialty gas manufacturer, specialty validation using the procedures described in chemical company, or chemical laboratory. Method 301. The candidate test method may You must also obtain the manufacturer’s be an alternative test method under 40 CFR certification of traceability, uncertainty, part 59, 60, 61, 63, or 65. and stability for the analyte concentration. Paired sampling system means a sampling 5.2 Tests for Other Waste Media. You must system capable of obtaining two replicate obtain the pure liquid components of each samples that are collected as closely as pos- analyte from an independent manufacturer. sible in sampling time and sampling location The manufacturer must certify the purity, (collocated). traceability, uncertainty, and shelf life of Quadruplicate sampling system means a sam- the pure liquid components. You must dilute pling system capable of obtaining four rep- the pure liquid components in the same type licate samples (e.g., two pairs of measured medium or matrix as the waste from the af- data, one pair from each method when com- fected source. paring a candidate test method against a 5.3 Surrogate Analytes. If you demonstrate validated test method, or analyte spiking to the Administrator’s satisfaction that a with two spiked and two unspiked samples) surrogate compound behaves as the analyte that are collected as close as possible in sam- does, then you may use surrogate compounds pling time and sampling location. for highly toxic or reactive compounds. A Surrogate compound means a compound surrogate may be an isotope or compound that serves as a model for the target com- that contains a unique element (e.g., chlo- pound(s) being measured (i.e., similar chem- rine) that is not present in the source or a ical structure, properties, behavior). The sur- derivation of the toxic or reactive compound rogate compound can be distinguished by the if the derivative formation is part of the candidate test method from the compounds method’s procedure. You may use laboratory being analyzed. experiments or literature data to show be- havioral acceptability. 4.0 How do I perform Method 301? 5.4 Isotopically-Labeled Materials. Isotope First, you use a known concentration of an mixtures may contain the isotope and the analyte or compare the candidate test meth- natural analyte. The concentration of the od against a validated test method to deter- isotopically-labeled analyte must be more mine the bias of the candidate test method. than five times the concentration of the nat- Then, you collect multiple, collocated simul- urally-occurring analyte. taneous samples to determine the precision SAMPLING PROCEDURES of the candidate test method. Additional procedures, including validation testing over a 6.0 What sampling procedures must I use? broad range of concentrations over an extended time period are used to expand the You must determine bias and precision by applicability of a candidate test method to comparison against a validated test method multiple sources. Sections 5.0 through 17.0 of using isotopic spiking or using analyte spik- this method describe the procedures in de- ing (or the equivalent). Isotopic spiking can tail. only be used with candidate test methods capable of measuring multiple isotopes simul- REFERENCE MATERIALS taneously such as test methods using mass spectrometry or radiological procedures. 5.0 What reference materials must I use? You must collect samples according to the You must use reference materials (a mate- requirements specified in Table 301–1 of this rial or substance with one or more properties method. You must perform the sampling ac- that are sufficiently homogenous to the cording to the procedures in Sections 6.1 analyte) that are traceable to a national through 6.4 of this method. standards body (e.g., National Institute of 6.1 Isotopic Spiking. Spike all 12 samples Standards and Technology (NIST)) at the with isotopically-labelled analyte at an level of the applicable emission limitation or analyte mass or concentration level equiva- standard that the subpart in 40 CFR part 59, lent to the emission limitation or standard 60, 61, 63, or 65 requires. If you want to ex- specified in the applicable regulation. If pand the applicable range of the candidate there is no applicable emission limitation or test method, you must conduct additional standard, spike the analyte at the expected test runs using analyte concentrations high- level of the samples. Follow the applicable er and lower than the applicable emission spiking procedures in Section 6.3 of this limitation or the anticipated level of the tar- method. get analyte. You must obtain information 6.2 Analyte Spiking. In each quadruplicate about your analyte according to the proce- set, spike half of the samples (two out of the

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four samples) with the analyte according to the paired or quadruplicate probes according the applicable procedure in Section 6.3 of to the procedures in this subsection. You this method. You should spike at an analyte must place the probe tips in the same hori- mass or concentration level equivalent to zontal plane. Section 17.1 of Method 301 de- the emission limitation or standard specified scribes conditions for waivers. For example, in the applicable regulation. If there is no the Administrator may approve a validation applicable emission limitation or standard, request where other paired arrangements for spike the analyte at the expected level of the the probe tips or pitot tubes (where required) samples. Follow the applicable spiking pro- are used. cedures in Section 6.3 of this method. 6.4.1 Paired Sampling Probes. For paired 6.3 Spiking Procedure. sampling probes, the first probe tip should be 6.3.1 Gaseous Analyte with Sorbent or Im- 2.5 centimeters (cm) from the outside edge of pinger Sampling Train. Sample the analyte the second probe tip, with a pitot tube on the being spiked (in the laboratory or preferably outside of each probe. in the field) at a mass or concentration that 6.4.2 Quadruplicate Sampling Probes. For is approximately equivalent to the applica- quadruplicate sampling probes, the tips ble emission limitation or standard (or the should be in a 6.0 cm × 6.0 cm square area expected sample concentration or mass measured from the center line of the opening where there is no standard) for the time re- of the probe tip with a single pitot tube, quired by the candidate test method, and where required, in the center of the probe then sample the stack gas stream for an tips or two pitot tubes, where required, with equal amount of time. The time for sampling their location on either side of the probe tip both the analyte and stack gas stream configuration. Section 17.1 of Method 301 de- should be equal; however, you must adjust scribes conditions for waivers. For example, the sampling time to avoid sorbent break- you must propose an alternative arrange- through. You may sample the stack gas and ment whenever the cross-sectional area of the gaseous analyte at the same time. You the probe tip configuration is approximately must introduce the analyte as close to the five percent or more of the stack or duct tip of the sampling probe as possible. cross-sectional area. 6.3.2 Gaseous Analyte with Sample Con- tainer (Bag or Canister). Spike the sample 7.0 How do I ensure sample stability? containers after completion of each test run 7.1 Developing Sample Storage and Thresh- with an analyte mass or concentration to old Procedures. If the candidate test method yield a concentration approximately equiva- includes well-established procedures sup- lent to the applicable emission limitation or ported by experimental data for sample stor- standard (or the expected sample concentra- age and the time within which the collected tion or mass where there is no standard). samples must be analyzed, you must store Thus, the final concentration of the analyte the samples according to the procedures in in the sample container would be approxi- the candidate test method and you are not mately equal to the analyte concentration in required to conduct the procedures specified the stack gas plus the equivalent of the ap- in Section 7.2 or 7.3 of this method. If the plicable emission standard (corrected for candidate test method does not include such spike volume). The volume amount of spiked procedures, your candidate method must in- gas must be less than 10 percent of the sam- clude procedures for storing and analyzing ple volume of the container. samples to ensure sample stability. At a 6.3.3 Liquid or Solid Analyte with Sorbent or minimum, your proposed procedures must Impinger Trains. Spike the sampling trains meet the requirements in Section 7.2 or 7.3 of with an amount approximately equivalent to this method. The minimum duration be- the mass or concentration in the applicable tween sample collection and storage must be emission limitation or standard (or the ex- as soon as possible, but no longer than 72 pected sample concentration or mass where hours after collection of the sample. The there is no standard) before sampling the maximum storage duration must not be stack gas. If possible, do the spiking in the longer than 2 weeks. field. If it is not possible to do the spiking in 7.2 Storage and Sampling Procedures for the field, you must spike the sampling trains Stack Test Emissions. You must store and ana- in the laboratory. lyze samples of stack test emissions accord- 6.3.4 Liquid and Solid Analyte with Sample ing to Table 301–2 of this method. You may Container (Bag or Canister). Spike the con- reanalyze the same sample at both the min- tainers at the completion of each test run imum and maximum storage durations for: with an analyte mass or concentration ap- (1) Samples collected in containers such as proximately equivalent to the applicable bags or canisters that are not subject to di- emission limitation or standard in the sub- lution or other preparation steps, or (2) im- part (or the expected sample concentration pinger samples not subjected to preparation or mass where there is no standard). steps that would affect stability of the sam- 6.4 Probe Placement and Arrangement for ple such as extraction or digestion. For can- Stationary Source Stack or Duct Sampling. To didate test method samples that do not meet sample a stationary source, you must place either of these criteria, you must analyze

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one of a pair of replicate samples at the min- duration and the other replicate (other half imum storage duration and the other rep- of samples) at the maximum storage dura- licate at the proposed storage duration but tion or within 2 weeks of the initial analysis no later than 2 weeks of the initial analysis to identify the effect of storage duration on to identify the effect of storage duration on analyte samples. The minimum time period analyte samples. If you are using the iso- between collection and storage should be as topic spiking procedure, then you must ana- soon as possible, but no longer than 72 hours lyze each sample for the spiked analyte and after collection of the sample. the native analyte. 7.4 Sample Stability. After you have con- 7.3 Storage and Sampling Procedures for ducted sampling and analysis according to Testing Other Waste Media (e.g., Soil/Sediment, Section 7.2 or 7.3 of this method, compare Solid Waste, Water/Liquid). You must analyze the results at the minimum and maximum one of each pair of replicate samples (half storage durations. Calculate the difference the total samples) at the minimum storage in the results using Equation 301–1.

Where: canister samples and impinger samples that th di = Difference between the results of the i do not require digestion or extraction), the replicate pair of samples. values for Rmini and Rmaxi will be obtained th Rmini = Results from the i replicate sample from the same sample rather than replicate pair at the minimum storage duration. samples. th Rmaxi = Results from the i replicate sample 7.4.1 Standard Deviation. Determine the pair at the maximum storage duration. standard deviation of the paired samples For single samples that can be reanalyzed using Equation 301–2. for sample stability assessment (e.g., bag or

Where: 7.4.2 T Test. Test the difference in the results for statistical significance by calcu- SDd = Standard deviation of the differences of the paired samples. lating the t-statistic and determining if the mean of the differences between the results d = Difference between the results of the ith i at the minimum storage duration and the re- replicate pair of samples. sults after the maximum storage duration is dm = Mean of the paired sample differences. significant at the 95 percent confidence level n = Total number of paired samples. and n–1 degrees of freedom. Calculate the value of the t-statistic using Equation 301–3.

Where: dm = The mean of the paired sample dif- t = t-statistic. ferences.

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SDd = Standard deviation of the differences data collected in the future using the can- of the paired samples. didate test method. If the bias is more than n = Total number of paired samples. ±30 percent, the candidate test method is un- Compare the calculated t-statistic with the acceptable. critical value of the t-statistic from Table 9.0 What are the requirements for precision? 301–3 of this method. If the calculated t-value is less than the critical value, the difference You may use a paired sampling system or is not statistically significant. Therefore, a quadruplicate sampling system to establish the sampling, analysis, and sample storage precision for isotopic spiking. You must use procedures ensure stability, and you may a quadruplicate sampling system to establish submit a request for validation of the can- precision for analyte spiking or when com- didate test method. If the calculated t-value paring a candidate test method to a vali- is greater than the critical value, the dif- dated method. If you are using analyte spik- ference is statistically significant, and you ing or isotopic spiking, the precision, ex- must repeat the procedures in Section 7.2 or pressed as the relative standard deviation 7.3 of this method with new samples using a (RSD) of the candidate test method, must be shorter proposed maximum storage duration less than or equal to 20 percent. If you are or improved handling and storage proce- comparing the candidate test method to a dures. validated test method, the candidate test method must be at least as precise as the DETERMINATION OF BIAS AND PRECISION validated method as determined by an F test 8.0 What are the requirements for bias? (see Section 11.2.2 of this method). You must determine bias by comparing the 10.0 What calculations must I perform for results of sampling and analysis using the isotopic spiking? candidate test method against a reference value. The bias must be no more than ±10 You must analyze the bias, RSD, precision, percent for the candidate test method to be and data acceptance for isotopic spiking considered for application to multiple tests according to the provisions in Sections sources. A candidate test method with a bias 10.1 through 10.4 of this method. greater than ±10 percent and less than or 10.1 Numerical Bias. Calculate the numer- equal to ±30 percent can only be applied on a ical value of the bias using the results from source-specific basis at the facility at which the analysis of the isotopic spike in the field the validation testing was conducted. In this samples and the calculated value of the case, you must use a correction factor for all spike according to Equation 301–4.

Where: CS = Calculated value of the isotopically-la- B = Bias at the spike level. beled spike level.

Sm = Mean of the measured values of the 10.2 Standard Deviation. Calculate the isotopically-labeled analyte in the sam- standard deviation of the Si values according ples. to Equation 301–5.

Where: Sm = Mean of the measured values of the SD = Standard deviation of the candidate isotopically-labeled analyte in the sam- test method. ples. n = Number of isotopically-spiked samples. Si = Measured value of the isotopically-labeled analyte in the ith field sample.

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10.3 T Test. Test the bias for statistical ation determined in Section 10.2 of this significance by calculating the t-statistic method and the numerical bias determined using Equation 301–6. Use the standard devi- in Section 10.1 of this method.

Where: according to the procedures specified in Sec- t = Calculated t-statistic. tions 6.1 and 6.3 of this method as required, B = Bias at the spike level. this critical value is 2.201 for 11 degrees of SD = Standard deviation of the candidate freedom. If the calculated t-value is less test method. than or equal to the critical value, the bias n = Number of isotopically spike samples. is not statistically significant, and the bias Compare the calculated t-value with the of the candidate test method is acceptable. If critical value of the two-sided t-distribution the calculated t-value is greater than the at the 95 percent confidence level and n–1 de- critical value, the bias is statistically sig- grees of freedom (see Table 301–3 of this nificant, and you must evaluate the relative method). When you conduct isotopic spiking magnitude of the bias using Equation 301–7.

Where: using the source-specific correction factor

BR = Relative bias. determined in Equation 301–8, the candidate B = Bias at the spike level. test method is acceptable only for applica- CS = Calculated value of the spike level. tion to the source at which the validation testing was conducted and may not be ap- If the relative bias is less than or equal to 10 percent, the bias of the candidate test plied to any other sites. If either of the pre- method is acceptable for use at multiple ceding two cases applies, you may continue sources. If the relative bias is greater than 10 to evaluate the candidate test method by percent but less than or equal to 30 percent, calculating its precision. If not, the can- and if you correct all data collected with the didate test method does not meet the re- candidate test method in the future for bias quirements of Method 301.

Where: 10.4 Precision. Calculate the RSD accord- CF = Source-specific bias correction factor. ing to Equation 301–9. B = Bias at the spike level. CS = Calculated value of the spike level. If the CF is outside the range of 0.70 to 1.30, the data and method are considered unacceptable.

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Where: visions in this section. If the data from the RSD = Relative standard deviation of the candidate test method fail either the bias or candidate test method. precision test, the data and the candidate SD = Standard deviation of the candidate test method are unacceptable. If the Admin- test method calculated in Equation 301–5. istrator determines that the affected source Sm = Mean of the measured values of the has highly variable emission rates, the Ad- spike samples. ministrator may require additional precision The data and candidate test method are checks. unacceptable if the RSD is greater than 20 11.1 Bias Analysis. Test the bias for statis- percent. tical significance at the 95 percent confidence level by calculating the t-statistic. 11.0 What calculations must I perform for 11.1.1 Bias. Determine the bias, which is comparison with a validated method? defined as the mean of the differences be- If you are comparing a candidate test tween the candidate test method and the method to a validated method, then you validated method (dm). Calculate di according must analyze the data according to the pro- to Equation 301–10.

Where: P1i = First measured value with the candidate test method in the ith quadruplicate di = Difference in measured value between the candidate test method and the validated sampling train. method for each quadruplicate sampling P2i = Second measured value with the can- train. didate test method in the ith quadruplicate V1i = First measured value with the vali- sampling train. dated method in the ith quadruplicate sampling train. Calculate the numerical value of the bias V2i = Second measured value with the vali- using Equation 301–11. dated method in the ith quadruplicate sampling train.

Where: n = Number of quadruplicate sampling B = Numerical bias. trains. di = Difference between the candidate test 11.1.2 Standard Deviation of the Differences. method and the validated method for the ith Calculate the standard deviation of the dif- quadruplicate sampling train. ferences, SDd, using Equation 301–12.

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Where: dm = Mean of the differences, di, between the

SDd = Standard deviation of the differences candidate test method and the validated between the candidate test method and method. the validated method. n = Number of quadruplicate sampling di = Difference in measured value between the trains. candidate test method and the validated method for each quadruplicate sampling 11.1.3 T Test. Calculate the t-statistic train. using Equation 301–13.

Where: critical value of the t-statistic, and deter- t = Calculated t-statistic. mine if the bias is significant at the 95 per- dm = The mean of the differences, di, between cent confidence level (see Table 301–3 of this the candidate test method and the vali- method). When six runs are conducted, as dated method. specified in Table 301–1 of this method, the SDd = Standard deviation of the differences critical value of the t-statistic is 2.571 for between the candidate test method and five degrees of freedom. If the calculated t- the validated method. value is less than or equal to the critical n = Number of quadruplicate sampling value, the bias is not statistically significant trains. and the data are acceptable. If the calculated For the procedure comparing a candidate t-value is greater than the critical value, the test method to a validated test method listed bias is statistically significant, and you in Table 301–1 of this method, n equals six. must evaluate the magnitude of the relative Compare the calculated t-statistic with the bias using Equation 301–14.

Where: termined in Equation 301–8 (using VS for CS), the bias of the candidate test method is BR = Relative bias. B = Bias as calculated in Equation 301–11. acceptable for application to the source at VS = Mean of measured values from the vali- which the validation testing was conducted. dated method. If either of the preceding two cases applies, you may continue to evaluate the candidate If the relative bias is less than or equal to test method by calculating its precision. If 10 percent, the bias of the candidate test not, the candidate test method does not method is acceptable. On a source-specific meet the requirements of Method 301. basis, if the relative bias is greater than 10 11.2 Precision. Compare the estimated percent but less than or equal to 30 percent, variance (or standard deviation) of the can- and if you correct all data collected in the didate test method to that of the validated future with the candidate test method for test method according to Sections 11.2.1 and the bias using the correction factor, CF, de-

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11.2.2 of this method. If a significant dif- 11.2.1 Candidate Test Method Variance. Cal- ference is determined using the F test, the culate the estimated variance of the can- candidate test method and the results are re- didate test method according to Equation jected. If the F test does not show a signifi- 301–15. cant difference, then the candidate test method has acceptable precision.

Where: n = Total number of paired samples (quadru- P = Estimated variance of the candidate test plicate trains). method. Calculate the estimated variance of the d = The difference between the ith pair of i validated test method according to Equation samples collected with the candidate test method in a single quadruplicate train. 301–16.

Where: n = Total number of paired samples (quadru- V = Estimated variance of the validated test plicate trains). method. 11.2.2 The F test. Determine if the esti- th di = The difference between the i pair of mated variance of the candidate test method samples collected with the validated test is greater than that of the validated method method in a single quadruplicate train. by calculating the F-value using Equation 301–17.

Where: data and the candidate test method are un- F = Calculated F value. acceptable. P = The estimated variance of the candidate 12.0 What calculations must I perform for test method. analyte spiking? V = The estimated variance of the validated method. You must analyze the data for analyte spike testing according to this section. Compare the calculated F value with the 12.1 Bias Analysis. Test the bias for statis- one-sided confidence level for F from Table tical significance at the 95 percent con- 301–4 of this method. The upper one-sided fidence level by calculating the t-statistic. confidence level of 95 percent for F( ) is 4.28 6,6 12.1.1 Bias. Determine the bias, which is when the procedure specified in Table 301–1 defined as the mean of the differences be- of this method for quadruplicate sampling tween the spiked samples and the unspiked trains is followed. If the calculated F value samples in each quadruplicate sampling is greater than the critical F value, the dif- train minus the spiked amount, using Equa- ference in precision is significant, and the tion 301–18.

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Where: M1i = Measured value of the first unspiked th di = Difference between the spiked samples sample in the i quadruplicate sampling and unspiked samples in each quadru- train. plicate sampling train minus the spiked M2i = Measured value of the second unspiked amount. sample in the ith quadruplicate sampling S1i = Measured value of the first spiked sam- train. ple in the ith quadruplicate sampling CS = Calculated value of the spike level. train. S2i = Measured value of the second spiked Calculate the numerical value of the bias sample in the ith quadruplicate sampling using Equation 301–19. train.

Where: n = Number of quadruplicate sampling B = Numerical value of the bias. trains. d = Difference between the spiked samples i 12.1.2 Standard Deviation of the Differences. and unspiked samples in each quadru- Calculate the standard deviation of the dif- plicate sampling train minus the spiked amount. ferences using Equation 301–20.

Where: n = Total number of quadruplicate sampling

SDd = Standard deviation of the differences trains. of paired samples. 12.1.3 T Test. Calculate the t-statistic d = Difference between the spiked samples i using Equation 301–21, where n is the total and unspiked samples in each quadru- number of test sample differences (d ). For plicate sampling train minus the spiked i amount. the quadruplicate sampling system procedure in Table 301–1 of this method, n equals dm = The mean of the differences, di, between the spiked samples and unspiked sam- six. ples.

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Where: cent confidence level. When six quadru- t = Calculated t-statistic. plicate runs are conducted, as specified in Table 301–1 of this method, the 2-sided con- dm = Mean of the difference, di, between the spiked samples and unspiked samples. fidence level critical value is 2.571 for the five degrees of freedom. If the calculated t- SDd = Standard deviation of the differences of paired samples. value is less than the critical value, the bias is not statistically significant and the data n = Number of quadruplicate sampling are acceptable. If the calculated t-value is trains. greater than the critical value, the bias is Compare the calculated t-statistic with the statistically significant and you must evalu- critical value of the t-statistic, and deter- ate the magnitude of the relative bias using mine if the bias is significant at the 95 per- Equation 301–22.

Where: and if you correct all data collected with the

BR = Relative bias. candidate test method in the future for the B = Bias at the spike level from Equation magnitude of the bias using Equation 301–8, 301–19. the bias of the candidate test method is ac- CS = Calculated value at the spike level. ceptable for application to the tested source If the relative bias is less than or equal to at which the validation testing was con- 10 percent, the bias of the candidate test ducted. Proceed to evaluate precision of the method is acceptable. On a source-specific candidate test method. basis, if the relative bias is greater than 10 12.2 Precision. Calculate the standard devi- percent but less than or equal to 30 percent, ation using Equation 301–23.

Where: ministrator as described in Section 17.1.1 of SD = Standard deviation of the candidate this method. test method. th OPTIONAL REQUIREMENTS Si = Measured value of the analyte in the i spiked sample. 14.0 How do I use and conduct ruggedness Sm = Mean of the measured values of the testing? analyte in all the spiked samples. n = Number of spiked samples. Ruggedness testing is an optional requirement for validation of a candidate test meth- Calculate the RSD of the candidate test od that is intended for the source where the method using Equation 301–9, where SD and validation testing was conducted. Rugged- S are the values from Equation 301–23. The m ness testing is required for validation of a data and candidate test method are unacceptable if the RSD is greater than 20 per- candidate test method intended to be used at cent. multiple sources. If you want to use a validated test method at a concentration that is 13.0 How do I conduct tests at similar sources? different from the concentration in the applicable emission limitation under 40 CFR If the Administrator has approved the use part 59, 60, 61, 63, or 65, or for a source cat- of an alternative test method to a test meth- egory that is different from the source cat- od required in 40 CFR part 59, 60, 61, 63, or 65 egory that the test method specifies, then for an affected source, and you would like to apply the alternative test method to a simi- you must conduct ruggedness testing accord- lar source, then you must petition the Ad- ing to the procedures in Reference 18.16 of

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Section 18.0 of this method and submit a re- these parts until the Administrator has ap- quest for a waiver for conducting Method 301 proved your request. The request must in- at that different source category according clude a field validation report containing the to Section 17.1.1 of this method. information in Section 16.2 of this method. Ruggedness testing is a study that can be You must submit the request to the Group conducted in the laboratory or the field to Leader, Measurement Technology Group, determine the sensitivity of a method to pa- U.S. Environmental Protection Agency, rameters such as analyte concentration, E143–02, Research Triangle Park, NC 27711. sample collection rate, interferent con- 16.2 Field Validation Report. The field vali- centration, collection medium temperature, dation report must contain the information and sample recovery temperature. You con- in Sections 16.2.1 through 16.2.8 of this meth- duct ruggedness testing by changing several od. variables simultaneously instead of changing 16.2.1 Regulatory objectives for the testing, one variable at a time. For example, you can including a description of the reasons for the determine the effect of seven variables in test, applicable emission limits, and a descrip- only eight experiments. (W.J. Youden, Sta- tion of the source. tistical Manual of the Association of Official 16.2.2 Summary of the results and calcula- Analytical Chemists, Association of Official tions shown in Sections 6.0 through 16.0 of this Analytical Chemists, Washington, DC, 1975, method, as applicable. pp. 33–36). 16.2.3 Reference material certification and value(s). 15.0 How do I determine the Limit of Detection 16.2.4 Discussion of laboratory evaluations. for the candidate test method? 16.2.5 Discussion of field sampling. Determination of the Limit of Detection 16.2.6 Discussion of sample preparation and (LOD) as specified in Sections 15.1 and 15.2 of analysis. this method is required for source-specific 16.2.7 Storage times of samples (and extracts, method validation and validation of a can- if applicable). didate test method intended to be used for 16.2.8 Reasons for eliminating any results. multiple sources. 17.0 How do I request a waiver? 15.1 Limit of Detection. The LOD is the minimum concentration of a substance that 17.1 Conditions for Waivers. If you meet can be measured and reported with 99 per- one of the criteria in Section 17.1.1 or 17.1.2 cent confidence that the analyte concentra- of this method, the Administrator may tion is greater than zero. For this protocol, waive the requirement to use the procedures the LOD is defined as three times the stand- in this method to validate an alternative or ard deviation, So, at the blank level. other candidate test method. In addition, if 15.2 Purpose. The LOD establishes the the EPA currently recognizes an appropriate lower detection limit of the candidate test test method or considers the candidate test method. You must calculate the LOD using method to be satisfactory for a particular the applicable procedures found in Table 301– source, the Administrator may waive the use 5 of this method. For candidate test methods of this protocol or may specify a less rig- that collect the analyte in a sample matrix orous validation procedure. prior to an analytical measurement, you 17.1.1 Similar Sources. If the alternative or must determine the LOD using Procedure I other candidate test method that you want in Table 301–5 of this method by calculating to use was validated for source-specific ap- a method detection limit (MDL) as described plication at another source and you can dem- in 40 CFR part 136, appendix B. For the pur- onstrate to the Administrator’s satisfaction poses of this section, the LOD is equivalent that your affected source is similar to that to the calculated MDL. For radiochemical validated source, then the Administrator methods, use the Multi-Agency Radiological may waive the requirement for you to vali- Laboratory Analytical Protocols (MARLAP) date the alternative or other candidate test Manual (i.e., use the minimum detectable method. One procedure you may use to dem- concentration (MDC) and not the LOD) avail- onstrate the applicability of the method to able at https://www.epa.gov/radiation/marlap- your affected source is to conduct a rugged- manual-and-supporting-documents. ness test as described in Section 14.0 of this method. OTHER REQUIREMENTS AND INFORMATION 17.1.2 Documented Methods. If the bias, precision, LOD, or ruggedness of the alter- 16.0 How do I apply for approval to use a native or other candidate test method that candidate test method? you are proposing have been demonstrated 16.1 Submitting Requests. You must request through laboratory tests or protocols dif- to use a candidate test method according to ferent from this method, and you can dem- the procedures in § 63.7(f) or similar sections onstrate to the Administrator’s satisfaction of 40 CFR parts 59, 60, 61, and 65 (§ 59.104, that the bias, precision, LOD, or ruggedness § 59.406, § 60.8(b), § 61.13(h)(1)(ii), or apply to your application, then the Adminis- § 65.158(a)(2)(iii)). You cannot use a candidate trator may waive the requirement to use test method to meet any requirement under this method or to use part of this method.

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17.2 Submitting Applications for Waivers. Triangle Institute, Research Triangle You must sign and submit each request for a Park, NC. September. waiver from the requirements in this method 18.2 ASTM Standard E 1169–89 (current in writing. The request must be submitted to version), ‘‘Standard Guide for Con- the Group Leader, Measurement Technology ducting Ruggedness Tests,’’ available Group, U.S. Environmental Protection Agen- from ASTM, 100 Barr Harbor Drive, West cy, E143–02, Research Triangle Park, NC Conshohoken, PA 19428. 27711. 18.3 DeWees, W.G., P.M. Grohse, K.K. Luk, 17.3 Information Application for Waiver. and F.E. Butler. 1989. Laboratory and The request for a waiver must contain a Field Evaluation of a Methodology for thorough description of the candidate test Speciating Nickel Emissions from Sta- method, the intended application, and re- tionary Sources. EPA Contract 68–02– sults of any validation or other supporting 4442. Prepared for Atmospheric Research documents. The request for a waiver must and Environmental Assessment Labora- contain, at a minimum, the information in tory, Office of Research and Develop- Sections 17.3.1 through 17.3.4 of this method. ment, U.S. Environmental Protection The Administrator may request additional Agency, Research Triangle Park, NC information if necessary to determine 27711. January. whether this method can be waived for a par- 18.4 International Conference on Harmoni- ticular application. zation of Technical Requirements for the 17.3.1 A Clearly Written Test Method. The Registration of Pharmaceuticals for candidate test method should be written Human Use, ICH–Q2A, ‘‘Text on Valida- preferably in the format of 40 CFR part 60, tion of Analytical Procedures,’’ 60 FR appendix A, Test Methods. Additionally, the 11260 (March 1995). candidate test must include an applicability 18.5 International Conference on Harmoni- statement, concentration range, precision, zation of Technical Requirements for the bias (accuracy), and minimum and maximum Registration of Pharmaceuticals for storage durations in which samples must be Human Use, ICH–Q2b, ‘‘Validation of An- analyzed. alytical Procedures: Methodology,’’ 62 17.3.2 Summaries of Previous Validation FR 27464 (May 1997). Tests or Other Supporting Documents. If you 18.6 Keith, L.H., W. Crummer, J. Deegan use a different procedure from that described Jr., R.A. Libby, J.K. Taylor, and G. in this method, you must submit documents Wentler. 1983. Principles of Environ- substantiating the bias and precision values mental Analysis. American Chemical So- to the Administrator’s satisfaction. ciety, Washington, DC. 17.3.3 Ruggedness Testing Results. You 18.7 Maxwell, E.A. 1974. Estimating must submit results of ruggedness testing variances from one or two measurements conducted according to Section 14.0 of this on each sample. Amer. Statistician 28:96– method, sample stability conducted accord- 97. ing to Section 7.0 of this method, and detec- 18.8 Midgett, M.R. 1977. How EPA Validates tion limits conducted according to Section NSPS Methodology. Environ. Sci. & 15.0 of this method, as applicable. For exam- Technol. 11(7):655–659. ple, you would not need to submit rugged- 18.9 Mitchell, W.J., and M.R. Midgett. 1976. ness testing results if you will be using the Means to evaluate performance of sta- method at the same affected source and level tionary source test methods. Environ. at which it was validated. Sci. & Technol. 10:85–88. 17.3.4 Applicability Statement and Basis for 18.10 Plackett, R.L., and J.P. Burman. 1946. Waiver Approval. Discussion of the applica- The design of optimum multifactorial ex- bility statement and basis for approval of periments. Biometrika, 33:305. the waiver. This discussion should address as 18.11 Taylor, J.K. 1987. Quality Assurance of applicable the following: applicable regula- Chemical Measurements. Lewis Pub- tion, emission standards, effluent character- lishers, Inc., pp. 79–81. istics, and process operations. 18.12 U.S. Environmental Protection Agen- cy. 1978. Quality Assurance Handbook for 18.0 Where can I find additional information? Air Pollution Measurement Systems: Volume III. Stationary Source Specific You can find additional information in the Methods. Publication No. EPA–600/4–77– references in Sections 18.1 through 18.18 of 027b. Office of Research and Development this method. Publications, 26 West St. Clair St., Cin- 18.1 Albritton, J.R., G.B. Howe, S.B. Tomp- cinnati, OH 45268. kins, R.K.M. Jayanty, and C.E. Decker. 18.13 U.S. Environmental Protection Agen- 1989. Stability of Parts-Per-Million Or- cy. 1981. A Procedure for Establishing ganic Cylinder Gases and Results of Traceability of Gas Mixtures to Certain Source Test Analysis Audits, Status Re- National Bureau of Standards Standard port No. 11. Environmental Protection Reference Materials. Publication No. Agency Contract 68–02–4125. Research EPA–600/7–81–010. Available from the U.S.

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EPA, Quality Assurance Division (MD– 18.16 Youden, W.J. Statistical techniques 77), Research Triangle Park, NC 27711. for collaborative tests. In: Statistical 18.14 U.S. Environmental Protection Agen- Manual of the Association of Official An- cy. 1991. Protocol for The Field Valida- alytical Chemists, Association of Official tion of Emission Concentrations from Analytical Chemists, Washington, DC, Stationary Sources. Publication No. 450/ 1975, pp. 33–36. 4–90–015. Available from the U.S. EPA, 18.17 NIST/SEMATECH (current version), Emission Measurement Technical Infor- ‘‘e-Handbook of Statistical Methods,’’ mation Center, Technical Support Divi- sion (MD–14), Research Triangle Park, available from NIST, http:// NC 27711. www.itl.nist.gov/div898/handbook/. 18.15 Wernimont, G.T., ‘‘Use of Statistics to 18.18 Statistical Table, http:// Develop and Evaluate Analytical Meth- www.math.usask.ca/∼szafron/Stats244/ ods,’’ AOAC, 1111 North 19th Street, fltablel0l05.pdf. Suite 210, Arlington, VA 22209, USA, 78–82 (1987). 19.0 Tables.

TABLE 301–1—SAMPLING PROCEDURES

If you are... You must collect...

Comparing the candidate test method against a validated A total of 24 samples using a quadruplicate sampling system method. (a total of six sets of replicate samples). In each quadruplicate sample set, you must use the validated test method to collect and analyze half of the samples. Using isotopic spiking (can only be used with methods capable A total of 12 samples, all of which are spiked with isotopically- of measurement of multiple isotopes simultaneously). labeled analyte. You may collect the samples either by obtaining six sets of paired samples or three sets of quadruplicate samples. Using analyte spiking ...... A total of 24 samples using the quadruplicate sampling system (a total of six sets of replicate samples—two spiked and two unspiked).

TABLE 301–2—STORAGE AND SAMPLING PROCEDURES FOR STACK TEST EMISSIONS

If you are... With... Then you must...

Using isotopic or analyte spik- Sample container (bag or can- Analyze six of the samples within 7 days and then analyze ing procedures. ister) or impinger sampling the same six samples at the proposed maximum storage systems that are not subject duration or 2 weeks after the initial analysis. to dilution or other preparation steps. Sorbent and impinger sam- Extract or digest six of the samples within 7 days and extract pling systems that require or digest six other samples at the proposed maximum stor- extraction or digestion. age duration or 2 weeks after the first extraction or digestion. Analyze an aliquot of the first six extracts (digestates) within 7 days and proposed maximum storage duration or 2 weeks after the initial analysis. This will allow analysis of extract storage impacts. Sorbent sampling systems that Analyze six samples within 7 days. Analyze another set of six require thermal desorption. samples at the proposed maximum storage time or within 2 weeks of the initial analysis. Comparing a candidate test Sample container (bag or can- Analyze at least six of the candidate test method samples method against a validated ister) or impinger sampling within 7 days and then analyze the same six samples at test method. systems that are not subject the proposed maximum storage duration or within 2 weeks to dilution or other prepara- of the initial analysis. tion steps. Sorbent and impinger sam- Extract or digest six of the candidate test method samples pling systems that require within 7 days and extract or digest six other samples at the extraction or digestion. proposed maximum storage duration or within 2 weeks of the first extraction or digestion. Analyze an aliquot of the first six extracts (digestates) within 7 days and an aliquot at the proposed maximum storage durations or within 2 weeks of the initial analysis. This will allow analysis of extract storage impacts. Sorbent systems that require Analyze six samples within 7 days. Analyze another set of six thermal desorption. samples at the proposed maximum storage duration or within 2 weeks of the initial analysis.

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TABLE 301–3—CRITICAL VALUES OF t FOR THE TWO-TAILED 95 PERCENT CONFIDENCE LIMIT 1

Degrees of freedom t95

1 ...... 12.706 2 ...... 4.303 3 ...... 3.182 4 ...... 2.776 5 ...... 2.571 6 ...... 2.447 7 ...... 2.365 8 ...... 2.306 9 ...... 2.262 10 ...... 2.228 11 ...... 2.201 12 ...... 2.179 13 ...... 2.160 14 ...... 2.145 15 ...... 2.131 16 ...... 2.120 17 ...... 2.110 18 ...... 2.101 19 ...... 2.093 20 ...... 2.086 1 Adapted from Reference 18.17 in section 18.0.

TABLE 301–4—UPPER CRITICAL VALUES OF THE F DISTRIBUTION FOR THE 95 PERCENT CONFIDENCE LIMIT 1

Numerator (k1) and denominator (k2) degrees of freedom F{F>F.05(k1,k2)}

1,1 ...... 161.40 2,2 ...... 19.00 3,3 ...... 9.28 4,4 ...... 6.39 5,5 ...... 5.05 6,6 ...... 4.28 7,7 ...... 3.79 8,8 ...... 3.44 9,9 ...... 3.18 10,10 ...... 2.98 11,11 ...... 2.82 12,12 ...... 2.69 13,13 ...... 2.58 14,14 ...... 2.48 15,15 ...... 2.40 16,16 ...... 2.33 17,17 ...... 2.27 18,18 ...... 2.22 19,19 ...... 2.17 20,20 ...... 2.12 1 Adapted from References 18.17 and 18.18 in section 18.0.

TABLE 301–5—PROCEDURES FOR ESTIMATING So

If the estimated LOD (LOD1, expected approxi- If the estimated LOD (LOD1, expected approx- mate LOD concentration level) is no more imate LOD concentration level) is greater than twice the calculated LOD or an analyte than twice the calculated LOD, use Proce- in a sample matrix was collected prior to an dure II as follows. analytical measurement, use Procedure I as follows. Procedure I: Procedure II: Determine the LOD by calculating a Prepare two additional standards (LOD2 method detection limit (MDL) as de- and LOD3) at concentration levels lower scribed in 40 CFR part 136, appen- than the standard used in Procedure I dix B. (LOD1). Sample and analyze each of these standards (LOD2 and LOD3) at least seven times.

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TABLE 301–5—PROCEDURES FOR ESTIMATING So—Continued

Calculate the standard deviation (S2 and S3) for each concentration level. Plot the standard deviations of the three test standards (S1, S2 and S3) as a function of concentration. Draw a best-fit straight line through the data points and extrapolate to zero concentration. The standard deviation at zero concentration is So. Calculate the LOD0 (referred to as the calculated LOD) as 3 times So.

METHOD 303—DETERMINATION OF VISIBLE 3.4 Charging system means an apparatus EMISSIONS FROM BY-PRODUCT COKE OVEN used to charge coal to a coke oven (e.g., a BATTERIES larry car for wet coal charging systems). 3.5 Coke oven door means each end enclo- NOTE: This method is not inclusive with re- sure on the push side and the coking side of spect to observer certification. Some mate- an oven. The chuck, or leveler-bar, door is rial is incorporated by reference from other methods in appendix A to 40 CFR part 60. considered part of the push side door. The Therefore, to obtain reliable results, persons coke oven door area includes the entire area using this method should have a thorough on the vertical face of a coke oven between knowledge of Method 9. the bench and the top of the battery between two adjacent buck stays. 1.0 Scope and Application 3.6 Coke side means the side of a battery from which the coke is discharged from 1.1 Applicability. This method is applica- ovens at the end of the coking cycle. ble for the determination of visible emis- 3.7 Collecting main means any apparatus sions (VE) from the following by-product that is connected to one or more offtake sys- coke oven battery sources: charging systems tems and that provides a passage for con- during charging; doors, topside port lids, and veying gases under positive pressure from offtake systems on operating coke ovens; the by-product coke oven battery to the by- and collecting mains. This method is also ap- product recovery system. plicable for qualifying observers for visually 3.8 Consecutive charges means charges ob- determining the presence of VE. In order for served successively, excluding any charge the test method results to be indicative of plant performance, the time of day of the during which the observer’s view of the run should vary. charging system or topside ports is obscured. 3.9 Damper-off means to close off the gas 2.0 Summary of Method passage between the coke oven and the collecting main, with no flow of raw coke oven 2.1 A certified observer visually deter- gas from the collecting main into the oven mines the VE from coke oven battery or into the oven’s offtake system(s). sources. Certification procedures are pre- 3.10 Decarbonization period means the pe- sented. This method does not require that riod of time for combusting oven carbon that opacity of emissions be determined or that commences when the oven lids are removed magnitude be differentiated. from an empty oven or when standpipe caps of an oven are opened. The period ends with 3.0 Definitions the initiation of the next charging period for 3.1 Bench means the platform structure in that oven. front of the oven doors. 3.11 Larry car means an apparatus used to 3.2 By-product Coke Oven Battery means a charge coal to a coke oven with a wet coal source consisting of a group of ovens con- charging system. nected by common walls, where coal under- 3.12 Log average means logarithmic aver- goes destructive distillation under positive age as calculated in Section 12.4. pressure to produce coke and coke oven gas, 3.13 Offtake system means any individual from which by-products are recovered. oven apparatus that is stationary and pro- 3.3 Charge or charging period means the pe- vides a passage for gases from an oven to a riod of time that commences when coal be- coke oven battery collecting main or to an- gins to flow into an oven through a topside other oven. Offtake system components in- port and ends when the last charging port is clude the standpipe and standpipe caps, recapped. goosenecks, stationary jumper pipes, mini-

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standpipes, and standpipe and gooseneck 6.0 Equipment and Supplies [Reserved] connections. 3.14 Operating oven means any oven not 7.0 Reagents and Standards [Reserved] out of operation for rebuild or maintenance 8.0 Sample Collection, Preservation, Transport, work extensive enough to require the oven to and Storage [Reserved] be skipped in the charging sequence. 3.15 Oven means a chamber in the coke 9.0 Quality Control [Reserved] oven battery in which coal undergoes destructive distillation to produce coke. 10.0 Calibration and Standardization 3.16 Push side means the side of the bat- Observer certification and training re- tery from which the coke is pushed from quirements are as follows: ovens at the end of the coking cycle. 10.1 Certification Procedures. This meth- 3.17 Run means the observation of visible od requires only the determination of wheth- emissions from topside port lids, offtake sys- er VE occur and does not require the deter- tems, coke oven doors, or the charging of a mination of opacity levels; therefore, ob- single oven in accordance with this method. server certification according to Method 9 in 3.18 Shed means an enclosure that covers appendix A to part 60 of this chapter is not the side of the coke oven battery, captures required to obtain certification under this emissions from pushing operations and from method. However, in order to receive Method leaking coke oven doors on the coke side or 303 observer certification, the first-time ob- push side of the coke oven battery, and server (trainee) shall have attended the lec- routes the emissions to a control device or ture portion of the Method 9 certification system. course. In addition, the trainee shall success- 3.19 Standpipe cap means An apparatus fully complete the Method 303 training used to cover the opening in the gooseneck course, satisfy the field observation require- of an offtake system. ment, and demonstrate adequate perform- 3.20 Topside port lid means a cover, re- ance and sufficient knowledge of Method 303. moved during charging or decarbonizing, The Method 303 training provider and course that is placed over the opening through shall be approved by the Administrator and shall consist of classroom instruction, field which coal can be charged into the oven of a training, and a proficiency test. In order to by-product coke oven battery. apply for approval as a Method 303 training 3.21 Traverse time means accumulated provider, an applicant must submit their cre- time for a traverse as measured by a stop- dentials and the details of their Method 303 watch. Traverse time includes time to stop training course to Group Leader, Measure- and write down oven numbers but excludes ment Technology Group (E143–02), Office of time waiting for obstructions of view to Air Quality Planning and Standards, U.S. clear or for time to walk around obstacles. Environmental Protection Agency, Research 3.22 Visible Emissions or VE means any Triangle Park, NC 27711. Those details emission seen by the unaided (except for cor- should include, at a minimum: rective lenses) eye, excluding steam or con- (a) A detailed list of the provider’s creden- densing water. tials. (b) An outline of the classroom and the 4.0 Interferences [Reserved] field portions of the class. 5.0 Safety (c) Copies of the written training and lecture materials, to include: 5.1 Disclaimer. This method may involve (1) The classroom audio-visual presen- hazardous materials, operations, and equip- tation(s). ment. This test method may not address all (2) A classroom course manual with in- of the safety problems associated with its structional text, practice questions and use. It is the responsibility of the user of this problems for each of the elements of the test method to establish appropriate safety Method 303 inspection (i.e., charging, doors, and health practices and determine the ap- lids and offtakes, and collecting mains). A plicability of regulatory limitations prior to copy of Method 303 and any related guidance performing this test method. documents should be included as appendices. 5.2 Safety Training. Because coke oven (3) A copy of the Method 303 demonstration batteries have hazardous environments, the video, if not using the one available at: http:// training materials and the field training www3.epa.gov/ttn/emc/methods/ (section 10.0) shall cover the precautions re- method303trainingvideo.mp4. quired to address health and safety hazards. (4) Multiple-choice certification tests, with questions sufficient to demonstrate knowledge of the method, as follows: One (1) Initial certification test and three (3) third-year recertification tests (the questions on any one

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recertification test must be at least 25 per- point under Method 303 or a predecessor cent different from those on the other recer- state or local method. A ‘‘day’s experience’’ tification tests). does not mean 8 or 10 hours performing in- (5) A field certification checklist and inspections, or any particular time expressed spection forms for each of the elements of in minutes or hours that may have been the Method 303 inspection (i.e., charging, spent performing them. Thus, it would be doors, lids and offtakes, and collecting possible for an individual to qualify as a mains). Method 303 panel member for some emission (6) The criteria used to determine pro- points, but not others (e.g., an individual ficiency. might satisfy the experience requirement for (7) The panel members to be utilized (see coke oven doors, but not topside port lids). Section 10.1.3) along with their qualifica- Until November 15, 1994, the EPA may waive tions. the certification requirement (but not the (8) An example certificate of successful experience requirement) for panel members. course completion. The composition of the panel shall be ap- 10.1.1 A trainee must verify completion of proved by the EPA. at least 12 hours of field observation prior to The panel shall observe the trainee in a se- attending the Method 303 certification ries of training runs and a series of certifi- course. Trainees shall observe the operation cation runs. There shall be a minimum of 1 of a coke oven battery as it pertains to training run for doors, topside port lids, and Method 303, including topside operations, offtake systems, and a minimum of 5 train- and shall also practice conducting Method ing runs (i.e., 5 charges) for charging. During 303 or similar methods. During the field ob- training runs, the panel can advise the train- servations, trainees unfamiliar with coke ee on proper procedures. There shall be a battery operations shall receive instruction minimum of 3 certification runs for doors, from an experienced coke oven observer who topside port lids, and offtake systems, and a is familiar with Method 303 or similar meth- minimum of 15 certification runs for charg- ods and with the operation of coke batteries. ing (i.e., 15 charges). The certification runs 10.1.2 The classroom instruction shall fa- shall be unassisted. Following the certifi- miliarize the trainees with Method 303 cation test runs, the panel shall approve or through lecture, written training materials, disapprove certification based on the train- and a Method 303 demonstration video. Suc- ee’s performance during the certification cessful completion of the classroom portion runs. To obtain certification, the trainee of the Method 303 training course shall be shall demonstrate, to the satisfaction of the demonstrated by a perfect score on the ini- panel, a high degree of proficiency in per- tial certification test. Those attending the forming Method 303. To aid in evaluating the course for third-year recertification must trainee’s performance, a checklist, approved complete one of the recertification tests se- by the EPA, will be used by the panel mem- lected at random. bers. 10.1.3 All trainees must demonstrate pro- 10.1.4 Those successfully completing the ficiency in the application of Method 303 to initial certification or third-year recertifi- a panel of three certified Method 303 observ- cation requirements shall receive a certifi- ers, including an ability to differentiate coke cate showing certification as a Method 303 oven emissions from condensing water vapor observer and the beginning and ending dates and smoldering coal. The composition of the of the certification period. panel must be approved by the Adminis- 10.1.5 The training provider will submit to trator as part of the training course approval the EPA or its designee the following infor- process. The panel members will be EPA, mation for each trainee successfully com- state or local agency personnel, or industry pleting initial certification or third-year re- contractors listed in 59 FR 11960 (March 15, certification training: Name, employer, ad- 1994) or qualified as part of the training pro- dress, telephone, cell and/or fax numbers, vider approval process of section 10.1 of this email address, beginning and ending dates of method. certification, and whether training was for 3- Each panel member shall have at least 120 year certification or 1-year recertification. days experience in reading visible emissions This information must be submitted within from coke ovens. The visible emissions in- 30 days of the course completion. spections that will satisfy the experience re- 10.1.6 The training provider will maintain quirement must be inspections of coke oven the following records, to be made available battery fugitive emissions from the emission to EPA or its designee on request (within 30 points subject to emission standards under days of a request): subpart L of this part (i.e., coke oven doors, (a) A file for each Method 303 observer con- topside port lids, offtake system(s), and taining the signed certification checklists, charging operations), using either Method certification forms and test results for their 303 or predecessor state or local test meth- initial certification, and any subsequent ods. A ‘‘day’s experience’’ for a particular in- third-year recertifications. Initial certifi- spection is a day on which one complete in- cation records must also include documenta- spection was performed for that emission tion showing successful completion of the

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training prerequisites. Testing results from obstructed view of the emission points of the any interim recertifications must also be in- charging system, including larry car hop- cluded, along with any relevant communica- pers, drop sleeves, and the topside ports of tions. the oven being charged. Some charging sys- (b) A searchable master electronic data- tems are configured so that all emission base of all persons for whom initial certifi- points can only be seen from a distance of cation, third-year recertification or interim five ovens. For other batteries, distances of 8 recertification. Information contained there- to 12 ovens are adequate. in must include: The observer’s name, em- 11.1.4 Observation. The charging period ployer, address, telephone, cell and fax num- begins when coal begins to flow into the oven bers and email address, along with the begin- and ends when the last charging port is re- ning and ending dates for each successfully capped. During the charging period, observe completed initial, third-year and interim re- all of the potential sources of VE from the certification. 10.1.7 Failure by the training provider to entire charging system. For wet coal charg- submit example training course materials ing systems or non-pipeline coal charging and/or requested training records to the Ad- systems, sources of VE typically include the ministrator may result in suspension of the larry car hoppers, drop sleeves, slide gates, approval of the provider and course. and topside ports on the oven being charged. 10.2 Observer Certification/Recertifi- Any VE from an open standpipe cap on the cation. The coke oven observer certification oven being charged is included as charging is valid for 1 year. The observer shall recer- VE. tify annually by reviewing the training ma- 11.1.4.1 Using an accumulative-type stop- terial, viewing the training video and an- watch with unit divisions of at least 0.5 sec- swering all of the questions on the recertifi- onds, determine the total time VE are ob- cation test correctly. Every 3 years, an observed as follows. Upon observing any VE server shall be required to pass the pro- emerging from any part of the charging sys- ficiency test in section 10.1.3 in order to be tem, start the stopwatch. Stop the watch certified. The years between proficiency when VE are no longer observed emerging, tests are referred to as interim years. and restart the watch when VE reemerges. 10.3 The EPA (or applicable enforcement 11.1.4.2 When VE occur simultaneously agency) shall maintain records reflecting a from several points during a charge, consider certified observer’s successful completion of the sources as one. Time overlapping VE as the proficiency test, which shall include the continuous VE. Time single puffs of VE only completed proficiency test checklists for the for the time it takes for the puff to emerge certification runs. 10.4 An owner or operator of a coke oven from the charging system. Continue to time battery subject to subpart L of this part may VE in this manner for the entire charging observe a training and certification program period. Record the accumulated time to the under this section. nearest 0.5 second under ‘‘Visible emissions, seconds’’ on Figure 303–1. 11.0 Procedure 11.1.5 Visual Interference. If fugitive VE 11.1 Procedure for Determining VE from from other sources at the coke oven battery Charging Systems During Charging. site (e.g., door leaks or condensing water 11.1.1 Number of Oven Charges. Refer to vapor from the coke oven wharf) prevent a § 63.309(c)(1) of this part for the number of clear view of the charging system during a oven charges to observe. The observer shall charge, stop the stopwatch and make an ap- observe consecutive charges. Charges that propriate notation under ‘‘Comments’’ on are nonconsecutive can only be observed Figure 303–1. Label the observation an obser- when necessary to replace observations ter- vation of an incomplete charge, and observe minated prior to the completion of a charge another charge to fulfill the requirements of because of visual interferences. (See Section Section 11.1.1. 11.1.5). 11.1.6 VE Exemptions. Do not time the 11.1.2 Data Records. Record all the infor- following VE: mation requested at the top of the charging 11.1.6.1 The VE from burning or smol- system inspection sheet (Figure 303–1). For dering coal spilled on top of the oven, topside each charge, record the identification num- port lid, or larry car surfaces; ber of the oven being charged, the approxi- NOTE: The VE from smoldering coal are mate beginning time of the charge, and the generally white or gray. These VE generally identification of the larry car used for the have a plume of less than 1 meter long. If the charge. 11.1.3 Observer Position. Stand in an area observer cannot safely and with reasonable or move to positions on the topside of the confidence determine that VE are from coke oven battery with an unobstructed view charging, do not count them as charging of the entire charging system. For wet coal emissions. charging systems or non-pipeline coal charg- 11.1.6.2 The VE from the coke oven doors ing systems, the observer should have an un- or from the leveler bar; or

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11.1.6.3 The VE that drift from the top of on the outside of the pusher machine and a larry car hopper if the emissions had al- quench car tracks at a steady, normal walk- ready been timed as VE from the drop sleeve. ing pace, pausing to make appropriate en- NOTE: When the slide gate on a larry car tries on the door area inspection sheet (Fig- hopper closes after the coal has been added ure 303–2). A single test run consists of two to the oven, the seal may not be airtight. On timed traverses, one for the coke side and occasions, a puff of smoke observed at the one for the push side. The walking pace shall drop sleeves is forced past the slide gate up be such that the duration of the traverse into the larry car hopper and may drift from does not exceed an average of 4 seconds per the top; time these VE either at the drop oven door, excluding time spent moving sleeves or the hopper. If the larry car hopper around stationary obstructions or waiting does not have a slide gate or the slide gate is for other obstructions to move from posi- left open or partially closed, VE may quickly tions blocking the view of a series of doors. pass through the larry car hopper without Extra time is allowed for each leak (a max- being observed at the drop sleeves and will imum of 10 additional seconds for each leak- appear as a strong surge of smoke; time ing door) for the observer to make the proper these as charging VE. notation. A walking pace of 3 seconds per oven door has been found to be typical. 11.1.7 Total Time Record. Record the Record the actual traverse time with a stop- total time that VE were observed for each watch. charging operation in the appropriate col- 11.2.2.1 Include in the traverse time only umn on the charging system inspection the time spent observing the doors and re- sheet. cording door leaks. To measure actual tra- 11.1.8 Determination of Validity of a Set verse time, use an accumulative-type stop- of Observations. Five charging observations watch with unit divisions of 0.5 seconds or (runs) obtained in accordance with this less. Exclude interruptions to the traverse method shall be considered a valid set of ob- and time required for the observer to move servations for that day. No observation of an to positions where the view of the battery is incomplete charge shall be included in a unobstructed, or for obstructions, such as daily set of observations that is lower than the door machine, to move from positions the lowest reading for a complete charge. If blocking the view of a series of doors. both complete and incomplete charges have 11.2.2.2 Various situations may arise that been observed, the daily set of observations will prevent the observer from viewing a shall include the five highest values ob- door or a series of doors. Prior to the door in- served. Four or three charging observations spection, the owner or operator may elect to (runs) obtained in accordance with this temporarily suspend charging operations for method shall be considered a valid set of the duration of the inspection, so that all of charging observations only where it is not the doors can be viewed by the observer. The possible to obtain five charging observations, observer has two options for dealing with ob- because visual interferences (see Section structions to view: (a) Stop the stopwatch 11.1.5) or inclement weather prevent a clear and wait for the equipment to move or the view of the charging system during charging. fugitive emissions to dissipate before com- However, observations from three or four pleting the traverse; or (b) stop the stop- charges that satisfy these requirements shall watch, skip the affected ovens, and move to not be considered a valid set of charging ob- an unobstructed position to continue the servations if use of such set of observations traverse. Restart the stopwatch and con- in a calculation under Section 12.4 would tinue the traverse. After the completion of cause the value of A to be less than 145. the traverse, if the equipment has moved or 11.1.9 Log Average. For each day on which the fugitive emissions have dissipated, in- a valid daily set of observations is obtained, spect the affected doors. If the equipment is calculate the daily 30-day rolling log average still preventing the observer from viewing of seconds of visible emissions from the the doors, then the affected doors may be charging operation for each battery using counted as not observed. If option (b) is used these data and the 29 previous valid daily because of doors blocked by machines during sets of observations, in accordance with Sec- charging operations, then, of the affected tion 12.4. doors, exclude the door from the most re- 11.2. Procedure for Determining VE from cently charged oven from the inspection. Coke Oven Door Areas. The intent of this Record the oven numbers and make an ap- procedure is to determine VE from coke oven propriate notation under ‘‘Comments’’ on door areas by carefully observing the door the door area inspection sheet (Figure 303–2). area from a standard distance while walking 11.2.2.3 When batteries have sheds to con- at a normal pace. trol emissions, conduct the inspection from 11.2.1 Number of Runs. Refer to outside the shed unless the doors cannot be § 63.309(c)(1) of this part for the appropriate adequately viewed. In this case, conduct the number of runs. inspection from the bench. Be aware of spe- 11.2.2 Battery Traverse. To conduct a bat- cial safety considerations pertinent to walk- tery traverse, walk the length of the battery ing on the bench and follow the instructions

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of company personnel on the required equip- each battery using these data and the 29 pre- ment and procedures. If possible, conduct the vious valid daily observations, in accordance bench traverse whenever the bench is clear with Section 12.5. of the door machine and hot coke guide. 11.3 Procedure for Determining VE from 11.2.3 Observations. Record all the infor- Topside Port Lids and Offtake Systems. mation requested at the top of the door area 11.3.1 Number of Runs. Refer to inspection sheet (Figure 303–2), including the § 63.309(c)(1) of this part for the number of number of non-operating ovens. Record the runs to be conducted. Simultaneous runs or clock time at the start of the traverse on separate runs for the topside port lids and each side of the battery. Record which side is offtake systems may be conducted. being inspected (i.e., coke side or push side). 11.3.2 Battery Traverse. To conduct a top- Other information may be recorded at the side traverse of the battery, walk the length discretion of the observer, such as the loca- of the battery at a steady, normal walking tion of the leak (e.g., top of the door, chuck pace, pausing only to make appropriate en- door, etc.), the reason for any interruption of tries on the topside inspection sheet (Figure the traverse, or the position of the sun rel- 303–3). The walking pace shall not exceed an ative to the battery and sky conditions (e.g., average rate of 4 seconds per oven, excluding overcast, partly sunny, etc.). time spent moving around stationary ob- 11.2.3.1 Begin the test run by starting the structions or waiting for other obstructions stopwatch and traversing either the coke to move from positions blocking the view. side or the push side of the battery. After Extra time is allowed for each leak for the completing one side, stop the watch. Com- observer to make the proper notation. A plete this procedure on the other side. If in- walking pace of 3 seconds per oven is typical. specting more than one battery, the observer Record the actual traverse time with a stop- may view the push sides and the coke sides watch. sequentially. 11.3.3 Topside Port Lid Observations. To 11.2.3.2 During the traverse, look around observe lids of the ovens involved in the the entire perimeter of each oven door. The charging operation, the observer shall wait door is considered leaking if VE are detected to view the lids until approximately 5 min- in the coke oven door area. The coke oven utes after the completion of the charge. door area includes the entire area on the Record all the information requested on the vertical face of a coke oven between the topside inspection sheet (Figure 303–3). bench and the top of the battery between two Record the clock time when traverses begin adjacent buck stays (e.g., the oven door, and end. If the observer’s view is obstructed chuck door, between the masonry brick, during the traverse (e.g., steam from the buck stay or jamb, or other sources). Record coke wharf, larry car, etc.), follow the guide- the oven number and make the appropriate lines given in Section 11.2.2.2. notation on the door area inspection sheet 11.3.3.1 To perform a test run, conduct a (Figure 303–2). single traverse on the topside of the battery. NOTE: Multiple VE from the same door The observer shall walk near the center of area (e.g., VE from both the chuck door and the battery but may deviate from this path the push side door) are counted as only one to avoid safety hazards (such as open or emitting door, not as multiple emitting closed charging ports, luting buckets, lid re- doors. moval bars, and topside port lids that have been removed) and any other obstacles. Upon 11.2.3.3 Do not record the following noting VE from the topside port lid(s) of an sources as door area VE: oven, record the oven number and port num- 11.2.3.3.1 VE from ovens with doors re- ber, then resume the traverse. If any oven is moved. Record the oven number and make dampered-off from the collecting main for an appropriate notation under ‘‘Comments;’’ decarbonization, note this under ‘‘Com- 11.2.3.3.2 VE from ovens taken out of serv- ments’’ for that particular oven. ice. The owner or operator shall notify the observer as to which ovens are out of service. NOTE: Count the number of topside ports, Record the oven number and make an appro- not the number of points, exhibiting VE, i.e., priate notation under ‘‘Comments;’’ or if a topside port has several points of VE, 11.2.3.3.3 VE from hot coke that has been count this as one port exhibiting VE. spilled on the bench as a result of pushing. 11.3.3.2 Do not count the following as top- 11.2.4 Criteria for Acceptance. After com- side port lid VE: pleting the run, calculate the maximum 11.3.3.2.1 VE from between the brickwork time allowed to observe the ovens using the and oven lid casing or VE from cracks in the equation in Section 12.2. If the total traverse oven brickwork. Note these VE under ‘‘Com- time exceeds T, void the run, and conduct ments;’’ another run to satisfy the requirements of 11.3.3.2.2 VE from topside ports involved § 63.309(c)(1) of this part. in a charging operation. Record the oven 11.2.5 Percent Leaking Doors. For each number, and make an appropriate notation day on which a valid observation is obtained, (e.g., not observed because ports open for calculate the daily 30-day rolling average for charging) under ‘‘Comments;’’

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11.3.3.2.3 Topside ports having mainte- systems, do not include topside port lids or nance work done. Record the oven number offtake systems with VE from the following and make an appropriate notation under ovens: ‘‘Comments;’’ or 11.3.6.1 Empty ovens, including ovens un- 11.3.3.2.4 Condensing water from wet-seal- dergoing maintenance, which are properly ing material. Ports with only visible con- dampered off from the main. densing water from wet-sealing material are 11.3.6.2 Ovens being charged or being counted as observed but not as having VE. pushed. 11.3.3.2.5 Visible emissions from the flue 11.3.6.3 Up to 3 full ovens that have been inspection ports and caps. dampered off from the main prior to pushing. 11.3.4 Offtake Systems Observations. To 11.3.6.4 Up to 3 additional full ovens in the perform a test run, traverse the battery as in pushing sequence that have been dampered Section 11.3.3.1. Look ahead and back two to off from the main for offtake system clean- four ovens to get a clear view of the entire ing, for decarbonization, for safety reasons, offtake system for each oven. Consider visi- or when a charging/pushing schedule in- ble emissions from the following points as volves widely separated ovens (e.g., a offtake system VE: (a) the flange between Marquard system); or that have been the gooseneck and collecting main (‘‘sad- dampered off from the main for maintenance dle’’), (b) the junction point of the standpipe near the end of the coking cycle. Examples and oven (‘‘standpipe base’’), (c) the other of reasons that ovens are dampered off for parts of the offtake system (e.g., the stand- safety reasons are to avoid exposing workers pipe cap), and (d) the junction points with in areas with insufficient clearance between ovens and flanges of jumper pipes. standpipes and the larry car, or in areas 11.3.4.1 Do not stray from the traverse where workers could be exposed to flames or line in order to get a ‘‘closer look’’ at any hot gases from open standpipes, and to avoid part of the offtake system unless it is to dis- the potential for removing a door on an oven tinguish leaks from interferences from other that is not dampered off from the main. sources or to avoid obstacles. 11.3.7 Percent Leaking Topside Port Lids 11.3.4.2 If the centerline does not provide and Offtake Systems. For each day on which a clear view of the entire offtake system for a valid observation is obtained, calculate the each oven (e.g., when standpipes are longer daily 30-day rolling average for each battery than 15 feet), the observer may conduct the using these data and the 29 previous valid traverse farther from (rather than closer to) daily observations, in accordance with Sec- the offtake systems. tions 12.6 and 12.7. 11.3.4.3 Upon noting a leak from an 11.4 Procedure for Determining VE from offtake system during a traverse, record the Collecting Mains. 11.4.1 Traverse. To perform a test run, oven number. Resume the traverse. If the traverse both the collecting main catwalk oven is dampered-off from the collecting and the battery topside along the side clos- main for decarbonization and VE are ob- est to the collecting main. If the battery has served, note this under ‘‘Comments’’ for that a double main, conduct two sets of traverses particular oven. for each run, i.e., one set for each main. 11.3.4.4 If any part or parts of an offtake 11.4.2 Data Recording. Upon noting VE system have VE, count it as one emitting from any portion of a collection main, iden- offtake system. Each stationary jumper pipe tify the source and approximate location of is considered a single offtake system. the source of VE and record the time under 11.3.4.5 Do not count standpipe caps open ‘‘Collecting main’’ on Figure 303–3; then re- for a decarbonization period or standpipes of sume the traverse. an oven being charged as source of offtake 11.4.3 Collecting Main Pressure Check. system VE. Record the oven number and After the completion of the door traverse, write ‘‘Not observed’’ and the reason (i.e., the topside port lids, and offtake systems, decarb or charging) under ‘‘Comments.’’ compare the collecting main pressure during NOTE: VE from open standpipes of an oven the inspection to the collecting main pres- being charged count as charging emissions. sure during the previous 8 to 24 hours. All VE from closed standpipe caps count as Record the following: (a) the pressure during offtake leaks. inspection, (b) presence of pressure deviation 11.3.5 Criteria for Acceptance. After com- from normal operations, and (c) the expla- pleting the run (allow 2 traverses for bat- nation for any pressure deviation from nor- teries with double mains), calculate the mal operations, if any, offered by the opera- maximum time allowed to observe the top- tors. The owner or operator of the coke bat- side port lids and/or offtake systems using tery shall maintain the pressure recording the equation in Section 12.3. If the total tra- equipment and conduct the quality assur- verse time exceeds T, void the run and con- ance/quality control (QA/QC) necessary to duct another run to satisfy the requirements ensure reliable pressure readings and shall of § 63.309(c)(1) of this part. keep the QA/QC records for at least 6 11.3.6 In determining the percent leaking months. The observer may periodically topside port lids and percent leaking offtake check the QA/QC records to determine their

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completeness. The owner or operator shall Ly = Number of doors with VE observed from provide access to the records within 1 hour of the yard.

an observer’s request. Ly = Number of doors with VE observed from the yard on the push side. 12.0 Data Analysis and Calculations ln = Natural logarithm. 12.1 Nomenclature. N = Total number of ovens in the battery. A = 150 or the number of valid observations Ni = Total number of inoperable ovens. (runs). The value of A shall not be less PNO = Number of ports not observed. than 145, except for purposes of determina- Povn = Number of ports per oven. tions under § 63.306(c) (work practice plan PVE = Number of topside port lids with VE. implementation) or § 63.306(d) (work prac- PLD = Percent leaking coke oven doors for tice plan revisions) of this part. No set of the test run. observations shall be considered valid for PLL = Percent leaking topside port lids for such a recalculation that otherwise would the run. not be considered a valid set of observa- PLO = Percent leaking offtake systems. tions for a calculation under this para- T = Total time allowed for traverse, seconds. graph. Tovn = Number of offtake systems (excluding Di = Number of doors on non-operating jumper pipes) per oven. ovens. TNO = Number of offtake systems not ob- Dno = Number of doors not observed. served. D = Total number of doors observed on op- ob T = Number of offtake systems with VE. erating ovens. VE Xi = Seconds of VE during the ith charge. Dt = Total number of oven doors on the battery. Z = Number of topside port lids or offtake e = 2.72 systems with VE. J = Number of stationary jumper pipes. 12.2 Criteria for Acceptance for VE Deter- L = Number of doors with VE. minations from Coke Oven Door Areas. After Lb = Yard-equivalent reading. completing the run, calculate the maximum Ls = Number of doors with VE observed from time allowed to observe the ovens using the the bench under sheds. following equation:

=× +× T()4 Dt () 10 L Eq. 303-1

12.3 Criteria for Acceptance for VE Deter- mains), calculate the maximum time allowed minations from Topside Port Lids and to observe the topside port lids and/or Offtake Systems. After completing the run offtake systems by the following equation: (allow 2 traverses for batteries with double

T=×()()4 N + 10 × Z Eq. 303-2

12.4 Average Duration of VE from Charg- ing operation for each battery using these ing Operations. Use Equation 303–3 to cal- current day’s observations and the 29 pre- culate the daily 30-day rolling log average of vious valid daily sets of observations. seconds of visible emissions from the charg-

12.5 Percent Leaking Doors (PLD). Deter- servations were made on the coke oven bat- mine the total number of doors for which ob- tery as follows:

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=× −+ Dob()2 N() D i D no Eq. 303-4

12.5.1 For each test run (one run includes this part, calculate the push side and the both the coke side and the push side tra- coke side PLD separately. verses), sum the number of doors with door 12.5.2 Calculate percent leaking doors by area VE. For batteries subject to an ap- using Equation 303–5: proved alternative standard under § 63.305 of

L PLD =×y 100Eq. 303-5 Dob

12.5.3 When traverses are conducted from tion 303–6 to calculate a yard-equivalent the bench under sheds, calculate the coke reading: side and the push side separately. Use Equa-

=− × Lbs L(.) N0 06 Eq. 303-6

If Lb is less than zero, use zero for Lb in 12.5.3.1 Use Equation 303–7 to calculate Equation 303–7 in the calculation of PLD. PLD:

LL+ PLD = by× 100Eq. 303-7 Dob

Round off PLD to the nearest hundredth of 1 day rolling average percent leaking doors for percent and record as the percent leaking each battery using these current day’s obser- coke oven doors for the run. vations and the 29 previous valid daily sets 12.5.3.2 Average Percent Leaking Doors. of observations. Use Equation 303–8 to calculate the daily 30-

()PLD++ PLD . . . + PLD PLD = 12 30 Eq. 303-8 (30-day) 30

12.6 Topside Port Lids. Determine the percent leaking topside port lids for each run as follows:

P PLL = VE × 100Eq. 303-9 − − PNNPovn() i NO

12.6.1 Round off this percentage to the this percentage as the percent leaking top- nearest hundredth of 1 percent and record side port lids for the run.

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12.6.2 Average Percent Leaking Topside using these current day’s observations and Port Lids. Use Equation 303–10 to calculate the 29 previous valid daily sets of observa- the daily 30-day rolling average percent tions. leaking topside port lids for each battery

()PLL++ PLL . . .+PLL PLL (30-day) = 12 30 Eq. 303-10 30

12.7 Offtake Systems. Determine the percent leaking offtake systems for the run as follows:

T PLO = VE × 100Eq. 303-11 − +− TNNJTovn() i NO

12.7.1 Round off this percentage to the the daily 30-day rolling average percent nearest hundredth of 1 percent and record leaking offtake systems for each battery this percentage as the percent leaking using these current day’s observations and offtake systems for the run. the 29 previous valid daily sets of observa- 12.7.2 Average Percent Leaking Offtake tions. Systems. Use Equation 303–12 to calculate

()PLO+ PLO . . . + PLO PLO (30-day) = 12 30 Eq. 303-12 30

13.0 Method Performance [Reserved] 3. U.S. Occupational Safety and Health Ad- ministration. Code of Federal Regulations. 14.0 Pollution Prevention [Reserved] Title 29, Chapter XVII, Section 1910.1029(g). Washington, D.C. Government Printing Of- 15.0 Waste Management [Reserved] fice. July 1, 1990. 4. U.S. Environmental Protection Agency. 16.0 References. National Emission Standards for Hazardous 1. Missan, R., and A. Stein. Guidelines for Air Pollutants; Coke Oven Emissions from Evaluation of Visible Emissions Certifi- Wet-Coal Charged By-Product Coke Oven cation, Field Procedures, Legal Aspects, and Batteries; Proposed Rule and Notice of Pub- Background Material. U.S. Environmental lic Hearing. Washington, D.C. FEDERAL REG- Protection Agency. EPA Publication No. ISTER. Vol. 52, No. 78 (13586). April 23, 1987. EPA–340/1–75–007. April 1975. 17.0 Tables, Diagrams, Flowcharts, and 2. Wohlschlegel, P., and D. E. Wagoner. Validation Data Guideline for Development of a Quality As- surance Program: Volume IX—Visual Deter- Company name: lllllllllllllll mination of Opacity Emission from Sta- Battery no.: lll Date: lll Run no.: lll tionary Sources. U.S. Environmental Protec- City, State: lllllllllllllllll tion Agency. EPA Publication No. EPA–650/ Observer name: lllllllllllllll 4–74–005i. November 1975. Company representative(s): lllllllll

Visible Charge No. Oven Clock time emissions, Comments No. seconds

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Visible Charge No. Oven Clock time emissions, Comments No. seconds

Figure 303–1. Charging System Inspection Company name: llllllllllllllllllllllllllllllllllllllll Battery no.: llllllllllllllllllllllllllllllllllllllllll Date: llllllllllllllllllllllllllllllllllllllllllllll City, State: lllllllllllllllllllllllllllllllllllllllllll Total no. of ovens in battery: lllllllllllllllllllllllllllllllll Observer name: lllllllllllllllllllllllllllllllllllllllll Certification expiration date: lllllllllllllllllllllllllllllllll Inoperable ovens: llllllllllllllllllllllllllllllllllllllll Company representative(s): llllllllllllllllllllllllllllllllll Traverse time CS: lllllllllllllllllllllllllllllllllllllll Traverse time PS: lllllllllllllllllllllllllllllllllllllll Valid run (Y or N): lllllllllllllllllllllllllllllllllllllll

Time traverse started/ Comments completed PS/CS Door No. (No. of blocked doors, interruptions to traverse, etc.)

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Time traverse started/ Comments completed PS/CS Door No. (No. of blocked doors, interruptions to traverse, etc.)

Figure 303–2. Door Area Inspection. Company name: llllllllllllllllllllllllllllllllllllllll Battery no.: llllllllllllllllllllllllllllllllllllllllll Date: llllllllllllllllllllllllllllllllllllllllllllll City, State: lllllllllllllllllllllllllllllllllllllllllll Total no. of ovens in battery: lllllllllllllllllllllllllllllllll Observer name: lllllllllllllllllllllllllllllllllllllllll Certification expiration date: lllllllllllllllllllllllllllllllll Inoperable ovens: llllllllllllllllllllllllllllllllllllllll Company representative(s): llllllllllllllllllllllllllllllllll Total no. of lids: llllllllllllllllllllllllllllllllllllllll Total no. of offtakes: llllllllllllllllllllllllllllllllllllll Total no. of jumper pipes: lllllllllllllllllllllllllllllllllll Ovens not observed: llllllllllllllllllllllllllllllllllllll Total traverse time: llllllllllllllllllllllllllllllllllllll Valid run (Y or N): lllllllllllllllllllllllllllllllllllllll

Time traverse started/ Type of Inspection Location of VE completed (lids, offtakes, collecting main) (Oven #/Port #) Comments

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Figure 303–3. Topside Inspection 3.10 Traverse time means accumulated time for a traverse as measured by a stop- METHOD 303A—DETERMINATION OF VISIBLE watch. Traverse time includes time to stop EMISSIONS FROM NONRECOVERY COKE OVEN and write down oven numbers but excludes BATTERIES time waiting for obstructions of view to NOTE: This method does not include all of clear or for time to walk around obstacles. the specifications pertaining to observer cer- 3.11 Visible Emissions or VE means any tification. Some material is incorporated by emission seen by the unaided (except for cor- reference from other methods in this part rective lenses) eye, excluding steam or con- and in appendix A to 40 CFR Part 60. There- densing water. fore, to obtain reliable results, persons using this method should have a thorough knowl- 4.0 Interferences [Reserved] edge of Method 9 and Method 303. 5.0 Safety 1.0 Scope and Application 5.1 Disclaimer. This method may involve 1.1 Applicability. This method is applica- hazardous materials, operations, and equip- ble for the determination of visible emis- ment. This test method may not address all sions (VE) from leaking doors at non- of the safety problems associated with its recovery coke oven batteries. use. It is the responsibility of the user of this test method to establish appropriate safety 2.0 Summary of Method and health practices and determine the applicability of regulatory limitations prior to 2.1 A certified observer visually deter- performing this test method. mines the VE from coke oven battery sources while walking at a normal pace. This 5.2 Safety Training. Because coke oven method does not require that opacity of batteries have hazardous environments, the emissions be determined or that magnitude training materials and the field training be differentiated. (Section 10.0) shall cover the precautions required by the company to address health and 3.0 Definitions safety hazards. Special emphasis shall be given to the Occupational Safety and Health 3.1 Bench means the platform structure in Administration (OSHA) regulations per- front of the oven doors. taining to exposure of coke oven workers 3.2 Coke oven door means each end enclo- (see Reference 3 in Section 16.0). In general, sure on the push side and the coking side of the regulation requires that special fire-re- an oven. tardant clothing and respirators be worn in 3.3 Coke side means the side of a battery certain restricted areas of the coke oven bat- from which the coke is discharged from tery. The OSHA regulation also prohibits ovens at the end of the coking cycle. certain activities, such as chewing gum, 3.4 Nonrecovery coke oven battery means a smoking, and eating in these areas. source consisting of a group of ovens connected by common walls and operated as a 6.0 Equipment and Supplies [Reserved] unit, where coal undergoes destructive distillation under negative pressure to produce 7.0 Reagents and Standards [Reserved] coke, and which is designed for the combustion of coke oven gas from which by-prod- 8.0 Sample Collection, Preservation, Transport, ucts are not recovered. and Storage [Reserved] 3.5 Operating oven means any oven not out of operation for rebuild or maintenance work 9.0 Quality Control [Reserved] extensive enough to require the oven to be 10.0 Calibration and Standardization. skipped in the charging sequence. 3.6 Oven means a chamber in the coke 10.1 Training. This method requires only oven battery in which coal undergoes de- the determination of whether VE occur and structive distillation to produce coke. does not require the determination of opac- 3.7 Push side means the side of the battery ity levels; therefore, observer certification from which the coke is pushed from ovens at according to Method 9 in Appendix A to Part the end of the coking cycle. 60 is not required. However, the first-time 3.8 Run means the observation of visible observer (trainee) shall have attended the emissions from coke oven doors in accord- lecture portion of the Method 9 certification ance with this method. course. Furthermore, before conducting any 3.9 Shed means an enclosure that covers VE observations, an observer shall become the side of the coke oven battery, captures familiar with nonrecovery coke oven battery emissions from pushing operations and from operations and with this test method by ob- leaking coke oven doors on the coke side or serving for a minimum of 4 hours the oper- push side of the coke oven battery, and ation of a nonrecovery coke oven battery in routes the emissions to a control device or the presence of personnel experienced in per- system. forming Method 303 assessments.

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11.0 Procedure If possible, conduct the bench traverse whenever the bench is clear of the door machine The intent of this procedure is to deter- and hot coke guide. mine VE from coke oven door areas by carefully observing the door area while walking 11.3 Observations. Record all the informa- at a normal pace. tion requested at the top of the door area in- 11.1 Number of Runs. Refer to § 63.309(c)(1) spection sheet (Figure 303A–1), including the of this part for the appropriate number of number of non-operating ovens. Record runs. which side is being inspected, i.e., coke side 11.2 Battery Traverse. To conduct a bat- or push side. Other information may be re- tery traverse, walk the length of the battery corded at the discretion of the observer, such on the outside of the pusher machine and as the location of the leak (e.g., top of the quench car tracks at a steady, normal walk- door), the reason for any interruption of the ing pace, pausing to make appropriate en- traverse, or the position of the sun relative tries on the door area inspection sheet (Fig- to the battery and sky conditions (e.g., over- ure 303A–1). The walking pace shall be such cast, partly sunny, etc.). that the duration of the traverse does not ex- 11.3.1 Begin the test run by traversing ei- ceed an average of 4 seconds per oven door, ther the coke side or the push side of the excluding time spent moving around sta- battery. After completing one side, traverse tionary obstructions or waiting for other ob- the other side. structions to move from positions blocking 11.3.2 During the traverse, look around the view of a series of doors. Extra time is the entire perimeter of each oven door. The allowed for each leak (a maximum of 10 addi- door is considered leaking if VE are detected tional seconds for each leaking door) for the in the coke oven door area. The coke oven observer to make the proper notation. A door area includes the entire area on the walking pace of 3 seconds per oven door has vertical face of a coke oven between the been found to be typical. Record the actual bench and the top of the battery and the ad- traverse time with a stopwatch. A single test jacent doors on both sides. Record the oven run consists of two timed traverses, one for number and make the appropriate notation the coke side and one for the push side. on the door area inspection sheet (Figure 11.2.1 Various situations may arise that 303A–1). will prevent the observer from viewing a 11.3.3 Do not record the following sources door or a series of doors. The observer has as door area VE: two options for dealing with obstructions to 11.3.3.1 VE from ovens with doors review: (a) Wait for the equipment to move or moved. Record the oven number and make the fugitive emissions to dissipate before an appropriate notation under ‘‘Comments’’; completing the traverse; or (b) skip the af- 11.3.3.2 VE from ovens where maintenance fected ovens and move to an unobstructed work is being conducted. Record the oven position to continue the traverse. Continue number and make an appropriate notation the traverse. After the completion of the tra- under ‘‘Comments’’; or verse, if the equipment has moved or the fu- 11.3.3.3 VE from hot coke that has been gitive emissions have dissipated, complete spilled on the bench as a result of pushing. the traverse by inspecting the affected doors. Record the oven numbers and make an ap- 12.0 Data Analysis and Calculations propriate notation under ‘‘Comments’’ on the door area inspection sheet (Figure 303A– Same as Method 303, Section 12.1, 12.2, 12.3, 1). 12.4, and 12.5. NOTE: Extra time incurred for handling ob- 13.0 Method Performance [Reserved] structions is not counted in the traverse time. 14.0 Pollution Prevention [Reserved] 11.2.2 When batteries have sheds to control pushing emissions, conduct the inspec- 15.0 Waste Management [Reserved] tion from outside the shed, if the shed allows such observations, or from the bench. Be 16.0 References aware of special safety considerations perti- Same as Method 303, Section 16.0. nent to walking on the bench and follow the instructions of company personnel on the re- 17.0 Tables, Diagrams, Flowcharts, and quired equipment and operations procedures. Validation Data

Company name: llllllllllllllllllllllllllllllllllllllll Battery no.: llllllllllllllllllllllllllllllllllllllllll Date: llllllllllllllllllllllllllllllllllllllllllllll City, State: lllllllllllllllllllllllllllllllllllllllllll Total no. of ovens in battery: lllllllllllllllllllllllllllllllll Observer name: lllllllllllllllllllllllllllllllllllllllll Certification expiration date: lllllllllllllllllllllllllllllllll

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Inoperable ovens: llllllllllllllllllllllllllllllllllllllll Company representative(s): llllllllllllllllllllllllllllllllll Traverse time CS: lllllllllllllllllllllllllllllllllllllll Traverse time PS: lllllllllllllllllllllllllllllllllllllll Valid run (Y or N): lllllllllllllllllllllllllllllllllllllll

Time traverse started/ Comments completed PS/CS Door No. (No. of blocked doors, interruptions to traverse, etc.)

Figure 303A–1. Door Area Inspection 2.0 Summary of Method

METHOD 304A: DETERMINATION OF BIO- 2.1 A self-contained benchtop bioreactor DEGRADATION RATES OF ORGANIC COM- system is assembled in the laboratory. A POUNDS (VENT OPTION) sample of mixed liquor is added and the waste stream is then fed continuously. The 1.0 Scope and Application benchtop bioreactor is operated under condi- 1.1 Applicability. This method is applications nearly identical to the target full-scale ble for the determination of biodegradation activated sludge process. Bioreactor tem- rates of organic compounds in an activated perature, dissolved oxygen concentration, sludge process. The test method is designed average residence time in the reactor, waste to evaluate the ability of an aerobic biologi- composition, biomass concentration, and cal reaction system to degrade or destroy biomass composition of the full-scale process specific components in waste streams. The are the parameters which are duplicated in method may also be used to determine the the benchtop bioreactor. Biomass shall be re- effects of changes in wastewater composition moved from the target full-scale activated on operation. The biodegradation rates de- sludge unit and held for no more than 4 termined by utilizing this method are not hours prior to use in the benchtop bio- representative of a full-scale system. The reactor. If antifoaming agents are used in rates measured by this method shall be used the full-scale system, they shall also be used in conjunction with the procedures listed in appendix C of this part to calculate the frac- in the benchtop bioreactor. The feed flowing tion emitted to the air versus the fraction into and the effluent exiting the benchtop biodegraded. bioreactor are analyzed to determine the

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biodegradation rates of the target com- suspension. Provide an exit for the aeration pounds. The flow rate of the exit vent is used gas from the top flange of the benchtop bio- to calculate the concentration of target reactor through a water-cooled (e.g., Allihn- compounds (utilizing Henry’s law) in the exit type) vertical condenser. Install the con- gas stream. If Henry’s law constants for the denser through a gas-tight fitting in the compounds of interest are not known, this benchtop bioreactor closure. Install a split- method cannot be used in the determination ter which directs a portion of the gas to an of the biodegradation rate and Method 304B exit vent and the rest of the gas through an is the suggested method. The choice of ana- air recycle pump back to the benchtop bio- lytical methodology for measuring the com- reactor. Monitor and record the flow rate pounds of interest at the inlet and outlet to through the exit vent at least 3 times per the benchtop bioreactor are left to the dis- day throughout the day. cretion of the source, except where validated 6.3 Wastewater Feed. Supply the waste- methods are available. water feed to the benchtop bioreactor in a collapsible low-density polyethylene con- 3.0 Definitions [Reserved] tainer or collapsible liner in a container (e.g., 20 L) equipped with a spigot cap (col- 4.0 Interferences [Reserved] lapsible containers or liners of other mate- 5.0 Safety rial may be required due to the permeability of some volatile compounds through poly- 5.1 If explosive gases are produced as a by- ethylene). Obtain the wastewater feed by product of biodegradation and could realisti- sampling the wastewater feed in the target cally pose a hazard, closely monitor process. A representative sample of waste- headspace concentration of these gases to water shall be obtained from the piping lead- ensure laboratory safety. Placement of the ing to the aeration tank. This sample may be benchtop bioreactor system inside a labora- obtained from existing sampling valves at tory hood is recommended regardless of by- the discharge of the wastewater feed pump, products produced. or collected from a pipe discharging to the aeration tank, or by pumping from a well- 6.0. Equipment and Supplies mixed equalization tank upstream from the NOTE: Figure 304A–1 illustrates a typical aeration tank. Alternatively, wastewater laboratory apparatus used to measure bio- can be pumped continuously to the labora- degradation rates. While the following de- tory apparatus from a bleed stream taken scription refers to Figure 304A–1, the EPA from the equalization tank of the full-scale recognizes that alternative reactor configu- treatment system. rations, such as alternative reactor shapes 6.3.1 Refrigeration System. Keep the and locations of probes and the feed inlet, wastewater feed cool by ice or by refrigera- will also meet the intent of this method. En- tion to 4 °C. If using a bleed stream from the sure that the benchtop bioreactor system is equalization tank, refrigeration is not re- self-contained and isolated from the atmos- quired if the residence time in the bleed phere (except for the exit vent stream) by stream is less than five minutes. leak-checking fittings, tubing, etc. 6.3.2 Wastewater Feed Pump. The waste- 6.1 Benchtop Bioreactor. The biological water is pumped from the refrigerated con- reaction is conducted in a biological oxida- tainer using a variable-speed peristaltic tion reactor of at least 6 liters capacity. The pump drive equipped with a peristaltic pump benchtop bioreactor is sealed and equipped head. Add the feed solution to the benchtop with internal probes for controlling and bioreactor through a fitting on the top monitoring dissolved oxygen and internal flange. Determine the rate of feed addition temperature. The top of the reactor is to provide a retention time in the benchtop equipped for aerators, gas flow ports, and in- bioreactor that is numerically equivalent to strumentation (while ensuring that no leaks the retention time in the full-scale system. to the atmosphere exist around the fittings). The wastewater shall be fed at a rate suffi- 6.2 Aeration gas. Aeration gas is added to cient to achieve 90 to 100 percent of the full- the benchtop bioreactor through three dif- scale system residence time. fusers, which are glass tubes that extend to 6.3.3 Treated wastewater feed. The the bottom fifth of the reactor depth. A pure benchtop bioreactor effluent exits at the bot- oxygen pressurized cylinder is recommended tom of the reactor through a tube and pro- in order to maintain the specified oxygen ceeds to the clarifier. concentration. Install a blower (e.g., Dia- 6.4 Clarifier. The effluent flows to a sepa- phragm Type, 15 SCFH capacity) to blow the rate closed clarifier that allows separation of aeration gas into the reactor diffusers. Meas- biomass and effluent (e.g., 2-liter pear-shaped ure the aeration gas flow rate with a rotam- glass separatory funnel, modified by remov- eter (e.g., 0–15 SCFH recommended). The aer- ing the stopcock and adding a 25-mm OD ation gas will rise through the benchtop bio- glass tube at the bottom). Benchtop bioreactor, dissolving oxygen into the mixture reactor effluent enters the clarifier through in the process. The aeration gas must pro- a tube inserted to a depth of 0.08 m (3 in.) vide sufficient agitation to keep the solids in through a stopper at the top of the clarifier.

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System effluent flows from a tube inserted valve (normally closed), admitting oxygen to through the stopper at the top of the clari- the system. The vacuum setpoint controlling fier to a drain (or sample bottle when sam- oxygen addition to the system shall be set at pling). The underflow from the clarifier approximately 2.5 ±0.5 cm water and main- leaves from the glass tube at the bottom of tained at this setting except during brief pe- the clarifier. Flexible tubing connects this riods when the dissolved oxygen concentra- fitting to the sludge recycle pump. This tion is adjusted. pump is coupled to a variable speed pump 6.7 Connecting Tubing. All connecting drive. The discharge from this pump is re- tubing shall be Teflon or equivalent in im- turned through a tube inserted in a port on permeability. The only exception to this the side of the benchtop bioreactor. An addi- specification is the tubing directly inside the tional port is provided near the bottom of pump head of the wastewater feed pump, the benchtop bioreactor for sampling the re- which may be Viton, Silicone or another actor contents. The mixed liquor from the type of flexible tubing. benchtop bioreactor flows into the center of NOTE: Mention of trade names or products the clarifier. The clarified system effluent does not constitute endorsement by the U.S. separates from the biomass and flows Environmental Protection Agency. through an exit near the top of the clarifier. There shall be no headspace in the clarifier. 7.0 Reagents and Standards 6.5 Temperature Control Apparatus. Capa- 7.1 Wastewater. Obtain a representative ble of maintaining the system at a tempera- sample of wastewater at the inlet to the full- ture equal to the temperature of the full- scale treatment plant if there is an existing scale system. The average temperature full-scale treatment plant (see section 6.3). If should be maintained within ±2 °C of the set there is no existing full-scale treatment point. plant, obtain the wastewater sample as close 6.5.1 Temperature Monitoring Device. A to the point of determination as possible. resistance type temperature probe or a ther- Collect the sample by pumping the waste- mocouple connected to a temperature readout with a resolution of 0.1 °C or better. water into the 20-L collapsible container. 6.5.2 Benchtop Bioreactor Heater. The The loss of volatiles shall be minimized from heater is connected to the temperature con- the wastewater by collapsing the container trol device. before filling, by minimizing the time of fill- 6.6 Oxygen Control System. Maintain the ing, and by avoiding a headspace in the con- dissolved oxygen concentration at the levels tainer after filling. If the wastewater represent in the full-scale system. Target full- quires the addition of nutrients to support scale activated sludge systems with dis- the biomass growth and maintain biomass solved oxygen concentration below 2 mg/L characteristics, those nutrients are added are required to maintain the dissolved oxy- and mixed with the container contents after gen concentration in the benchtop ioreactor the container is filled. within 0.5 mg/L of the target dissolved oxy- 7.2 Biomass. Obtain the biomass or acti- gen level. Target full-scale activated sludge vated sludge used for rate constant deter- systems with dissolved oxygen concentration mination in the bench-scale process from the above 2 mg/L are required to maintain the existing full-scale process or from a rep- dissolved oxygen concentration in the resentative biomass culture (e.g., biomass benchtop bioreactor within 1.5 mg/L of the that has been developed for a future full- target dissolved oxygen concentration; how- scale process). This biomass is preferentially ever, for target full-scale activated sludge obtained from a thickened acclimated mixed systems with dissolved oxygen concentra- liquor sample. Collect the sample either by tions above 2 mg/L, the dissolved oxygen bailing from the mixed liquor in the aeration concentration in the benchtop bioreactor tank with a weighted container, or by col- may not drop below 1.5 mg/L. If the benchtop lecting aeration tank effluent at the effluent bioreactor is outside the control range, the overflow weir. Transport the sample to the dissolved oxygen is noted and the reactor op- laboratory within no more than 4 hours of eration is adjusted. collection. Maintain the biomass concentra- 6.6.1 Dissolved Oxygen Monitor. Dissolved tion in the benchtop bioreactor at the level oxygen is monitored with a polarographic of the full-scale system + 10 percent through- probe (gas permeable membrane) connected out the sampling period of the test method. to a dissolved oxygen meter (e.g., 0 to 15 mg/ 8.0 Sample Collection, Preservation, Storage, L, 0 to 50 °C). and Transport 6.6.2 Benchtop Bioreactor Pressure Mon- itor. The benchtop bioreactor pressure is 8.1 Benchtop Bioreactor Operation. monitored through a port in the top flange of Charge the mixed liquor to the benchtop bio- the reactor. This is connected to a gauge reactor, minimizing headspace over the liq- control with a span of 13-cm water vacuum uid surface to minimize entrainment of to 13-cm water pressure or better. A relay is mixed liquor in the circulating gas. Fasten activated when the vacuum exceeds an ad- the benchtop bioreactor headplate to the re- justable setpoint which opens a solenoid actor over the liquid surface. Maintain the

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temperature of the contents of the benchtop 8.1.2 Wastewater Flow Rate. bioreactor system at the temperature of the 8.1.2.1 The hydraulic residence time of the target full-scale system, ±2 °C, throughout aeration tank is calculated as the ratio of the testing period. Monitor and record the the volume of the tank (L) to the flow rate temperature of the benchtop bioreactor con- (L/min). At the beginning of a test, the con- ° tents at least to the nearest 0.1 C. tainer shall be connected to the feed pump 8.1.1 Wastewater Storage. Collect the and solution shall be pumped to the wastewater sample in the 20-L collapsible benchtop bioreactor at the required flow rate container. Store the container at 4 °C to achieve the calculated hydraulic residence throughout the testing period. Connect the container to the benchtop bioreactor feed time of wastewater in the aeration tank. pump.

= L QQtest fs Eq. 304A-1 Vfs

Where: suspended solids gravimetrically by the Gooch crucible/glass fiber filter method for Qtest = wastewater flow rate (L/min) total suspended solids, in accordance with Qfs = average flow rate of full-scale process (L/min) Standard Methods3 or equivalent. When nec- Vfs = volume of full-scale aeration tank (L) essary, sludge shall be wasted from the lower 8.1.2.2 The target flow rate in the test ap- side port of the benchtop bioreactor, and the paratus is the same as the flow rate in the volume that is wasted shall be replaced with target full-scale process multiplied by the an equal volume of the reactor effluent. Add ratio of benchtop bioreactor volume (e.g., 6 thickened activated sludge mixed liquor as L) to the volume of the full-scale aeration necessary to the benchtop bioreactor to in- tank. The hydraulic residence time shall be crease the suspended solids concentration to maintained at 90 to 100 percent of the resi- the desired level. Pump this mixed liquor to dence time maintained in the full-scale unit. the benchtop bioreactor through the upper A nominal flow rate is set on the pump based side port (Item 24 in Figure 304A–1). Change on a pump calibration. Changes in the elas- the membrane on the dissolved oxygen probe ticity of the tubing in the pump head and the before starting the test. Calibrate the oxy- accumulation of material in the tubing af- gen probe immediately before the start of fect this calibration. The nominal pumping the test and each time the membrane is rate shall be changed as necessary based on changed. volumetric flow measurements. Discharge 8.1.5 Inspection and Correction Proce- the benchtop bioreactor effluent to a waste- dures. If the feed line tubing becomes water storage, treatment, or disposal facil- clogged, replace with new tubing. If the feed ity, except during sampling or flow measure- flow rate is not within 5 percent of target ment periods. flow any time the flow rate is measured, 8.1.3 Sludge Recycle Rate. Set the sludge reset pump or check the flow measuring de- recycle rate at a rate sufficient to prevent vice and measure flow rate again until target accumulation in the bottom of the clarifier. flow rate is achieved. Set the air circulation rate sufficient to 8.2 Test Sampling. At least two and one maintain the biomass in suspension. half hydraulic residence times after the sys- 8.1.4 Benchtop Bioreactor Operation and tem has reached the targeted specifications Maintenance. Temperature, dissolved oxygen shall be permitted to elapse before the first concentration, exit vent flow rate, benchtop sample is taken. Effluent samples of the bioreactor effluent flow rate, and air circula- clarifier discharge (Item 20 in Figure 304A–1) tion rate shall be measured and recorded and the influent wastewater feed are col- three times throughout each day of benchtop lected in 40-mL septum vials to which two bioreactor operation. If other parameters drops of 1:10 hydrochloric acid (HCl) in water (such as pH) are measured and maintained in have been added. Sample the clarifier dis- the target full-scale unit, these parameters, charge directly from the drain line. These where appropriate, shall be monitored and samples will be composed of the entire flow maintained to target full-scale specifications from the system for a period of several min- in the benchtop bioreactor. At the beginning utes. Feed samples shall be taken from the of each sampling period (Section 8.2), sample feed pump suction line after temporarily the benchtop bioreactor contents for sus- stopping the benchtop bioreactor feed, re- pended solids analysis. Take this sample by moving a connector, and squeezing the col- loosening a clamp on a length of tubing at- lapsible feed container. Store both influent tached to the lower side port. Determine the and effluent samples at 4 °C immediately

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after collection and analyze within 8 hours of effluent flow rate, and overcorrection due to collection. faulty or sluggish dissolved oxygen probe re- 8.2.1 Frequency of Sampling. During the sponse. Control the dissolved oxygen con- test, sample and analyze the wastewater feed centration in the benchtop bioreactor by and the clarifier effluent at least six times. changing the proportion of oxygen in the cir- The sampling intervals shall be separated by culating aeration gas. Should the dissolved at least 8 hours. During any individual sam- oxygen concentration drift below the des- pling interval, sample the wastewater feed ignated experimental condition, bleed a simultaneously with or immediately after small amount of aeration gas from the sys- the effluent sample. Calculate the relative tem on the pressure side (i.e., immediately standard deviation (RSD) of the amount re- upstream of one of the diffusers). This will moved (i.e., effluent concentration—waste- create a vacuum in the system, triggering water feed concentration). The RSD values the pressure sensitive relay to open the sole- shall be <15 percent. If an RSD value is >15 noid valve and admit oxygen to the system. percent, continue sampling and analyzing in- Should the dissolved oxygen concentration fluent and effluent sets of samples until the RSD values are within specifications. drift above the designated experimental con- 8.2.2 Sampling After Exposure of System dition, slow or stop the oxygen input to the to Atmosphere. If, after starting sampling system until the dissolved oxygen concentra- procedures, the benchtop bioreactor system tion approaches the correct level. is exposed to the atmosphere (due to leaks, 9.2 Sludge Wasting. maintenance, etc.), allow at least one hy- 9.2.1 Determine the suspended solids con- draulic residence time to elapse before re- centration (section 8.1.4) at the beginning of suming sampling. a test, and once per day thereafter during the test. If the test is completed within a 9.0 Quality Control two day period, determine the suspended sol- 9.1 Dissolved Oxygen. Fluctuation in dis- ids concentration after the final sample set solved oxygen concentration may occur for is taken. If the suspended solids concentra- numerous reasons, including undetected gas tion exceeds the specified concentration, re- leaks, increases and decreases in mixed liq- move a fraction of the sludge from the uor suspended solids resulting from cell benchtop bioreactor. The required volume of growth and solids loss in the effluent stream, mixed liquor to remove is determined as fol- changes in diffuser performance, cycling of lows:

⎛ − ⎞ = SSms VVwr⎜ ⎟ Eq. 304A-2 ⎝ Sm ⎠

Where: ume has been wasted. Replace the volume of the liquid wasted by pouring the same vol- Vw is the wasted volume (Liters), Vr is the volume of the benchtop bioreactor ume of effluent back into the benchtop bio- (Liters), reactor. Dispose of the waste sludge prop- Sm is the measured solids (g/L), and erly. Ss is the specified solids (g/L). 9.3 Sludge Makeup. In the event that the 9.2.2 Remove the mixed liquor from the suspended solids concentration is lower than benchtop bioreactor by loosening a clamp on the specifications, add makeup sludge back the mixed liquor sampling tube and allowing into the benchtop bioreactor. Determine the the required volume to drain to a graduated amount of sludge added by the following flask. Clamp the tube when the correct vol- equation:

⎛ − ⎞ = SSsm VVwr⎜ ⎟ Eq. 304A-3 ⎝ Sw ⎠

Where: Sw is the solids in the makeup sludge (g/L),

Vw is the volume of sludge to add (Liters), Sm is the measured solids (g/L), and Ss is the Vr is the volume of the benchtop bioreactor specified solids (g/L). (Liters),

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10.0 Calibration and Standardization below the limit of quantitation determined for that compound, the operation of the 10.1 Wastewater Pump Calibration. Deter- Method 304 unit may be altered to attempt mine the wastewater flow rate by collecting to increase the effluent concentration above the system effluent for a time period of at the limit of quantitation. Modifications to least one hour, and measuring the volume the method shall be approved prior to the with a graduated cylinder. Record the collec- test. The request should be addressed to tion time period and volume collected. De- termine flow rate. Adjust the pump speed to Method 304 contact, Emissions Measurement deliver the specified flow rate. Center, Mail Drop 19, U.S. Environmental 10.2 Calibration Standards. Prepare cali- Protection Agency, Research Triangle Park, bration standards from pure certified stand- NC 27711. ards in an aqueous medium. Prepare and 12.0 Data Analysis and Calculations analyze three concentrations of calibration standards for each target component (or for 12.1 Nomenclature. The following symbols a mixture of components) in triplicate daily are used in the calculations. throughout the analyses of the test samples. C = Average inlet feed concentration for a At each concentration level, a single calibra- i compound of interest, as analyzed (mg/L) tion shall be within 5 percent of the average of the three calibration results. The low and Co = Average outlet (effluent) concentration medium calibration standards shall bracket for a compound of interest, as analyzed the expected concentration of the effluent (mg/L) (treated) wastewater. The medium and high X = Biomass concentration, mixed liquor standards shall bracket the expected influent suspended solids (g/L) concentration. t = Hydraulic residence time in the benchtop bioreactor (hours) 11.0 Analytical Procedures V = Volume of the benchtop bioreactor (L) 11.1 Analysis. If the identity of the com- Q = Flow rate of wastewater into the pounds of interest in the wastewater is not benchtop bioreactor, average (L/hour) known, a representative sample of the waste- 12.2 Residence Time. The hydraulic resi- water shall be analyzed in order to identify dence time of the benchtop bioreactor is all of the compounds of interest present. A equal to the ratio of the volume of the gas chromatography/mass spectrometry benchtop bioreactor (L) to the flow rate (L/ screening method is recommended. h): 11.1.1 After identifying the compounds of interest in the wastewater, develop and/or V use one or more analytical techniques capa- t = Eq. 304A-4 ble of measuring each of those compounds Q (more than one analytical technique may be 12.3 Rate of Biodegradation. Calculate the required, depending on the characteristics of rate of biodegradation for each component the wastewater). Test Method 18, found in appendix A of 40 CFR 60, may be used as a with the following equation: guideline in developing the analytical tech- ⎛ mg ⎞ CC− nique. Purge and trap techniques may be Rate = io Eq. 304A-5 used for analysis providing the target com- ⎝ − ⎠ ponents are sufficiently volatile to make Lh t this technique appropriate. The limit of 12.4 First-Order Biorate Constant. Cal- quantitation for each compound shall be de- culate the first-order biorate constant (K1) termined (see reference 1). If the effluent for each component with the following equa- concentration of any target compound is tion:

⎛ L ⎞ CC− K1⎜ ⎟ = io Eq. 304A-6 ⎝ − ⎠ gh tCo X

12.5 Relative Standard Deviation (RSD). the influent and effluent sample concentra- Determine the standard deviation of both tions (S) using the following equation:

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2 12 ⎛ n − ⎞ 100 ()SSi RSD = ⎜∑ ⎟ Eq. 304A-7 ⎜ ()− ⎟ S ⎝ i=1 n 1 ⎠

12.6 Determination of Percent Air Emis- 2. Test Method 18, 40 CFR 60, appendix A. sions and Percent Biodegraded. Use the re- 3. Standard Methods for the Examination sults from this test method and follow the of Water and Wastewater, 16th Edition, applicable procedures in appendix C of 40 Method 209C, Total Suspended Solids Dried CFR part 63, entitled, ‘‘Determination of the at 103–105 °C, APHA, 1985. Fraction Biodegraded (Fbio) in a Biological 4. Water7, Hazardous Waste Treatment, Treatment Unit’’ to determine Fbio. Storage, and Disposal Facilities (TSDF)—Air 13.0 Method Performance [Reserved] Emission Models, U.S. Environmental Pro- tection Agency, EPA–450/3–87–026, Review 14.0 Pollution Prevention [Reserved] Draft, November 1989. 5. Chemdat7, Hazardous Waste Treatment, 15.0 Waste Management [Reserved] Storage, and Disposal Facilities (TSDF)—Air 16.0 References Emission Models, U.S. Environmental Pro- tection Agency, EPA–450/3–87–026, Review 1. ‘‘Guidelines for data acquisition and Draft, November 1989. data quality evaluation in Environmental Chemistry,’’ Daniel MacDoughal, Analytical 17.0 Tables, Diagrams, Flowcharts, and Chemistry, Volume 52, p. 2242, 1980. Validation Data

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METHOD 304B: DETERMINATION OF BIO- to evaluate the ability of an aerobic biologi- DEGRADATION RATES OF ORGANIC COM- cal reaction system to degrade or destroy POUNDS (SCRUBBER OPTION) specific components in waste streams. The method may also be used to determine the 1.0 Scope and Application effects of changes in wastewater composition 1.1 Applicability. This method is applica- on operation. The biodegradation rates de- ble for the determination of biodegradation termined by utilizing this method are not rates of organic compounds in an activated representative of a full-scale system. Full- sludge process. The test method is designed scale systems embody biodegradation and air

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emissions in competing reactions. This tion reactor of at least 6-liters capacity. The method measures biodegradation in absence benchtop bioreactor is sealed and equipped of air emissions. The rates measured by this with internal probes for controlling and method shall be used in conjunction with the monitoring dissolved oxygen and internal procedures listed in appendix C of this part temperature. The top of the benchtop bio- to calculate the fraction emitted to the air reactor is equipped for aerators, gas flow versus the fraction biodegraded. ports, and instrumentation (while ensuring that no leaks to the atmosphere exist around 2.0 Summary of Method the fittings). 2.1 A self-contained benchtop bioreactor 6.2 Aeration gas. Aeration gas is added to system is assembled in the laboratory. A the benchtop bioreactor through three dif- sample of mixed liquor is added and the fusers, which are glass tubes that extend to waste stream is then fed continuously. The the bottom fifth of the reactor depth. A pure benchtop bioreactor is operated under condi- oxygen pressurized cylinder is recommended tions nearly identical to the target full-scale in order to maintain the specified oxygen activated sludge process, except that air concentration. Install a blower (e.g., Dia- emissions are not a factor. The benchtop bio- phragm Type, 15 SCFH capacity) to blow the reactor temperature, dissolved oxygen con- aeration gas into the benchtop bioreactor centration, average residence time in the re- diffusers. Measure the aeration gas flow rate actor, waste composition, biomass con- with a rotameter (e.g., 0–15 SCFH rec- centration, and biomass composition of the ommended). The aeration gas will rise target full-scale process are the parameters through the benchtop bioreactor, dissolving which are duplicated in the laboratory sys- oxygen into the mixture in the process. The tem. Biomass shall be removed from the tar- aeration gas must provide sufficient agita- get full-scale activated sludge unit and held tion to keep the solids in suspension. Provide for no more than 4 hours prior to use in the an exit for the aeration gas from the top benchtop bioreactor. If antifoaming agents flange of the benchtop bioreactor through a are used in the full-scale system, they shall water-cooled (e.g., Allihn-type) vertical con- also be used in the benchtop bioreactor. The denser. Install the condenser through a gas- feed flowing into and the effluent exiting the tight fitting in the benchtop bioreactor clo- benchtop bioreactor are analyzed to deter- sure. Design the system so that at least 10 mine the biodegradation rates of the target percent of the gas flows through an alkaline compounds. The choice of analytical meth- scrubber containing 175 mL of 45 percent by odology for measuring the compounds of in- weight solution of potassium hydroxide terest at the inlet and outlet to the benchtop (KOH) and 5 drops of 0.2 percent alizarin yel- bioreactor are left to the discretion of the low dye. Route the balance of the gas source, except where validated methods are through an adjustable scrubber bypass. available. Route all of the gas through a 1-L knock-out flask to remove entrained moisture and then 3.0 Definitions [Reserved] to the intake of the blower. The blower recir- culates the gas to the benchtop bioreactor. 4.0 Interferences [Reserved] 6.3 Wastewater Feed. Supply the wastewater feed to the benchtop bioreactor in a 5.0 Safety collapsible low-density polyethylene con- 5.1 If explosive gases are produced as a by- tainer or collapsible liner in a container product of biodegradation and could realisti- (e.g., 20 L) equipped with a spigot cap (col- cally pose a hazard, closely monitor lapsible containers or liners of other mate- headspace concentration of these gases to rial may be required due to the permeability ensure laboratory safety. Placement of the of some volatile compounds through poly- benchtop bioreactor system inside a labora- ethylene). Obtain the wastewater feed by tory hood is recommended regardless of by- sampling the wastewater feed in the target products produced. process. A representative sample of wastewater shall be obtained from the piping lead- 6.0 Equipment and Supplies ing to the aeration tank. This sample may be NOTE: Figure 304B–1 illustrates a typical obtained from existing sampling valves at laboratory apparatus used to measure bio- the discharge of the wastewater feed pump, degradation rates. While the following de- or collected from a pipe discharging to the scription refers to Figure 304B–1, the EPA aeration tank, or by pumping from a well- recognizes that alternative reactor configu- mixed equalization tank upstream from the rations, such as alternative reactor shapes aeration tank. Alternatively, wastewater and locations of probes and the feed inlet, can be pumped continuously to the labora- will also meet the intent of this method. En- tory apparatus from a bleed stream taken sure that the benchtop bioreactor system is from the equalization tank of the full-scale self-contained and isolated from the atmos- treatment system. phere by leak-checking fittings, tubing, etc. 6.3.1 Refrigeration System. Keep the 6.1 Benchtop Bioreactor. The biological wastewater feed cool by ice or by refrigera- reaction is conducted in a biological oxidation to 4 °C. If using a bleed stream from the

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equalization tank, refrigeration is not re- gen concentration in the benchtop bioreactor quired if the residence time in the bleed within 0.5 mg/L of the target dissolved oxy- stream is less than five minutes. gen level. Target full-scale activated sludge 6.3.2 Wastewater Feed Pump. The waste- systems with dissolved oxygen concentration water is pumped from the refrigerated con- above 2 mg/L are required to maintain the tainer using a variable-speed peristaltic dissolved oxygen concentration in the pump drive equipped with a peristaltic pump benchtop bioreactor within 1.5 mg/L of the head. Add the feed solution to the benchtop target dissolved oxygen concentration; how- bioreactor through a fitting on the top ever, for target full-scale activated sludge flange. Determine the rate of feed addition systems with dissolved oxygen concentra- to provide a retention time in the benchtop tions above 2 mg/L, the dissolved oxygen bioreactor that is numerically equivalent to concentration in the benchtop bioreactor the retention time in the target full-scale may not drop below 1.5 mg/L. If the benchtop system. The wastewater shall be fed at a rate bioreactor is outside the control range, the sufficient to achieve 90 to 100 percent of the dissolved oxygen is noted and the reactor op- target full-scale system residence time. eration is adjusted. 6.3.3 Treated wastewater feed. The 6.6.1 Dissolved Oxygen Monitor. Dissolved benchtop bioreactor effluent exits at the bot- oxygen is monitored with a polarographic tom of the reactor through a tube and proceeds to the clarifier. probe (gas permeable membrane) connected 6.4 Clarifier. The effluent flows to a sepa- to a dissolved oxygen meter (e.g., 0 to 15 mg/ ° rate closed clarifier that allows separation of L, 0 to 50 C). biomass and effluent (e.g., 2-liter pear-shaped 6.6.2 Benchtop Bioreactor Pressure Mon- glass separatory funnel, modified by remov- itor. The benchtop bioreactor pressure is ing the stopcock and adding a 25-mm OD monitored through a port in the top flange of glass tube at the bottom). Benchtop bio- the reactor. This is connected to a gauge reactor effluent enters the clarifier through control with a span of 13-cm water vacuum a tube inserted to a depth of 0.08 m (3 in.) to 13-cm water pressure or better. A relay is through a stopper at the top of the clarifier. activated when the vacuum exceeds an ad- System effluent flows from a tube inserted justable setpoint which opens a solenoid through the stopper at the top of the clari- valve (normally closed), admitting oxygen to fier to a drain (or sample bottle when sam- the system. The vacuum setpoint controlling pling). The underflow from the clarifier oxygen addition to the system shall be set at leaves from the glass tube at the bottom of approximately 2.5 ±0.5 cm water and main- the clarifier. Flexible tubing connects this tained at this setting except during brief pe- fitting to the sludge recycle pump. This riods when the dissolved oxygen concentra- pump is coupled to a variable speed pump tion is adjusted. drive. The discharge from this pump is re- 6.7 Connecting Tubing. All connecting turned through a tube inserted in a port on tubing shall be Teflon or equivalent in im- the side of the benchtop bioreactor. An addi- permeability. The only exception to this tional port is provided near the bottom of specification is the tubing directly inside the the benchtop bioreactor for sampling the re- pump head of the wastewater feed pump, actor contents. The mixed liquor from the which may be Viton, Silicone or another benchtop bioreactor flows into the center of type of flexible tubing. the clarifier. The clarified system effluent NOTE: Mention of trade names or products separates from the biomass and flows does not constitute endorsement by the U.S. through an exit near the top of the clarifier. Environmental Protection Agency. There shall be no headspace in the clarifier. 6.5 Temperature Control Apparatus. Capa- 7.0. Reagents and Standards ble of maintaining the system at a temperature equal to the temperature of the full- 7.1 Wastewater. Obtain a representative scale system. The average temperature sample of wastewater at the inlet to the full- should be maintained within ±2 °C of the set scale treatment plant if there is an existing point. full-scale treatment plant (See Section 6.3). 6.5.1 Temperature Monitoring Device. A If there is no existing full-scale treatment resistance type temperature probe or a ther- plant, obtain the wastewater sample as close mocouple connected to a temperature read- to the point of determination as possible. out with a resolution of 0.1 °C or better. Collect the sample by pumping the waste- 6.5.2 Benchtop Bioreactor Heater. The water into the 20-L collapsible container. heater is connected to the temperature con- The loss of volatiles shall be minimized from trol device. the wastewater by collapsing the container 6.6 Oxygen Control System. Maintain the before filling, by minimizing the time of fill- dissolved oxygen concentration at the levels ing, and by avoiding a headspace in the con- present in the full-scale system. Target full- tainer after filling. If the wastewater re- scale activated sludge systems with dis- quires the addition of nutrients to support solved oxygen concentration below 2 mg/L the biomass growth and maintain biomass are required to maintain the dissolved oxy- characteristics, those nutrients are added

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and mixed with the container contents after uid surface to minimize entrainment of the container is filled. mixed liquor in the circulating gas. Fasten 7.2 Biomass. Obtain the biomass or acti- the benchtop bioreactor headplate to the re- vated sludge used for rate constant deter- actor over the liquid surface. Maintain the mination in the bench-scale process from the temperature of the contents of the benchtop existing full-scale process or from a rep- bioreactor system at the temperature of the resentative biomass culture (e.g., biomass target full-scale system, ±2 °C, throughout that has been developed for a future full- the testing period. Monitor and record the scale process). This biomass is preferentially temperature of the reactor contents at least obtained from a thickened acclimated mixed to the nearest 0.1 °C. liquor sample. Collect the sample either by bailing from the mixed liquor in the aeration 8.1.1 Wastewater Storage. Collect the tank with a weighted container, or by col- wastewater sample in the 20-L collapsible ° lecting aeration tank effluent at the effluent container. Store the container at 4 C overflow weir. Transport the sample to the throughout the testing period. Connect the laboratory within no more than 4 hours of container to the benchtop bioreactor feed collection. Maintain the biomass concentra- pump. tion in the benchtop bioreactor at the level 8.1.2 Wastewater Flow Rate. of the target full-scale system + 10 percent 8.1.2.1 The hydraulic residence time of the throughout the sampling period of the test aeration tank is calculated as the ratio of method. the volume of the tank (L) to the flow rate (L/min). At the beginning of a test, the con- 8.0 Sample Collection, Preservation, Storage, tainer shall be connected to the feed pump and Transport and solution shall be pumped to the 8.1 Benchtop Bioreactor Operation. benchtop bioreactor at the required flow rate Charge the mixed liquor to the benchtop bio- to achieve the calculated hydraulic residence reactor, minimizing headspace over the liq- time of wastewater in the aeration tank.

= L QQtest fs Eq. 304B-1 Vfs

Where: 8.1.4 Benchtop Bioreactor Operation and Maintenance. Temperature, dissolved oxygen Qtest = wastewater flow rate (L/min) concentration, flow rate, and air circulation Qfs = average flow rate of full-scale process (L/min) rate shall be measured and recorded three times throughout each day of testing. If V = volume of full-scale aeration tank (L) fs other parameters (such as pH) are measured 8.1.2.2 The target flow rate in the test ap- and maintained in the target full-scale unit, paratus is the same as the flow rate in the these parameters shall, where appropriate, target full-scale process multiplied by the be monitored and maintained to full-scale ratio of benchtop bioreactor volume (e.g., 6 specifications in the benchtop bioreactor. At L) to the volume of the full-scale aeration the beginning of each sampling period (sec- tank. The hydraulic residence time shall be tion 8.2), sample the benchtop bioreactor maintained at 90 to 100 percent of the resi- contents for suspended solids analysis. Take dence time maintained in the target full- this sample by loosening a clamp on a length scale unit. A nominal flow rate is set on the of tubing attached to the lower side port. De- pump based on a pump calibration. Changes termine the suspended solids gravimetrically in the elasticity of the tubing in the pump by the Gooch crucible/glass fiber filter meth- head and the accumulation of material in od for total suspended solids, in accordance the tubing affect this calibration. The nomi- with Standard Methods 3 or equivalent. When nal pumping rate shall be changed as nec- necessary, sludge shall be wasted from the essary based on volumetric flow measure- lower side port of the benchtop bioreactor, ments. Discharge the benchtop bioreactor ef- and the volume that is wasted shall be re- fluent to a wastewater storage, treatment, placed with an equal volume of the benchtop or disposal facility, except during sampling bioreactor effluent. Add thickened activated or flow measurement periods. sludge mixed liquor as necessary to the 8.1.3 Sludge Recycle Rate. Set the sludge benchtop bioreactor to increase the sus- recycle rate at a rate sufficient to prevent pended solids concentration to the desired accumulation in the bottom of the clarifier. level. Pump this mixed liquor to the Set the air circulation rate sufficient to benchtop bioreactor through the upper side maintain the biomass in suspension. port (Item 24 in Figure 304B–1). Change the

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membrane on the dissolved oxygen probe be- analyzing influent and effluent sets of sam- fore starting the test. Calibrate the oxygen ples until the RSD values are within speci- probe immediately before the start of the fications. test and each time the membrane is changed. 8.2.2 Sampling After Exposure of System The scrubber solution shall be replaced each to Atmosphere. If, after starting sampling weekday with 175 mL 45 percent W/W KOH procedures, the benchtop bioreactor system solution to which five drops of 0.2 percent is exposed to the atmosphere (due to leaks, alizarin yellow indicator in water have been maintenance, etc.), allow at least one hy- added. The potassium hydroxide solution in draulic residence time to elapse before re- the alkaline scrubber shall be changed if the suming sampling. alizarin yellow dye color changes. 8.1.5 Inspection and Correction Proce- 9.0 Quality Control dures. If the feed line tubing becomes clogged, replace with new tubing. If the feed 9.1 Dissolved Oxygen. Fluctuation in dis- flow rate is not within 5 percent of target solved oxygen concentration may occur for flow any time the flow rate is measured, numerous reasons, including undetected gas reset pump or check the flow measuring de- leaks, increases and decreases in mixed liq- vice and measure flow rate again until target uor suspended solids resulting from cell flow rate is achieved. growth and solids loss in the effluent stream, 8.2 Test Sampling. At least two and one changes in diffuser performance, cycling of half hydraulic residence times after the sys- effluent flow rate, and overcorrection due to tem has reached the targeted specifications faulty or sluggish dissolved oxygen probe re- shall be permitted to elapse before the first sponse. Control the dissolved oxygen con- sample is taken. Effluent samples of the centration in the benchtop bioreactor by clarifier discharge (Item 20 in Figure 304B–1) changing the proportion of oxygen in the cir- and the influent wastewater feed are col- culating aeration gas. Should the dissolved lected in 40-mL septum vials to which two oxygen concentration drift below the des- drops of 1:10 hydrochloric acid (HCl) in water ignated experimental condition, bleed a have been added. Sample the clarifier dis- small amount of aeration gas from the sys- charge directly from the drain line. These tem on the pressure side (i.e., immediately samples will be composed of the entire flow upstream of one of the diffusers). This will from the system for a period of several min- create a vacuum in the system, triggering utes. Feed samples shall be taken from the the pressure sensitive relay to open the sole- feed pump suction line after temporarily noid valve and admit oxygen to the system. stopping the benchtop bioreactor feed, re- Should the dissolved oxygen concentration moving a connector, and squeezing the col- drift above the designated experimental con- lapsible feed container. Store both influent dition, slow or stop the oxygen input to the and effluent samples at 4 °C immediately system until the dissolved oxygen concentra- after collection and analyze within 8 hours of tion approaches the correct level. collection. 9.2 Sludge Wasting. 8.2.1 Frequency of Sampling. During the 9.2.1 Determine the suspended solids con- test, sample and analyze the wastewater feed centration (section 8.1.4) at the beginning of and the clarifier effluent at least six times. a test, and once per day thereafter during The sampling intervals shall be separated by the test. If the test is completed within a at least 8 hours. During any individual sam- two day period, determine the suspended sol- pling interval, sample the wastewater feed ids concentration after the final sample set simultaneously with or immediately after is taken. If the suspended solids concentra- the effluent sample. Calculate the RSD of tion exceeds the specified concentration, re- the amount removed (i.e., effluent concentra- move a fraction of the sludge from the tion—wastewater feed concentration). The benchtop bioreactor. The required volume of RSD values shall be <15 percent. If an RSD mixed liquor to remove is determined as fol- value is >15 percent, continue sampling and lows:

⎛ − ⎞ = SSms VVwr⎜ ⎟ Eq. 304B-2 ⎝ Sm ⎠

Where: Ss is the specified solids (g/L).

Vw is the wasted volume (Liters), 9.2.2 Remove the mixed liquor from the Vr is the volume of the benchtop bioreactor benchtop bioreactor by loosening a clamp on (Liters), the mixed liquor sampling tube and allowing

Sm is the measured solids (g/L), and the required volume to drain to a graduated

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flask. Clamp the tube when the correct vol- 9.3 Sludge Makeup. In the event that the ume has been wasted. Replace the volume of suspended solids concentration is lower than the liquid wasted by pouring the same vol- the specifications, add makeup sludge back ume of effluent back into the benchtop bio- into the benchtop bioreactor. Determine the reactor. Dispose of the waste sludge prop- amount of sludge added by the following erly. equation:

⎛ − ⎞ = SSsm VVwr⎜ ⎟ Eq. 304B-3 ⎝ Sw ⎠

Where: than one analytical technique may be required, depending on the characteristics of Vw is the volume of sludge to add (Liters), Vr is the volume of the benchtop bioreactor the wastewater). Method 18, found in appen- (Liters), dix A of 40 CFR 60, may be used as a guide- Sw is the solids in the makeup sludge (g/L), line in developing the analytical technique. Sm is the measured solids (g/L), and Purge and trap techniques may be used for Ss is the specified solids (g/L). analysis providing the target components are sufficiently volatile to make this tech- 10.0 Calibration and Standardizations nique appropriate. The limit of quantitation 10.1 Wastewater Pump Calibration. Deter- for each compound shall be determined.1 If mine the wastewater flow rate by collecting the effluent concentration of any target the system effluent for a time period of at compound is below the limit of quantitation least one hour, and measuring the volume determined for that compound, the operation with a graduated cylinder. Record the collec- of the Method 304 unit may be altered to at- tion time period and volume collected. De- tempt to increase the effluent concentration termine flow rate. Adjust the pump speed to above the limit of quantitation. Modifica- deliver the specified flow rate. tions to the method shall be approved prior 10.2 Calibration Standards. Prepare cali- to the test. The request should be addressed bration standards from pure certified stand- to Method 304 contact, Emissions Measure- ards in an aqueous medium. Prepare and ment Center, Mail Drop 19, U.S. Environ- analyze three concentrations of calibration mental Protection Agency, Research Tri- standards for each target component (or for angle Park, NC 27711. a mixture of components) in triplicate daily throughout the analyses of the test samples. 12.0 Data Analysis and Calculations At each concentration level, a single calibration shall be within 5 percent of the average 12.1 Nomenclature. The following symbols of the three calibration results. The low and are used in the calculations. medium calibration standards shall bracket Ci = Average inlet feed concentration for a the expected concentration of the effluent compound of interest, as analyzed (mg/L) (treated) wastewater. The medium and high Co = Average outlet (effluent) concentration standards shall bracket the expected influent for a compound of interest, as analyzed concentration. (mg/L) 11.0 Analytical Test Procedures X = Biomass concentration, mixed liquor suspended solids (g/L) 11.1 Analysis. If the identity of the com- t = Hydraulic residence time in the benchtop pounds of interest in the wastewater is not bioreactor (hours) known, a representative sample of the waste- V = Volume of the benchtop bioreactor (L) water shall be analyzed in order to identify all of the compounds of interest present. A Q = Flow rate of wastewater into the gas chromatography/mass spectrometry benchtop bioreactor, average (L/hour) screening method is recommended. 12.2 Residence Time. The hydraulic resi- 11.1.1 After identifying the compounds of dence time of the benchtop bioreactor is interest in the wastewater, develop and/or equal to the ratio of the volume of the use one or more analytical technique capable benchtop bioreactor (L) to the flow rate (L/ of measuring each of those compounds (more h)

V t = Eq. 304B-4 Q

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12.3 Rate of Biodegradation. Calculate the rate of biodegradation for each component with the following equation:

⎛ mg ⎞ CC− Rate = io Eq. 304B-5 ⎝ Lh− ⎠ t

12.4 First-Order Biorate Constant. Cal- for each component with the following equa- culate the first-order biorate constant (K1) tion:

⎛ L ⎞ CC− K1⎜ ⎟ = io Eq. 304B-6 ⎝ − ⎠ gh tCo X

12.5 Relative Standard Deviation (RSD). the influent and effluent sample concentra- Determine the standard deviation of both tions (S) using the following equation:

2 12 ⎛ n − ⎞ 100 ()SSi RSD = ⎜∑ ⎟ Eq. 304B-7 ⎜ ()− ⎟ S ⎝ i=1 n 1 ⎠

12.6 Determination of Percent Air Emis- 2. Test Method 18, 40 CFR 60, Appendix A. sions and Percent Biodegraded. Use the re- 3. Standard Methods for the Examination sults from this test method and follow the of Water and Wastewater, 16th Edition, applicable procedures in appendix C of 40 Method 209C, Total Suspended Solids Dried CFR Part 63, entitled, ‘‘Determination of the at 103–105 °C, APHA, 1985. Fraction Biodegraded (Fbio) in a Biological 4. Water—7, Hazardous Waste Treatment, Treatment Unit’’ to determine Fbio. Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Pro- 13.0 Method Performance [Reserved] tection Agency, EPA–450/3–87–026, Review Draft, November 1989. 14.0 Pollution Prevention [Reserved] 5. Chemdat7, Hazardous Waste Treatment, 15.0 Waste Management [Reserved] Storage, and Disposal Facilities (TSDF)—Air Emission Models, U.S. Environmental Pro- 16.0 References tection Agency, EPA–450/3–87–026, Review 1. ‘‘Guidelines for data acquisition and Draft, November 1989. data quality evaluation in Environmental 17.0 Tables, Diagrams, Flowcharts, and Chemistry’’, Daniel MacDoughal, Analytical Validation Data Chemistry, Volume 52, p. 2242, 1980.

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METHOD 305: MEASUREMENT OF EMISSION PO- A. Therefore, to obtain reliable results, per- TENTIAL OF INDIVIDUAL VOLATILE ORGANIC sons using this method should have a thor- COMPOUNDS IN WASTE ough knowledge of at least Method 25D.

NOTE: This method does not include all of 1.0 Scope and Application the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and ana- 1.1 Analyte. Volatile Organics. No CAS lytical) essential to its performance. Some No. assigned. material is incorporated by reference from other methods in 40 CFR Part 60, Appendix

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1.2 Applicability. This procedure is used 6.1.3 Coalescing Filter. The coalescing fil- to determine the emission potential of indi- ter serves to discourage aerosol formation of vidual volatile organics (VOs) in waste. sample gas once it leaves the purge chamber. 1.3 Data Quality Objectives. Adherence to The glass filter has a fritted disc mounted 10 the requirements of this method will en- cm (3.9 in) from the bottom. Two #7 Ace- hance the quality of the data obtained from threads are used for the inlet and outlet con- air pollutant sampling methods. nections. The dimensions of the chamber are shown in Figure 305–2. 2.0 Summary of Method 6.1.4 Oven. A forced convection airflow 2.1 The heated purge conditions estab- oven capable of maintaining the purge cham- lished by Method 25D (40 CFR Part 60, Appen- ber and coalescing filter at 75 ±2 °C (167 ±3.6 dix A) are used to remove VOs from a 10 °F). gram sample of waste suspended in a 50/50 so- 6.1.5 Toggle Valve. An on/off valve con- lution of polyethylene glycol (PEG) and structed from brass or stainless steel rated water. The purged VOs are quantified by to 100 psig. This valve is placed in line be- using the sample collection and analytical tween the purge nitrogen source and the flow techniques (e.g. gas chromatography) appro- controller. priate for the VOs present in the waste. The 6.1.6 Flow Controller. High-quality stain- recovery efficiency of the sample collection less steel flow controller capable of restrict- and analytical technique is determined for ing a flow of nitrogen to 6 ±0.06 L/min (0.2 each waste matrix. A correction factor is de- ±0.002 ft3/min) at 40 psig. termined for each compound (if acceptable 6.1.7 Polyethylene Glycol Cleaning Sys- recovery criteria requirements are met of 70 tem. to 130 percent recovery for every target com- 6.1.7.1 Round-Bottom Flask. One liter, pound), and the measured waste concentra- three-neck glass round-bottom flask for tion is corrected with the correction factor cleaning PEG. Standard taper 24/40 joints are for each compound. A minimum of three rep- mounted on each neck. licate waste samples shall be analyzed. 6.1.7.2 Heating Mantle. Capable of heating contents of the 1-L flask to 120 °C (248 °F). 3.0 Definitions [Reserved] 6.1.7.3 Nitrogen Bubbler. Teflon ® or glass 4.0 Interferences [Reserved] tube, 0.25 in OD (6.35 mm). 6.1.7.4 Temperature Sensor. Partial im- 5.0 Safety mersion glass thermometer. 6.1.7.5 Hose Adapter. Glass with 24/40 5.1 Disclaimer. This method may involve standard tapered joint. hazardous materials, operations, and equip- 6.2 Volatile Organic Recovery System. ment. This test method may not address all 6.2.1 Splitter Valve (Optional). Stainless of the safety problems associated with its steel cross-pattern valve capable of splitting use. It is the responsibility of the user of this nominal flow rates from the purge flow of 6 test method to establish appropriate safety L/min (0.2 ft3/min). The valve shall be main- and health practices and to determine the tained at 75 + 2 °C (167 ±3.6 °F) in the heated applicability of regulatory limitations prior zone and shall be placed downstream of the to performing this test method. coalescing filter. It is recommended that 6.0 Equipment and Supplies 0.125 in OD (3.175 mm) tubing be used to direct the split vent flow from the heated zone. 6.1 Method 25D Purge Apparatus. The back pressure caused by the 0.125 in OD 6.1.1 Purge Chamber. The purge chamber (3.175 mm) tubing is critical for maintaining shall accommodate the 10 gram sample of proper split valve operation. waste suspended in a matrix of 50 mL of PEG NOTE: The splitter valve design is optional; and 50 mL of deionized, hydrocarbon-free it may be used in cases where the concentra- water. Three fittings are used on the glass chamber top. Two #7 Ace-threads are used tion of a pollutant would saturate the ad- for the purge gas inlet and outlet connec- sorbents. tions. A #50 Ace-thread is used to connect 6.2.2 Injection Port. Stainless steel 1⁄4 in the top of the chamber to the base (see Fig- OD (6.35 mm) compression fitting tee with a ure 305–1). The base of the chamber has a 6 mm (0.2 in) septum fixed on the top port. side-arm equipped with a #22 Sovirel fitting The injection port is the point of entry for to allow for easy sample introductions into the recovery study solution. If using a gas- the chamber. The dimensions of the chamber eous standard to determine recovery effi- are shown in Figure 305–1. ciency, connect the gaseous standard to the 6.1.2 Flow Distribution Device (FDD). The injection port of the tee. FDD enhances the gas-to-liquid contact for 6.2.3 Knockout Trap (Optional but Rec- improved purging efficiency. The FDD is a 6 ommended). A 25 mL capacity glass reservoir mm OD (0.2 in) by 30 cm (12 in) long glass body with a full-stem impinger (to avoid tube equipped with four arm bubblers as leaks, a modified midget glass impinger with shown in Figure 305–1. Each arm shall have a screw cap and ball/socket clamps on the an opening of 1 mm (0.04 in) in diameter. inlet and outlet is recommended). The empty

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impinger is placed in an ice water bath be- and storing the signal generated by the de- tween the injection port and the sorbent car- tector. tridge. Its purpose is to reduce the water content of the purge gas (saturated at 75 °C 7.0 Reagents and Standards (167 °F)) before the sorbent cartridge. 7.1 Method 25D Purge Apparatus. 6.2.4 Insulated Ice Bath. A 350 mL dewar 7.1.1 Polyethylene Glycol (PEG). Ninety- or other type of insulated bath is used to eight percent pure organic polymer with an maintain ice water around the knockout average molecular weight of 400 g/mol. Vola- trap. tile organics are removed from the PEG 6.2.5 Sorbent Cartridges. Commercially prior to use by heating to 120 ±5 °C (248 ±9 °F) available glass or stainless steel cartridge and purging with pure nitrogen at 1 L/min packed with one or more appropriate (0.04 ft3/min) for 2 hours. After purging and sorbents. The amount of adsorbent packed in heating, the PEG is maintained at room the cartridge depends on the breakthrough temperature under a nitrogen purge main- volume of the test compounds but is limited tained at 1 L/min (0.04 ft3/min) until used. A by back pressure caused by the packing (not typical apparatus used to clean the PEG is to exceed 7 psig). More than one sorbent car- shown in Figure 305–3. tridge placed in series may be necessary de- 7.1.2 Water. Organic-free deionized water pending upon the mixture of the measured is required. components. 7.1.3 Nitrogen. High-purity nitrogen (less 6.2.6 Volumetric Glassware. Type A glass than 0.5 ppm total hydrocarbons) is used to 10 mL volumetric flasks for measuring a remove test compounds from the purge ma- final volume from the water catch in the trix. The source of nitrogen shall be regu- knockout trap. lated continuously to 40 psig before the on/ 6.2.7 Thermal Desorption Unit. A clam- off toggle valve. shell type oven, used for the desorption of di- 7.2 Volatile Organic Recovery System. rect thermal desorption sorbent tubes. The 7.2.1 Water. Organic-free deionized water oven shall be capable of increasing the tem- is required. perature of the desorption tubes rapidly to 7.2.2 Desorption Solvent (when used). Ap- recommended desorption temperature. propriate high-purity (99.99 percent) solvent 6.2.8 Ultrasonic Bath. Small bath used to for desorption shall be used. Analysis shall agitate sorbent material and desorption sol- be performed (utilizing the same analytical vent. Ice water shall be used in the bath be- technique as that used in the analysis of the cause of heat transfer caused by operation of waste samples) on each lot to determine pu- the bath. rity. 6.2.9 Desorption Vials. Four-dram (15 mL) 7.3 Analytical System. The gases required capacity borosilicate glass vials with Teflon- for GC operation shall be of the highest ob- lined caps. tainable purity (hydrocarbon free). Consult 6.3 Analytical System. A gas chro- the operating manual for recommended set- matograph (GC) is commonly used to sepa- tings. rate and quantify compounds from the sample collection and recovery procedure. Meth- 8.0 Sample Collection, Preservation, Storage, od 18 (40 CFR Part 60, Appendix A) may be and Transport used as a guideline for determining the ap- 8.1 Assemble the glassware and associated propriate GC column and GC detector based fittings (see Figures 305–3 and 305–4, as ap- on the test compounds to be determined. propriate) and leak-check the system (ap- Other types of analytical instrumentation proximately 7 psig is the target pressure). may be used (HPLC) in lieu of GC systems as After an initial leak check, mark the pres- long as the recovery efficiency criteria of sure gauge and use the initial checkpoint to this method are met. monitor for leaks throughout subsequent 6.3.1 Gas Chromatograph (GC). The GC analyses. If the pressure in the system drops shall be equipped with a constant-tempera- below the target pressure at any time during ture liquid injection port or a heated sam- analysis, that analysis shall be considered pling loop/valve system, as appropriate. The invalid. GC oven shall be temperature-programmable 8.2 Recovery Efficiency Determination. over the useful range of the GC column. The Determine the individual recovery efficiency choice of detectors is based on the test com- (RE) for each of the target compounds in du- pounds to be determined. plicate before the waste samples are ana- 6.3.2 GC Column. Select the appropriate lyzed. To determine the RE, generate a GC column based on (1) literature review or water blank (Section 11.1) and use the injec- previous experience, (2) polarity of the tion port to introduce a known volume of analytes, (3) capacity of the column, or (4) spike solution (or certified gaseous standard) resolving power (e.g., length, diameter, film containing all of the target compounds at thickness) required. the levels expected in the waste sample. In- 6.3.3 Data System. A programmable elec- troduce the spike solution immediately after tronic integrator for recording, analyzing, the nitrogen purge has been started (Section

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8.3.2). Follow the procedures outlined in Sec- sample from the container into the purge tion 8.3.3. Analyze the recovery efficiency flask. Rinse the sample container three samples using the techniques described in times with approximately 6 mL of PEG (or Section 11.2. Determine the recovery effi- the volume needed to total 50 mL of PEG in ciency (Equation 305–1, Section 12.2) by com- the purge flask), transferring the rinses to paring the amount of compound recovered to the purge flask. Add 50 mL of organic-free the theoretical amount spiked. Determine deionized water to the purge flask. Cap the the RE twice for each compound; the relative purge flask tightly in between each rinse and standard deviation, (RSD) shall be ≤10 per- after adding all the components into the cent for each compound. If the RSD for any flask. compound is not ≤10 percent, modify the 8.3.2 Allow the oven to equilibrate to 75 ±2 sampling/analytical procedure and complete °C (167 ±3.6 °F). Begin the sample recovery an RE study in duplicate, or continue deter- process by turning the toggle valve on, thus mining RE until the RSD meets the accept- allowing a 6 L/min flow of pure nitrogen able criteria. The average RE shall be 0.70 through the purge chamber. ≤ ≤ RE 1.30 for each compound. If the average 8.3.3 Stop the purge after 30 min. Imme- RE does not meet these criteria, an alter- diately remove the sorbent tube(s) from the native sample collection and/or analysis apparatus and cap both ends. Remove the technique shall be developed and the recov- knockout trap and transfer the water catch ery efficiency determination shall be re- to a 10 mL volumetric flask. Rinse the trap peated for that compound until the criteria with organic-free deionized water and trans- are met for every target compound. Example fer the rinse to the volumetric flask. Dilute modifications of the sampling/analytical sys- to the 10 mL mark with water. Transfer the tem include changing the adsorbent mate- water sample to a sample vial and store at 4 rial, changing the desorption solvent, uti- °C (39.2 °F) with zero headspace. The analysis lizing direct thermal desorption of test com- of the contents of the water knockout trap is pounds from the sorbent tubes, utilizing an- optional for this method. If the target com- other analytical technique. pounds are water soluble, analysis of the 8.3 Sample Collection and Recovery. 8.3.1 The sample collection procedure in water is recommended; meeting the recovery Method 25D shall be used to collect (into a efficiency criteria in these cases would be preweighed vial) 10 g of waste into PEG, difficult without adding the amount cap- cool, and ship to the laboratory. Remove the tured in the knockout trap. sample container from the cooler and wipe 9.0 Quality Control the exterior to remove any ice or water. Weigh the container and sample to the near- 9.1 Miscellaneous Quality Control Meas- est 0.01 g and record the weight. Pour the ures.

Section Quality control measure Effect

8.1 ...... Sampling equipment leak-check ...... Ensures accurate measurement of sample volume. 8.2 ...... Recovery efficiency (RE) determination Ensures accurate sample collection and analysis. for each measured compound.. 8.3 ...... Calibration of analytical instrument with Ensures linear measurement of compounds over the at least 3 calibration standards.. instrument span.

10.0 Calibration and Standardization 10.2 The analytical system shall be certified free from contaminants before a cali- 10.1 The analytical instrument shall be bration is performed (see Section 11.1). The calibrated with a minimum of three levels of calibration standards are used to determine standards for each compound whose con- the linearity of the analytical system. Per- centrations bracket the concentration of form an initial calibration and linearity test compounds from the sorbent tubes. Liq- check by analyzing the three calibration uid calibration standards shall be used for standards for each target compound in trip- calibration in the analysis of the solvent ex- licate starting with the lowest level and con- tracts. The liquid calibration standards shall tinuing to the highest level. If the triplicate be prepared in the desorption solvent matrix. The calibration standards may be prepared analyses do not agree within 5 percent of and injected individually or as a mixture. If their average, additional analyses will be thermal desorption and focusing (onto an- needed until the 5 percent criteria is met. other sorbent or cryogen focusing) are used, Calculate the response factor (Equation 305– a certified gaseous mixture or a series of gas- 3, Section 12.4) from the average area counts eous standards shall be used for calibration of the injections for each concentration of the instrument. The gaseous standards level. Average the response factors of the shall be focused and analyzed in the same standards for each compound. The linearity manner as the samples. of the detector is acceptable if the response

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factor of each compound at a particular con- (minimizing the amount of adsorbent mate- centration is within 10 percent of the overall rial taken) to another vial and store at 4 °C mean response factor for that compound. (39.2 °F). Analyze daily a mid-level calibration stand- 11.2.2 Analyze the desorption solvent or ard in duplicate and calculate a new response direct thermal desorption tubes from each factor. Compare the daily response factor av- sample using the same analytical param- erage to the average response factor cal- eters used for the calibration standard. Cal- culated for the mid-level calibration during culate the total weight detected for each the initial linearity check; repeat the three- compound (Equation 305–4, Section 12.5). The level calibration procedure if the daily aver- slope (area/amount) and y-intercept are cal- age response factor differs from the initial culated from the line bracketed between the linearity check mid-level response factor by two closest calibration points. Correct the more than 10 percent. Otherwise, proceed concentration of each waste sample with the with the sample analysis. appropriate recovery efficiency factor and the split flow ratio (if used). The final con- 11.0 Analytical Procedure centration of each individual test compound 11.1 Water Blank Analysis. A water blank is calculated by dividing the corrected meas- shall be analyzed daily to determine the ured weight for that compound by the weight cleanliness of the purge and recovery sys- of the original sample determined in Section tem. A water blank is generated by adding 60 8.3.1 (Equation 305–5, Section 12.6). mL of organic-free deionized water to 50 mL 11.2.3 Repeat the analysis for the three of PEG in the purge chamber. Treat the samples collected in Section 8.3. Report the blank as described in Sections 8.3.2 and 8.3.3. corrected concentration of each of the waste The purpose of the water blank is to insure samples, average waste concentration, and that no contaminants exist in the sampling relative standard deviation (Equation 305–6, and analytical apparatus which would inter- Section 12.7). fere with the quantitation of the target compounds. If contaminants are present, locate 12.0 Data Analysis and Calculations. the source of contamination, remove it, and 12.1 Nomenclature. repeat the water blank analysis. AS = Mean area counts of test compound in 11.2 Sample Analysis. Sample analysis in standard. the context of this method refers to tech- A = Mean area counts of test compound in niques to remove the target compounds from U sample desorption solvent. the sorbent tubes, separate them using a b = Y-intercept of the line formed between chromatography technique, and quantify the two closest calibration standards them with an appropriate detector. Two that bracket the concentration of the types of sample extraction techniques typi- sample. cally used for sorbents include solvent μ desorption or direct thermal desorption of CT = Amount of test compound ( g) in cali- test compounds to a secondary focusing unit bration standard. (either sorbent or cryogen based). The test CF = Correction for adjusting final amount of compounds are then typically transferred to sample detected for losses during indi- a GC system for analysis. Other analytical vidual sample runs. systems may be used (e.g., HPLC) in lieu of FP = Nitrogen flow through the purge cham- GC systems as long as the recovery effi- ber (6 L/min). ciency criteria of this method are met. FS = Nitrogen split flow directed to the sam- 11.2.1 Recover the test compounds from ple recovery system (use 6 L/min if split the sorbent tubes that require solvent flow design was not used). desorption by transferring the adsorbent ma- PPM = Final concentration of test compound terial to a sample vial containing the in waste sample [μg/g (which is equiva- desorption solvent. The desorption solvent lent to parts per million by weight shall be the same as the solvent used to pre- (ppmw))]. pare calibration standards. The volume of RE = Recovery efficiency for adjusting final solvent depends on the amount of adsorbed amount of sample detected for losses due material to be desorbed (1.0 mL per 100 mg of to inefficient trapping and desorption adsorbent material) and also on the amount techniques. of test compounds present. Final volume ad- R.F. = Response factor for test compound, justment and or dilution can be made so that calculated from a calibration standard. the concentration of test compounds in the S = Slope of the line (area counts/CT) formed desorption solvent is bracketed by the con- between two closest calibration points centration of the calibration solutions. that bracket the concentration of the Ultrasonicate the desorption solvent for 15 sample. min in an ice bath. Allow the sample to sit WC = Weight of test compound expected to be for a period of time so that the adsorbent recovered in spike solution based on the- material can settle to the bottom of the vial. oretical amount (μg). Transfer the solvent with a pasteur pipet WE = Weight of vial and PEG (g). 688

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WF = Weight of vial, PEG and waste sample WX = Weight of test compound measured dur- (g). ing analysis of recovery efficiency spike μ WS = Weight of original waste sample (g). samples ( g). WT = Corrected weight of test compound 12.2 Recovery efficiency for determining measured (μg) in sample. trapping/desorption efficiency of individual test compounds in the spike solution, decimal value.

W RE = X Eq. 305-1 WC

12.3 Weight of waste sample (g).

=− WWWSFEEq. 305-2

12.4 Response factor for individual test compounds.

C RF = T Eq. 305-3 AS

12.5 Corrected weight of a test compound in the sample, in μg.

− F = Abu ××1 p WT Eq. 305-4 SREFs

12.6 Final concentration of a test compound in the sample in ppmw.

W PPM = T Eq. 305-5 WS

12.7 Relative standard deviation (RSD) calculation.

n 2 ∑()PPM− PPM 100 i RSD = i=1 Eq. 305-6 PPM n −1

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13.0 Method Performance [Reserved] 14.0 Pollution Prevention [Reserved] 15.0 Waste Management [Reserved] 16.0 References [Reserved]

17.0 Tables, Diagrams, Flowcharts, and Validation Data

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METHOD 306—DETERMINATION OF CHROMIUM lytical) essential to its performance. Some EMISSIONS FROM DECORATIVE AND HARD material is incorporated by reference from CHROMIUM ELECTROPLATING AND CHROMIUM other methods in 40 CFR Part 60, Appendix ANODIZING OPERATIONS—ISOKINETIC METH- A. Therefore, to obtain reliable results, per- OD sons using this method should have a thorough knowledge of at least Method 5. NOTE: This method does not include all of the specifications (e.g., equipment and sup- 1.0 Scope and Application plies) and procedures (e.g., sampling and ana- 1.1 Analytes.

Analyte CAS No. Sensitivity

Chromium ...... 7440–47–3 ...... See Sec. 13.2.

1.2 Applicability. This method applies to hydroxide (NaOH) or 0.1 N sodium bicarbon- the determination of chromium (Cr) in emis- ate (NaHCO3). The collected samples are re- sions from decorative and hard chrome elec- covered using an alkaline solution and are troplating facilities, chromium anodizing op- then transported to the laboratory for anal- erations, and continuous chromium plating ysis. operations at iron and steel facilities. 2.2 Analysis. 1.3 Data Quality Objectives. [Reserved] 2.2.1 Total chromium samples with high chromium concentrations (≥35 μg/L) may be 2.0 Summary of Method analyzed using inductively coupled plasma 2.1 Sampling. An emission sample is ex- emission spectrometry (ICP) at 267.72 nm. tracted isokinetically from the source using NOTE: The ICP analysis is applicable for an unheated Method 5 sampling train (40 this method only when the solution analyzed CFR Part 60, Appendix A), with a glass noz- has a Cr concentration greater than or equal zle and probe liner, but with the filter omit- to 35 μg/L or five times the method detection ted. The sample time shall be at least two limit as determined according to appendix B hours. The Cr emissions are collected in an in 40 CFR part 136. Similarly, inductively alkaline solution containing 0.1 N sodium coupled plasma-mass spectroscopy (ICP–MS)

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may be used for total chromium analysis 3.13 Duplicate Sample Analysis—Either the provided the procedures for ICP–MS analysis repeat measurement of a single solution or described in Method 6020 or 6020A (EPA Of- the measurement of duplicate preparations fice of Solid Waste, publication SW–846) are of the same sample. It is important to be followed. aware of which approach is required for a 2.2.2 Alternatively, when lower total particular type of measurement. For exam- chromium concentrations (<35 μg/L) are en- ple, no digestion is required for the ICP de- countered, a portion of the alkaline sample termination and the duplicate instrument solution may be digested with nitric acid and measurement is therefore adequate whereas analyzed by graphite furnace atomic absorp- duplicate digestion/instrument measure- tion spectroscopy (GFAAS) at 357.9 nm. ments are required for GFAAS. 2.2.3 If it is desirable to determine 3.14 Matrix Spiking—Analytical spikes hexavalent chromium (Cr∂6) emissions, the that have been added to the actual sample samples may be analyzed using an ion chro- matrix either before (Section 9.2.5.2) or after matograph equipped with a post-column re- (Section 9.1.6). Spikes added to the sample actor (IC/PCR) and a visible wavelength de- prior to a preparation technique (e.g., diges- tector. To increase sensitivity for trace lev- tion) allow for the assessment of an overall ∂ els of Cr 6, a preconcentration system may method accuracy while those added after be used in conjunction with the IC/PCR. only provide for the measurement accuracy 3.0 Definitions determination. 3.1 Total Chromium—measured chromium 4.0 Interferences content that includes both major chromium 4.1 ICP Interferences. oxidation states (Cr∂3, Cr∂3). 3.2 May—Implies an optional operation. 4.1.1 ICP Spectral Interferences. Spectral 3.3 Digestion—The analytical operation in- interferences are caused by: overlap of a volving the complete (or nearly complete) spectral line from another element; unre- dissolution of the sample in order to ensure solved overlap of molecular band spectra; the complete solubilization of the element background contribution from continuous or (analyte) to be measured. recombination phenomena; and, stray light 3.4 Interferences—Physical, chemical, or from the line emission of high-concentrated spectral phenomena that may produce a high elements. Spectral overlap may be com- or low bias in the analytical result. pensated for by correcting the raw data with 3.5 Analytical System—All components of a computer and measuring the interfering the analytical process including the sample element. At the 267.72 nm Cr analytical digestion and measurement apparatus. wavelength, iron, manganese, and uranium 3.6 Sample Recovery—The quantitative are potential interfering elements. Back- transfer of sample from the collection appa- ground and stray light interferences can usu- ratus to the sample preparation (digestion, ally be compensated for by a background etc.) apparatus. This term should not be con- correction adjacent to the analytical line. fused with analytical recovery. Unresolved overlap requires the selection of 3.7 Matrix Modifier—A chemical modifica- an alternative chromium wavelength. Con- tion to the sample during GFAAS determina- sult the instrument manufacturer’s oper- tions to ensure that the analyte is not lost ation manual for interference correction pro- during the measurement process (prior to cedures. the atomization stage) 4.1.2 ICP Physical Interferences. High lev- 3.8 Calibration Reference Standards—Qual- els of dissolved solids in the samples may ity control standards used to check the accu- cause significant inaccuracies due to salt racy of the instrument calibration curve buildup at the nebulizer and torch tips. This prior to sample analysis. problem can be controlled by diluting the 3.9 Continuing Check Standard—Quality sample or by extending the rinse times be- control standards used to verify that unac- tween sample analyses. Standards shall be ceptable drift in the measurement system prepared in the same solution matrix as the has not occurred. samples (i.e., 0.1 N NaOH or 0.1 N NaHCO ). 3.10 Calibration Blank—A blank used to 3 verify that there has been no unacceptable 4.1.3 ICP Chemical Interferences. These shift in the baseline either immediately fol- include molecular compound formation, ion- lowing calibration or during the course of ization effects and solute vaporization ef- the analytical measurement. fects, and are usually not significant in the 3.11 Interference Check—An analytical/ ICP procedure, especially if the standards measurement operation that ascertains and samples are matrix matched. whether a measurable interference in the 4.2 GFAAS Interferences. sample exists. 4.2.1 GFAAS Chemical Interferences. Low 3.12 Interelement Correction Factors—Fac- concentrations of calcium and/or phosphate tors used to correct for interfering elements may cause interferences; at concentrations that produce a false signal (high bias). above 200 μg/L, calcium’s effect is constant

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and eliminates the effect of phosphate. Cal- particulate filter is omitted, and quartz or cium nitrate is therefore added to the con- borosilicate glass must be used for the probe centrated analyte to ensure a known con- nozzle and liner in place of stainless steel. stant effect. Other matrix modifiers rec- 6.1.2 Probe fittings of plastic such as Tef- ommended by the instrument manufacturer lon, polypropylene, etc. are recommended may also be considered. over metal fittings to prevent contamina- 4.2.2 GFAAS Cyanide Band Interferences. tion. If desired, a single combined probe noz- Nitrogen should not be used as the purge gas zle and liner may be used, but such a single due to cyanide band interference. glass assembly is not a requirement of this 4.2.3 GFAAS Spectral Interferences. methodology. Background correction may be required be- 6.1.3 Use 0.1 N NaOH or 0.1 N NaHCO3 in cause of possible significant levels of nonspe- the impingers in place of water. cific absorption and scattering at the 357.9 6.1.4 Operating and maintenance proce- nm analytical wavelength. dures for the sampling train are described in 4.2.4 GFAAS Background Interferences. APTD–0576 of Method 5. Users should read Zeeman or Smith-Hieftje background correc- the APTD–0576 document and adopt the out- tion is recommended for interferences result- lined procedures. Alternative mercury-free ing from high levels of dissolved solids in the thermometers may be used if the thermom- alkaline impinger solutions. eters are, at a minimum, equivalent in terms 4.3 IC/PCR Interferences. of performance or suitably effective for the 4.3.1 IC/PCR Chemical Interferences. Com- specific temperature measurement applica- ponents in the sample matrix may cause tion. Cr∂6 to convert to trivalent chromium (Cr∂3) 6.1.5 Similar collection systems which or cause Cr∂3 to convert to Cr∂6. The have been approved by the Administrator chromatographic separation of Cr∂6 using may be used. ion chromatography reduces the potential 6.2 Sample Recovery. Same as Method 5, for other metals to interfere with the post [40 CFR Part 60, Appendix A], with the fol- column reaction. For the IC/PCR analysis, lowing exceptions: ∂ only compounds that coelute with Cr 6 and 6.2.1 Probe-Liner and Probe-Nozzle Brush- affect the diphenylcarbazide reaction will es. Brushes are not necessary for sample re- cause interference. covery. If a probe brush is used, it must be 4.3.2 IC/PCR Background Interferences. non-metallic. Periodic analyses of reagent water blanks 6.2.2 Sample Recovery Solution. Use 0.1 N are used to demonstrate that the analytical NaOH or 0.1 N NaHCO3, whichever is used as system is essentially free of contamination. the impinger absorbing solution, in place of Sample cross-contamination can occur when acetone to recover the sample. high-level and low-level samples or stand- 6.2.3 Sample Storage Containers. Poly- ards are analyzed alternately and can be ethylene, with leak-free screw cap, 250 mL, eliminated by thorough purging of the sam- 500 mL or 1,000 mL. ple loop. Purging of the sample can easily be 6.3 Analysis. achieved by increasing the injection volume 6.3.1 General. For analysis, the following to ten times the size of the sample loop. equipment is needed. 6.3.1.1 Phillips Beakers. (Phillips beakers 5.0 Safety are preferred, but regular beakers may also 5.1 Disclaimer. This method may involve be used.) hazardous materials, operations, and equip- 6.3.1.2 Hot Plate. ment. This test method may not address all 6.3.1.3 Volumetric Flasks. Class A, var- of the safety problems associated with its ious sizes as appropriate. use. It is the responsibility of the user to es- 6.3.1.4 Assorted Pipettes. tablish appropriate safety and health prac- 6.3.2 Analysis by ICP. tices and to determine the applicability of 6.3.2.1 ICP Spectrometer. Computer-con- regulatory limitations prior to performing trolled emission spectrometer with back- this test method. ground correction and radio frequency gener- 5.2 Hexavalent chromium compounds ator. have been listed as carcinogens although 6.3.2.2 Argon Gas Supply. Welding grade chromium (III) compounds show little or no or better. toxicity. Chromium can be a skin and res- 6.3.3 Analysis by GFAAS. piratory irritant. 6.3.3.1 Chromium Hollow Cathode Lamp or Electrodeless Discharge Lamp. 6.0 Equipment and Supplies 6.3.3.2 Graphite Furnace Atomic Absorp- 6.1 Sampling Train. tion Spectrophotometer. 6.1.1 A schematic of the sampling train 6.3.3.3 Furnace Autosampler. used in this method is shown in Figure 306– 6.3.4 Analysis by IC/PCR. 1. The train is the same as shown in Method 6.3.4.1 IC/PCR System. High performance 5, Section 6.0 (40 CFR part 60, appendix A) ex- liquid chromatograph pump, sample injec- cept that the probe liner is unheated, the tion valve, post-column reagent delivery and

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mixing system, and a visible detector, capa- 7.1.3 Sodium Bicarbonate (NaHCO3) Ab- ble of operating at 520 nm-540 nm, all with a sorbing Solution, 0.1 N. Dissolve approxi- non-metallic (or inert) flow path. An elec- mately 8.5 g of sodium bicarbonate in 1 liter tronic peak area mode is recommended, but of water to obtain a pH of approximately 8.3. other recording devices and integration tech- 7.1.4 Chromium Contamination. niques are acceptable provided the repeat- 7.1.4.1 The absorbing solution shall not ability criteria and the linearity criteria for exceed the QC criteria noted in Section 7.1.1 the calibration curve described in Section (≤3 times the instrument detection limit). 10.4 can be satisfied. A sample loading sys- 7.1.4.2 When the Cr∂6 content in the field tem is required if preconcentration is em- samples exceeds the blank concentration by ployed. at least a factor of ten (10), Cr∂6 blank con- 6.3.4.2 Analytical Column. A high per- centrations ≥10 times the detection limit will formance ion chromatograph (HPIC) non-me- be allowed. tallic column with anion separation charac- NOTE: At sources with high concentrations teristics and a high loading capacity de- of acids and/or SO2, the concentration of signed for separation of metal chelating NaOH or NaHCO3 should be ≥0.5 N to insure compounds to prevent metal interference. that the pH of the solution remains at or Resolution described in Section 11.6 must be above 8.5 for NaOH and 8.0 for NaHCO3 during obtained. A non-metallic guard column with and after sampling. the same ion-exchange material is rec- 7.1.5 Silica Gel. Same as in Method 5. ommended. 7.2 Sample Recovery. 6.3.4.3 Preconcentration Column (for older 7.2.1 0.1 N NaOH or 0.1 N NaHCO3. Use the instruments). An HPIC non-metallic column same solution for the sample recovery that with acceptable anion retention characteris- is used for the impinger absorbing solution. tics and sample loading rates must be used 7.2.2 pH Indicator Strip, for IC/PCR. pH as described in Section 11.6. indicator capable of determining the pH of 6.3.4.4 Filtration Apparatus for IC/PCR. solutions between the pH range of 7 and 12, 6.3.4.4.1 Teflon, or equivalent, filter hold- at 0.5 pH increments. er to accommodate 0.45-μm acetate, or equiv- 7.3 Sample Preparation and Analysis. alent, filter, if needed to remove insoluble 7.3.1 Nitric Acid (HNO3), Concentrated, for particulate matter. GFAAS. Trace metals grade or better HNO3 6.3.4.4.2 0.45-μm Filter Cartridge. For the must be used for reagent preparation. The removal of insoluble material. To be used ACS reagent grade HNO3 is acceptable for just prior to sample injection/analysis. cleaning glassware. 7.3.2 HNO3, 1.0% (v/v), for GFAAS. Pre- 7.0 Reagents and Standards pare, by slowly stirring, 10 mL of concentrated HNO ) into 800 mL of reagent NOTE: Unless otherwise indicated, all re- 3 water. Dilute to 1,000 mL with reagent water. agents should conform to the specifications The solution shall contain less than 0.001 mg established by the Committee on Analytical Cr/L. Reagents of the American Chemical Society 7.3.3 Calcium Nitrate Ca(NO ) Solution (ACS reagent grade). Where such specifica- 3 2 (10 μg Ca/mL) for GFAAS analysis. Prepare tions are not available, use the best avail- the solution by weighing 40.9 mg of Ca(NO ) able grade. Reagents should be checked by 3 2 into a 1 liter volumetric flask. Dilute with the appropriate analysis prior to field use to reagent water to 1 liter. assure that contamination is below the ana- 7.3.4 Matrix Modifier, for GFAAS. See in- lytical detection limit for the ICP or GFAAS strument manufacturer’s manual for sug- total chromium analysis; and that contami- gested matrix modifier. nation is below the analytical detection 7.3.5 Chromatographic Eluent, for IC/PCR. limit for Cr∂6 using IC/PCR for direct injec- The eluent used in the analytical system is tion or, if selected, preconcentration. ammonium sulfate based. 7.1 Sampling. 7.3.5.1 Prepare by adding 6.5 mL of 29 per- 7.1.1 Water. Reagent water that conforms cent ammonium hydroxide (NH4OH) and 33 g to ASTM Specification D1193–77 or 91 Type II of ammonium sulfate ((NH4)2SO4) to 500 mL (incorporated by reference see § 63.14). All of reagent water. Dilute to 1 liter with rea- references to water in the method refer to re- gent water and mix well. agent water unless otherwise specified. It is 7.3.5.2 Other combinations of eluents and/ recommended that water blanks be checked or columns may be employed provided peak prior to preparing the sampling reagents to resolution, repeatability, linearity, and ana- ensure that the Cr content is less than three lytical sensitivity as described in Sections (3) times the anticipated detection limit of 9.3 and 11.6 are acceptable. the analytical method. 7.3.6 Post-Column Reagent, for IC/PCR. 7.1.2 Sodium Hydroxide (NaOH) Absorbing An effective post-column reagent for use Solution, 0.1 N. Dissolve 4.0 g of sodium hy- with the chromatographic eluent described droxide in 1 liter of water to obtain a pH of in Section 7.3.5 is a diphenylcarbazide (DPC)- approximately 8.5. based system. Dissolve 0.5 g of 1,5-

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diphenylcarbazide in 100 mL of ACS grade three additional rinses with reagent water. methanol. Add 500 mL of reagent water con- Then soak the glassware in 10% (v/v) HNO3 taining 50 mL of 96 percent solution for a minimum of 4 hours, rinse spectrophotometric grade sulfuric acid. Di- three times with reagent water, and allow to lute to 1 liter with reagent water. air dry. Cover all glassware openings where 7.3.7 Chromium Standard Stock Solution contamination can occur with Parafilm, or (1000 mg/L). Procure a certified aqueous equivalent, until the sampling train is as- standard or dissolve 2.829 g of potassium di- sembled for sampling. chromate (K2Cr2O7), in reagent water and di- 8.1.3 Train Operation. Follow the basic lute to 1 liter. procedures outlined in Method 5 in conjunc- 7.3.8 Calibration Standards for ICP or IC/ tion with the following instructions. Train PCR. Prepare calibration standards for ICP sampling rate shall not exceed 0.030 m3/min or IC/PCR by diluting the Cr standard stock (1.0 cfm) during a run. solution (Section 7.3.7) with 0.1 N NaOH or 8.2 Sample Recovery. Follow the basic 0.1 N NaHCO3, whichever is used as the im- procedures of Method 5, with the exceptions pinger absorbing solution, to achieve a ma- noted. trix similar to the actual field samples. Sug- 8.2.1 A particulate filter is not recovered gested levels are 0, 50, 100, and 200 μg Cr/L for from this train. ICP, and 0, 1, 5, and 10 μg Cr∂6/L for IC/PCR. 8.2.2 Tester shall select either the total Cr 7.3.9 Calibration Standards for GFAAS. or Cr∂6 sample recovery option. Chromium solutions for GFAAS calibration 8.2.3 Samples to be analyzed for both ∂6 shall contain 1.0 percent (v/v) HNO3. The zero total Cr and Cr , shall be recovered using ∂6 standard shall be 1.0 percent (v/v) HNO3. Cali- the Cr sample option (Section 8.2.6). bration standards should be prepared daily 8.2.4 A field reagent blank shall be col- by diluting the Cr standard stock solution lected for either of the Cr or the Cr∂6 anal- ∂6 (Section 7.3.7) with 1.0 percent HNO3. Use at ysis. If both analyses (Cr and Cr ) are to be least four standards to make the calibration conducted on the samples, collect separate curve. Suggested levels are 0, 10, 50, and 100 reagent blanks for each analysis. μg Cr/L. NOTE: Since particulate matter is not usu- 7.4 Glassware Cleaning Reagents. ally present at chromium electroplating and/ 7.4.1 HNO3, Concentrated. ACS reagent or chromium anodizing operations, it is not grade or equivalent. necessary to filter the Cr∂6 samples unless 7.4.2 Water. Reagent water that conforms there is observed sediment in the collected to ASTM Specification D1193–77 or 91 Type solutions. If it is necessary to filter the Cr∂6 II. solutions, please refer to Method 0061, Deter- 7.4.3 HNO3, 10 percent (v/v). Add by stir- mination of Hexavalent Chromium Emis- ring 500 mL of concentrated HNO3 into a sions From Stationary Sources, Section 7.4, flask containing approximately 4,000 mL of Sample Preparation in SW–846 (see Reference reagent water. Dilute to 5,000 mL with rea- 1). gent water. Mix well. The reagent shall con- 8.2.5 Total Cr Sample Option. tain less than 2 μg Cr/L. 8.2.5.1 Container No. 1. Measure the vol- 8.0 Sample Collection, Preservation, Holding ume of the liquid in the first, second, and Times, Storage, and Transport third impingers and quantitatively transfer into a labeled sample container. NOTE: Prior to sample collection, consider- 8.2.5.2 Use approximately 200 to 300 mL of ation should be given to the type of analysis the 0.1 N NaOH or 0.1 N NaHCO absorbing ∂ 3 (Cr 6 or total Cr) that will be performed. solution to rinse the probe nozzle, probe Which analysis option(s) will be performed liner, three impingers, and connecting glass- will determine which sample recovery and ware; add this rinse to Container No. 1. storage procedures will be required to proc- 8.2.6 Cr∂6 Sample Option. ess the sample. 8.2.6.1 Container No. 1. Measure and 8.1 Sample Collection. Same as Method 5 record the pH of the absorbing solution con- (40 CFR part 60, appendix A), with the fol- tained in the first impinger at the end of the lowing exceptions. sampling run using a pH indicator strip. The 8.1.1 Omit the particulate filter and filter pH of the solution must be ≥8.5 for NaOH and holder from the sampling train. Use a glass ≥8.0 for NaHCO3. If it is not, discard the col- nozzle and probe liner instead of stainless lected sample, increase the normality of the steel. Do not heat the probe. Place 100 mL of NaOH or NaHCO3 impinger absorbing solu- 0.1 N NaOH or 0.1 N NaHCO3 in each of the tion to 0.5 N or to a solution normality ap- first two impingers, and record the data for proved by the Administrator and collect an- each run on a data sheet such as shown in other air emission sample. Figure 306–2. 8.2.6.2 After determining the pH of the 8.1.2 Clean all glassware prior to sampling first impinger solution, combine and meas- in hot soapy water designed for laboratory ure the volume of the liquid in the first, sec- cleaning of glassware. Next, rinse the glass- ond, and third impingers and quantitatively ware three times with tap water, followed by transfer into the labeled sample container.

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Use approximately 200 to 300 mL of the 0.1 N of the mean blank value. If not, analyze the NaOH or 0.1 N NaHCO3 absorbing solution to calibration blank two more times and aver- rinse the probe nozzle, probe liner, three age the results. If the average is not within impingers, and connecting glassware; add three standard deviations of the background this rinse to Container No. 1. mean, terminate the analyses, correct the 8.2.7 Field Reagent Blank. problem, recalibrate, and reanalyze all sam- 8.2.7.1 Container No. 2. ples analyzed subsequent to the last accept- 8.2.7.2 Place approximately 500 mL of the able calibration blank analysis. 0.1 N NaOH or 0.1 N NaHCO3 absorbing solu- 9.1.4 ICP Interference Check. Prepare an tion into a labeled sample container. interference check solution that contains 8.3 Sample Preservation, Storage, and known concentrations of interfering ele- Transport. ments that will provide an adequate test of 8.3.1 Total Cr Sample Option. Samples to the correction factors in the event of poten- be analyzed for total Cr need not be refrig- tial spectral interferences. erated. ∂ 9.1.4.1 Two potential interferences, iron 8.3.2 Cr 6 Sample Option. Samples to be and manganese, may be prepared as 1000 μg/ ∂6 analyzed for Cr must be shipped and stored mL and 200 μg/mL solutions, respectively. ° ∂6 at 4 C. Allow Cr samples to return to am- The solutions should be prepared in dilute bient temperature prior to analysis. HNO3 (1–5 percent). Particular care must be 8.4 Sample Holding Times. used to ensure that the solutions and/or salts 8.4.1 Total Cr Sample Option. Samples to used to prepare the solutions are of ICP be analyzed for total Cr shall be analyzed grade purity (i.e., that no measurable Cr con- within 60 days of collection. tamination exists in the salts/solutions). 8.4.2 Cr∂6 Sample Option. Samples to be Commercially prepared interfering element analyzed for Cr∂6 shall be analyzed within 14 check standards are available. days of collection. 9.1.4.2 Verify the interelement correction 9.0 Quality Control factors every three months by analyzing the interference check solution. The correction 9.1 ICP Quality Control. factors are calculated according to the in- 9.1.1 ICP Calibration Reference Stand- strument manufacturer’s directions. If the ards. Prepare a calibration reference stand- interelement correction factors are used ard using the same alkaline matrix as the properly, no false Cr should be detected. calibration standards; it should be at least 10 9.1.4.3 Negative results with an absolute times the instrumental detection limit. value greater than three (3) times the detec- 9.1.1.1 This reference standard must be tion limit are usually the results of the prepared from a different Cr stock solution background correction position being set in- source than that used for preparation of the correctly. Scan the spectral region to ensure calibration curve standards. 9.1.1.2 Prior to sample analysis, analyze that the correction position has not been at least one reference standard. placed on an interfering peak. 9.1.1.3 The calibration reference standard 9.1.5 ICP Duplicate Sample Analysis. Per- must be measured within 10 percent of it’s form one duplicate sample analysis for each true value for the curve to be considered compliance sample batch (3 runs). valid. 9.1.5.1 As there is no sample preparation 9.1.1.4 The curve must be validated before required for the ICP analysis, a duplicate sample analyses are performed. analysis is defined as a repeat analysis of one 9.1.2 ICP Continuing Check Standard. of the field samples. The selected sample 9.1.2.1 Perform analysis of the check shall be analyzed using the same procedures standard with the field samples as described that were used to analyze the original sam- in Section 11.2 (at least after every 10 sample. ples, and at the end of the analytical run). 9.1.5.2 Duplicate sample analyses shall 9.1.2.2 The check standard can either be agree within 10 percent of the original meas- the mid-range calibration standard or the urement value. reference standard. The results of the check 9.1.5.3 Report the original analysis value standard shall agree within 10 percent of the for the sample and report the duplicate anal- expected value; if not, terminate the analysis value as the QC check value. If agree- yses, correct the problem, recalibrate the in- ment is not achieved, perform the duplicate strument, and rerun all samples analyzed analysis again. If agreement is not achieved subsequent to the last acceptable check the second time, perform corrective action standard analysis. to identify and correct the problem before 9.1.3 ICP Calibration Blank. analyzing the sample for a third time. 9.1.3.1 Perform analysis of the calibration 9.1.6 ICP Matrix Spiking. Spiked samples blank with the field samples as described in shall be prepared and analyzed daily to en- Section 11.2 (at least after every 10 samples, sure that there are no matrix effects, that and at the end of the analytical run). samples and standards have been matrix- 9.1.3.2 The results of the calibration blank matched, and that the laboratory equipment shall agree within three standard deviations is operating properly.

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9.1.6.1 Spiked sample recovery analyses Section 11.4 (at least after every 10 samples, should indicate a recovery for the Cr spike of and at the end of the analytical run). between 75 and 125 percent. 9.2.3.2 The calibration blank is analyzed 9.1.6.2 Cr levels in the spiked sample to monitor the life and performance of the should provide final solution concentrations graphite tube as well as the existence of any that are within the linear portion of the cali- memory effects. Lack of reproducibility or a bration curve, as well as, at a concentration significant change in the signal, may indi- level at least: equal to that of the original cate that the graphite tube should be re- sample; and, ten (10) times the detection placed. limit. 9.2.3.3 The results of the calibration blank 9.1.6.3 If the spiked sample concentration shall agree within three standard deviations meets the stated criteria but exceeds the lin- of the mean blank value. ear calibration range, the spiked sample 9.2.3.4 If not, analyze the calibration must be diluted with the field absorbing so- blank two more times and average the re- lution. sults. If the average is not within three 9.1.6.4 If the recoveries for the Cr spiked standard deviations of the background mean, samples do not meet the specified criteria, terminate the analyses, correct the problem, perform corrective action to identify and recalibrate, and reanalyze all samples ana- correct the problem prior to reanalyzing the lyzed subsequent to the last acceptable cali- samples. bration blank analysis. 9.1.7 ICP Field Reagent Blank. 9.2.4 GFAAS Duplicate Sample Analysis. 9.1.7.1 Analyze a minimum of one matrix- Perform one duplicate sample analysis for matched field reagent blank (Section 8.2.4) each compliance sample batch (3 runs). per sample batch to determine if contamina- 9.2.4.1 A digested aliquot of the selected tion or memory effects are occurring. sample is processed and analyzed using the 9.1.7.2 If contamination or memory effects identical procedures that were used for the are observed, perform corrective action to whole sample preparation and analytical ef- identify and correct the problem before re- forts. analyzing the samples. 9.2.4.2 Duplicate sample analyses results 9.2 GFAAS Quality Control. incorporating duplicate digestions shall 9.2.1 GFAAS Calibration Reference Stand- agree within 20 percent for sample results ex- ards. The calibration curve must be verified ceeding ten (10) times the detection limit. by using at least one calibration reference 9.2.4.3 Report the original analysis value standard (made from a reference material or for the sample and report the duplicate anal- other independent standard material) at or ysis value as the QC check value. near the mid-range of the calibration curve. 9.2.1.1 The calibration curve must be vali- 9.2.4.4 If agreement is not achieved, per- dated before sample analyses are performed. form the duplicate analysis again. If agree- 9.2.1.2 The calibration reference standard ment is not achieved the second time, per- must be measured within 10 percent of its form corrective action to identify and cor- true value for the curve to be considered rect the problem before analyzing the sample valid. for a third time. 9.2.2 GFAAS Continuing Check Standard. 9.2.5 GFAAS Matrix Spiking. 9.2.2.1 Perform analysis of the check 9.2.5.1 Spiked samples shall be prepared standard with the field samples as described and analyzed daily to ensure that (1) correct in Section 11.4 (at least after every 10 sam- procedures are being followed, (2) there are ples, and at the end of the analytical run). no matrix effects and (3) all equipment is op- 9.2.2.2 These standards are analyzed, in erating properly. part, to monitor the life and performance of 9.2.5.2 Cr spikes are added prior to any the graphite tube. Lack of reproducibility or sample preparation. a significant change in the signal for the 9.2.5.3 Cr levels in the spiked sample check standard may indicate that the graph- should provide final solution concentrations ite tube should be replaced. that are within the linear portion of the cali- 9.2.2.3 The check standard may be either bration curve, as well as, at a concentration the mid-range calibration standard or the level at least: equal to that of the original reference standard. sample; and, ten (10) times the detection 9.2.2.4 The results of the check standard limit. shall agree within 10 percent of the expected 9.2.5.4 Spiked sample recovery analyses value. should indicate a recovery for the Cr spike of 9.2.2.5 If not, terminate the analyses, cor- between 75 and 125 percent. rect the problem, recalibrate the instrument, 9.2.5.5 If the recoveries for the Cr spiked and reanalyze all samples analyzed subse- samples do not meet the specified criteria, quent to the last acceptable check standard perform corrective action to identify and analysis. correct the problem prior to reanalyzing the 9.2.3 GFAAS Calibration Blank. samples. 9.2.3.1 Perform analysis of the calibration 9.2.6 GFAAS Method of Standard Addi- blank with the field samples as described in tions.

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9.2.6.1 Method of Standard Additions. Per- 9.3.3 IC/PCR Duplicate Sample Analysis. form procedures in Section 5.4 of Method 12 9.3.3.1 Perform one duplicate sample anal- (40 CFR Part 60, Appendix A) ysis for each compliance sample batch (3 9.2.6.2 Whenever sample matrix problems runs). are suspected and standard/sample matrix 9.3.3.2 An aliquot of the selected sample is matching is not possible or whenever a new prepared and analyzed using procedures iden- sample matrix is being analyzed, perform tical to those used for the emission samples referenced procedures to determine if the (for example, filtration and/or, if necessary, method of standard additions is necessary. preconcentration). 9.2.7 GFAAS Field Reagent Blank. 9.3.3.3 Duplicate sample injection results 9.2.7.1 Analyze a minimum of one matrix- shall agree within 10 percent for sample re- matched field reagent blank (Section 8.2.4) sults exceeding ten (10) times the detection per sample batch to determine if contamina- limit. tion or memory effects are occurring. 9.3.3.4 Report the original analysis value 9.2.7.2 If contamination or memory effects for the sample and report the duplicate anal- are observed, perform corrective action to ysis value as the QC check value. identify and correct the problem before re- 9.3.3.5 If agreement is not achieved, per- analyzing the samples. form the duplicate analysis again. 9.3 IC/PCR Quality Control. 9.3.3.6 If agreement is not achieved the 9.3.1 IC/PCR Calibration Reference Stand- second time, perform corrective action to ards. identify and correct the problem prior to 9.3.1.1 Prepare a calibration reference analyzing the sample for a third time. standard at a concentration that is at or 9.3.4 ICP/PCR Matrix Spiking. Spiked near the mid-point of the calibration curve samples shall be prepared and analyzed with using the same alkaline matrix as the cali- each sample set to ensure that there are no bration standards. This reference standard matrix effects, that samples and standards should be prepared from a different Cr stock have been matrix-matched, and that the solution than that used to prepare the cali- equipment is operating properly. bration curve standards. The reference 9.3.4.1 Spiked sample recovery analysis standard is used to verify the accuracy of the should indicate a recovery of the Cr∂6 spike calibration curve. between 75 and 125 percent. 9.3.1.2 The curve must be validated before 9.3.4.2 The spiked sample concentration sample analyses are performed. Prior to should be within the linear portion of the sample analysis, analyze at least one ref- calibration curve and should be equal to or erence standard with an expected value with- greater than the concentration of the origi- in the calibration range. nal sample. In addition, the spiked sample 9.3.1.3 The results of this reference stand- concentration should be at least ten (10) ard analysis must be within 10 percent of the times the detection limit. true value of the reference standard for the 9.3.4.3 If the recoveries for the Cr∂6 spiked calibration curve to be considered valid. samples do not meet the specified criteria, 9.3.2 IC/PCR Continuing Check Standard perform corrective action to identify and and Calibration Blank. correct the problem prior to reanalyzing the 9.3.2.1 Perform analysis of the check samples. standard and the calibration blank with the 9.3.5 IC/PCR Field Reagent Blank. field samples as described in Section 11.6 (at 9.3.5.1 Analyze a minimum of one matrix- least after every 10 samples, and at the end matched field reagent blank (Section 8.2.4) of the analytical run). per sample batch to determine if contamina- 9.3.2.2 The result from the check standard tion or memory effects are occurring. must be within 10 percent of the expected 9.3.5.2 If contamination or memory effects value. are observed, perform corrective action to 9.3.2.3 If the 10 percent criteria is exceed- identify and correct the problem before re- ed, excessive drift and/or instrument deg- analyzing the samples. radation may have occurred, and must be 10.0 Calibration and Standardization corrected before further analyses can be performed. 10.1 Sampling Train Calibration. Perform 9.3.2.4 The results of the calibration blank calibrations described in Method 5, (40 CFR analyses must agree within three standard part 60, appendix A). The alternate calibra- deviations of the mean blank value. tion procedures described in Method 5, may 9.3.2.5 If not, analyze the calibration also be used. blank two more times and average the re- 10.2 ICP Calibration. sults. 10.2.1 Calibrate the instrument according 9.3.2.6 If the average is not within three to the instrument manufacturer’s rec- standard deviations of the background mean, ommended procedures, using a calibration terminate the analyses, correct the problem, blank and three standards for the initial recalibrate, and reanalyze all samples ana- calibration. lyzed subsequent to the last acceptable cali- 10.2.2 Calibration standards should be pre- bration blank analysis. pared fresh daily, as described in Section

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7.3.8. Be sure that samples and calibration times the method detection limit as deter- standards are matrix matched. Flush the mined according to Appendix B in 40 CFR system with the calibration blank between Part 136 or by other commonly accepted ana- each standard. lytical procedures. 10.2.3 Use the average intensity of mul- 11.2 ICP Sample Analysis. tiple exposures (3 or more) for both standard- 11.2.1 The ICP analysis is applicable for ization and sample analysis to reduce ran- the determination of total chromium only. dom error. 11.2.2 ICP Blanks. Two types of blanks are 10.2.4 Employing linear regression, cal- required for the ICP analysis. culate the correlation coefficient . 11.2.2.1 Calibration Blank. The calibration 10.2.5 The correlation coefficient must blank is used in establishing the calibration equal or exceed 0.995. curve. For the calibration blank, use either 10.2.6 If linearity is not acceptable, pre- 0.1 N NaOH or 0.1 N NaHCO3, whichever is pare and rerun another set of calibration used for the impinger absorbing solution. standards or reduce the range of the calibra- The calibration blank can be prepared fresh tion standards, as necessary. in the laboratory; it does not have to be pre- 10.3 GFAAS Calibration. pared from the same batch of solution that 10.3.1 For instruments that measure di- was used in the field. A sufficient quantity rectly in concentration, set the instrument should be prepared to flush the system be- software to display the correct concentra- tween standards and samples. tion, if applicable. 11.2.2.2 Field Reagent Blank. The field re- 10.3.2 Curve must be linear in order to agent blank is collected in the field during correctly perform the method of standard ad- the testing program. The field reagent blank ditions which is customarily performed auto- (Section 8.2.4) is an aliquot of the absorbing matically with most instrument computer- solution prepared in Section 7.1.2. The rea- based data systems. gent blank is used to assess possible con- 10.3.3 The calibration curve (direct cali- tamination resulting from sample proc- bration or standard additions) must be pre- essing. pared daily with a minimum of a calibration blank and three standards that are prepared 11.2.3 ICP Instrument Adjustment. fresh daily. 11.2.3.1 Adjust the ICP instrument for 10.3.4 The calibration curve acceptance proper operating parameters including wave- criteria must equal or exceed 0.995. length, background correction settings (if 10.3.5 If linearity is not acceptable, pre- necessary), and interfering element correc- pare and rerun another set of calibration tion settings (if necessary). standards or reduce the range of calibration 11.2.3.2 The instrument must be allowed standards, as necessary. to become thermally stable before beginning 10.4 IC/PCR Calibration. measurements (usually requiring at least 30 10.4.1 Prepare a calibration curve using min of operation prior to calibration). Dur- the calibration blank and three calibration ing this warmup period, the optical calibra- standards prepared fresh daily as described tion and torch position optimization may be in Section 7.3.8. performed (consult the operator’s manual). 10.4.2 The calibration curve acceptance 11.2.4 ICP Instrument Calibration. criteria must equal or exceed 0.995. 11.2.4.1 Calibrate the instrument accord- 10.4.3 If linearity is not acceptable, re- ing to the instrument manufacturer’s rec- make and/or rerun the calibration standards. ommended procedures, and the procedures If the calibration curve is still unacceptable, specified in Section 10.2. reduce the range of the curve. 11.2.4.2 Prior to analyzing the field sam- 10.4.4 Analyze the standards with the field ples, reanalyze the highest calibration stand- samples as described in Section 11.6. ard as if it were a sample. 11.2.4.3 Concentration values obtained 11.0 Analytical Procedures should not deviate from the actual values or NOTE: The method determines the chro- from the established control limits by more mium concentration in μg Cr/mL. It is im- than 5 percent, whichever is lower (see Sec- portant that the analyst measure the field tions 9.1 and 10.2). sample volume prior to analyzing the sam- 11.2.4.4 If they do, follow the rec- ple. This will allow for conversion of μg Cr/ ommendations of the instrument manufac- mL to μg Cr/sample. turer to correct the problem. 11.1 ICP Sample Preparation. 11.2.5 ICP Operational Quality Control 11.1.1 The ICP analysis is performed di- Procedures. rectly on the alkaline impinger solution; 11.2.5.1 Flush the system with the calibra- acid digestion is not necessary, provided the tion blank solution for at least 1 min before samples and standards are matrix matched. the analysis of each sample or standard. 11.1.2 The ICP analysis should only be em- 11.2.5.2 Analyze the continuing check ployed when the solution analyzed has a Cr standard and the calibration blank after concentration greater than 35 μg/L or five each batch of 10 samples.

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11.2.5.3 Use the average intensity of mul- 11.4.3.2 Follow the manufacturer’s in- tiple exposures for both standardization and structions for all other spectrophotometer sample analysis to reduce random error. operating parameters. 11.2.6 ICP Sample Dilution. 11.4.4 Furnace Operational Parameters. 11.2.6.1 Dilute and reanalyze samples that Parameters suggested by the manufacturer are more concentrated than the linear cali- should be employed as guidelines. bration limit or use an alternate, less sen- 11.4.4.1 Temperature-sensing mechanisms sitive Cr wavelength for which quality con- and temperature controllers can vary be- trol data have already been established. tween instruments and/or with time; the va- 11.2.6.2 When dilutions are performed, the lidity of the furnace operating parameters appropriate factors must be applied to sam- must be periodically confirmed by system- ple measurement results. atically altering the furnace parameters 11.2.7 Reporting Analytical Results. All while analyzing a standard. In this manner, analytical results should be reported in μg losses of analyte due to higher-than-nec- Cr/mL using three significant figures. Field essary temperature settings or losses in sen- sample volumes (mL) must be reported also. sitivity due to less than optimum settings 11.3 GFAAS Sample Preparation. can be minimized. 11.3.1 GFAAS Acid Digestion. An acid di- 11.4.4.2 Similar verification of furnace op- gestion of the alkaline impinger solution is erating parameters may be required for com- required for the GFAAS analysis. plex sample matrices (consult instrument 11.3.1.1 In a beaker, add 10 mL of con- manual for additional information). Cali- centrated HNO3 to a 100 mL sample aliquot brate the GFAAS system following the pro- that has been well mixed. Cover the beaker cedures specified in Section 10.3. with a watch glass. Place the beaker on a 11.4.5 GFAAS Operational Quality Control hot plate and reflux the sample to near dry- Procedures. ness. Add another 5 mL of concentrated 11.4.5.1 Introduce a measured aliquot of HNO to complete the digestion. Again, care- 3 digested sample into the furnace and atom- fully reflux the sample volume to near dry- ize. ness. Rinse the beaker walls and watch glass 11.4.5.2 If the measured concentration ex- with reagent water. ceeds the calibration range, the sample 11.3.1.2 The final concentration of HNO in 3 should be diluted with the calibration blank the solution should be 1 percent (v/v). solution (1.0 percent HNO ) and reanalyzed. 11.3.1.3 Transfer the digested sample to a 3 11.4.5.3 Consult the operator’s manual for 50-mL volumetric flask. Add 0.5 mL of con- suggested injection volumes. The use of mul- centrated HNO and 1 mL of the 10 μg/mL of 3 tiple injections can improve accuracy and Ca(NO ) . Dilute to 50 mL with reagent 3 2 assist in detecting furnace pipetting errors. water. 11.4.5.4 Analyze a minimum of one ma- 11.3.2 HNO3 Concentration. A different final volume may be used based on the ex- trix-matched reagent blank per sample batch to determine if contamination or any mem- pected Cr concentration, but the HNO3 concentration must be maintained at 1 percent ory effects are occurring. (v/v). 11.4.5.5 Analyze a calibration blank and a 11.4 GFAAS Sample Analysis. continuing check standard after approxi- 11.4.1 The GFAAS analysis is applicable mately every batch of 10 sample injections. for the determination of total chromium 11.4.6 GFAAS Sample Dilution. only. 11.4.6.1 Dilute and reanalyze samples that 11.4.2 GFAAS Blanks. Two types of blanks are more concentrated than the instrument are required for the GFAAS analysis. calibration range. 11.4.2.1 Calibration Blank. The 1.0 percent 11.4.6.2 If dilutions are performed, the appropriate factors must be applied to sample HNO3 is the calibration blank which is used in establishing the calibration curve. measurement results. 11.4.2.2 Field Reagent Blank. An aliquot 11.4.7 Reporting Analytical Results. of the 0.1 N NaOH solution or the 0.1 N 11.4.7.1 Calculate the Cr concentrations NaHCO3 prepared in Section 7.1.2 is collected by the method of standard additions (see op- for the field reagent blank. The field reagent erator’s manual) or, from direct calibration. blank is used to assess possible contamina- All dilution and/or concentration factors tion resulting from processing the sample. must be used when calculating the results. 11.4.2.2.1 The reagent blank must be sub- 11.4.7.2 Analytical results should be re- jected to the entire series of sample prepara- ported in μg Cr/mL using three significant tion and analytical procedures, including the figures. Field sample volumes (mL) must be acid digestion. reported also. 11.4.2.2.2 The reagent blank’s final solu- 11.5 IC/PCR Sample Preparation. tion must contain the same acid concentra- 11.5.1 Sample pH. Measure and record the tion as the sample solutions. sample pH prior to analysis. 11.4.3 GFAAS Instrument Adjustment. 11.5.2 Sample Filtration. Prior to 11.4.3.1 The 357.9 nm wavelength line shall preconcentration and/or analysis, filter all be used. field samples through a 0.45-μm filter. The

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filtration step should be conducted just prior with the sample is thoroughly flushed with to sample injection/analysis. the new sample to prevent cross contamina- 11.5.2.1 Use a portion of the sample to tion. rinse the syringe filtration unit and acetate 11.6.5 IC/PCR Instrument Calibration. filter and then collect the required volume of 11.6.5.1 First, inject the calibration stand- filtrate. ards prepared, as described in Section 7.3.8 to 11.5.2.2 Retain the filter if total Cr is to correspond to the appropriate concentration be determined also. range, starting with the lowest standard 11.5.3 Sample Preconcentration (older in- first. struments). 11.6.5.2 Check the performance of the in- 11.5.3.1 For older instruments, a strument and verify the calibration using preconcentration system may be used in con- data gathered from analyses of laboratory junction with the IC/PCR to increase sensi- blanks, calibration standards, and a quality tivity for trace levels of Cr∂6. control sample. 11.5.3.2 The preconcentration is accom- 11.6.5.3 Verify the calibration by ana- plished by selectively retaining the analyte lyzing a calibration reference standard. If on a solid absorbent, followed by removal of the measured concentration exceeds the es- the analyte from the absorbent (consult in- tablished value by more than 10 percent, per- strument manual). form a second analysis. If the measured con- 11.5.3.3 For a manual system, position the centration still exceeds the established value injection valve so that the eluent displaces by more than 10 percent, terminate the anal- the concentrated Cr∂6 sample, transferring ysis until the problem can be identified and it from the preconcentration column and corrected. onto the IC anion separation column. 11.6.6 IC/PCR Instrument Operation. 11.6 IC/PCR Sample Analyses. 11.6.6.1 Inject the calibration reference 11.6.1 The IC/PCR analysis is applicable standard (as described in Section 9.3.1), fol- for hexavalent chromium measurements lowed by the field reagent blank (Section only. 8.2.4), and the field samples. 11.6.2 IC/PCR Blanks. Two types of blanks 11.6.6.1.1 Standards (and QC standards) are required for the IC/PCR analysis. and samples are injected into the sample 11.6.2.1 Calibration Blank. The calibration loop of the desired size (use a larger size loop ∂ blank is used in establishing the analytical for greater sensitivity). The Cr 6 is collected curve. For the calibration blank, use either on the resin bed of the column. 0.1 N NaOH or 0.1 N NaHCO , whichever is 11.6.6.1.2 After separation from other sam- 3 ∂ used for the impinger solution. The calibra- ple components, the Cr 6 forms a specific tion blank can be prepared fresh in the lab- complex in the post-column reactor with the oratory; it does not have to be prepared from DPC reaction solution, and the complex is the same batch of absorbing solution that is detected by visible absorbance at a max- used in the field. imum wavelength of 540 nm. 11.6.2.2 Field Reagent Blank. An aliquot 11.6.6.1.3 The amount of absorbance meas- of the 0.1 N NaOH solution or the 0.1 N ured is proportional to the concentration of the Cr∂6 complex formed. NaHCO3 solution prepared in Section 7.1.2 is collected for the field reagent blank. The 11.6.6.1.4 The IC retention time and the absorbance of the Cr∂6 complex with known field reagent blank is used to assess possible ∂ contamination resulting from processing the Cr 6 standards analyzed under identical con- sample. ditions must be compared to provide both 11.6.3 Stabilized Baseline. Prior to sample qualitative and quantitative analyses. analysis, establish a stable baseline with the 11.6.6.1.5 If a sample peak appears near ∂6 detector set at the required attenuation by the expected retention time of the Cr ion, setting the eluent and post-column reagent spike the sample according to Section 9.3.4 flow rates according to the manufacturers to verify peak identity. recommendations. 11.6.7 IC/PCR Operational Quality Control Procedures. NOTE: As long as the ratio of eluent flow 11.6.7.1 Samples should be at a pH ≥8.5 for rate to PCR flow rate remains constant, the NaOH and ≥8.0 if using NaHCO3; document standard curve should remain linear. Inject a any discrepancies. sample of reagent water to ensure that no 11.6.7.2 Refrigerated samples should be al- ∂ Cr 6 appears in the water blank. lowed to equilibrate to ambient temperature 11.6.4 Sample Injection Loop. Size of in- prior to preparation and analysis. jection loop is based on standard/sample con- 11.6.7.3 Repeat the injection of the cali- centrations and the selected attenuator set- bration standards at the end of the analyt- ting. ical run to assess instrument drift. Measure 11.6.4.1 A 50-μL loop is normally sufficient areas or heights of the Cr∂6/DPC complex for most higher concentrations. chromatogram peaks. 11.6.4.2 The sample volume used to load 11.6.7.4 To ensure the precision of the the injection loop should be at least 10 times sample injection (manual or autosampler), the loop size so that all tubing in contact the response for the second set of injected

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standards must be within 10 percent of the er will meet the needs of the source and the average response. enforcement authority. 11.6.7.5 If the 10 percent criteria duplicate 12.1.1.2 The pre-test protocol should in- injection cannot be achieved, identify the clude information on equipment, logistics, source of the problem and rerun the calibra- personnel, process operation, and other re- tion standards. sources necessary for an efficient and coordi- 11.6.7.6 Use peak areas or peak heights nated test. from the injections of calibration standards 12.1.1.3 At a minimum, the pre-test pro- to generate a linear calibration curve. From tocol should identify and be approved by the the calibration curve, determine the con- source, the tester, the analytical laboratory, centrations of the field samples. and the regulatory enforcement authority. 11.6.8 IC/PCR Sample Dilution. The tester should not proceed with the com- 11.6.8.1 Samples having concentrations pliance testing before obtaining approval higher than the established calibration range from the enforcement authority. must be diluted into the calibration range 12.1.2 Post Test Calculations. and re-analyzed. 12.1.2.1 Perform the calculations, retain- 11.6.8.2 If dilutions are performed, the ap- ing one extra decimal figure beyond that of propriate factors must be applied to sample the acquired data. Round off figures after measurement results. final calculations. 11.6.9 Reporting Analytical Results. Re- 12.1.2.2 Nomenclature. sults should be reported in μg Cr∂6/mL using three significant figures. Field sample vol- CS = Concentration of Cr in sample solution, μ umes (mL) must be reported also. g Cr/mL. Ccr = Concentration of Cr in stack gas, dry 12.0 Data Analysis and Calculations basis, corrected to standard conditions, mg/dscm. 12.1 Pretest Calculations. D = Digestion factor, dimension less. 12.1.1 Pretest Protocol (Site Test Plan). 12.1.1.1 The pretest protocol should define F = Dilution factor, dimension less. μ and address the test data quality objectives MCr = Total Cr in each sample, g. (DQOs), with all assumptions, that will be re- Vad = Volume of sample aliquot after diges- quired by the end user (enforcement author- tion, mL. ity); what data are needed? why are the data Vaf = Volume of sample aliquot after dilu- needed? how will the data be used? what are tion, mL. method detection limits? and what are esti- Vbd = Volume of sample aliquot submitted to mated target analyte levels for the following digestion, mL. test parameters. Vbf = Volume of sample aliquot before dilu- 12.1.1.1.1 Estimated source concentration tion, mL. for total chromium and/or Cr∂6. VmL = Volume of impinger contents plus 12.1.1.1.2 Estimated minimum sampling rinses, mL. time and/or volume required to meet method Vm(std) = Volume of gas sample measured by detection limit requirements (Appendix B 40 the dry gas meter, corrected to standard CFR Part 136) for measurement of total chro- conditions, dscm. mium and/or Cr∂6. 12.1.2.3 Dilution Factor. The dilution fac- 12.1.1.1.3 Demonstrate that planned sam- tor is the ratio of the volume of sample ali- pling parameters will meet DQOs. The pro- quot after dilution to the volume before dilu- tocol must demonstrate that the planned tion. This ratio is given by the following sampling parameters calculated by the test- equation:

V F = af Eq. 306-1 Vbf

12.1.2.4 Digestion Factor. The digestion digestion. This ratio is given by Equation factor is the ratio of the volume of sample 306–2. aliquot after digestion to the volume before

V D = ad Eq. 306-2 Vbd

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12.1.2.5 Total Cr in Sample. Calculate MCr, the total μg Cr in each sample, using the following equation:

=××× MVcr mL CFD S Eq. 306-3

12.1.2.6 Average Dry Gas Meter Tempera- 12.1.2.8 Cr Emission Concentration (CCr). ture and Average Orifice Pressure Drop. Calculate CCr, the Cr concentration in the Same as Method 5. stack gas, in mg/dscm on a dry basis, cor- 12.1.2.7 Dry Gas Volume, Volume of Water rected to standard conditions using the fol- Vapor, Moisture Content. Same as Method 5. lowing equation:

M − mg C =×Cr 10 3 Eq. 306 - 4 Cr μ Vm() std g

12.1.2.9 Isokinetic Variation, Acceptable tion <5 times the expected detection limit. Results. Same as Method 5. The detection limit is 3.14 times the standard deviation of these results. 13.0 Method Performance 13.2.2 In-stack Sensitivity. The in-stack 13.1 Range. The recommended working sensitivity depends upon the analytical de- range for all of the three analytical tech- tection limit, the volume of stack gas sam- niques starts at five times the analytical de- pled, the total volume of the impinger ab- tection limit (see also Section 13.2.2). The sorbing solution plus the rinses, and, in some upper limit of all three techniques can be ex- cases, dilution or concentration factors from tended indefinitely by appropriate dilution. sample preparation. Using the analytical de- 13.2 Sensitivity. tection limits given in Sections 13.2.1.1, 13.2.1 Analytical Sensitivity. The esti- 13.2.1.2, and 13.2.1.3; a stack gas sample vol- mated instrumental detection limits listed ume of 1.7 dscm; a total liquid sample vol- are provided as a guide for an instrumental ume of 500 mL; and the digestion concentra- limit. The actual method detection limits tion factor of 1⁄2 for the GFAAS analysis; the are sample and instrument dependent and corresponding in-stack detection limits are may vary as the sample matrix varies. 13.2.1.2 ICP Analytical Sensitivity. The 0.0014 mg Cr/dscm to 0.0021 mg Cr/dscm for ICP, 0.00015 mg Cr/dscm for GFAAS, and minimum estimated detection limits for ∂ ICP, as reported in Method 6010A and the re- 0.000015 mg Cr 6/dscm for IC/PCR with cently revised Method 6010B of SW–846 (Ref- preconcentration. erence 1), are 7.0 μg Cr/L and 4.7 μg Cr/L, re- NOTE: It is recommended that the con- spectively. centration of Cr in the analytical solutions 13.2.1.3 GFAAS Analytical Sensitivity. be at least five times the analytical detec- The minimum estimated detection limit for tion limit to optimize sensitivity in the GFAAS, as reported in Methods 7000A and analyses. Using this guideline and the same 7191 of SW–846 (Reference 1), is 1 μg Cr/L. assumptions for impinger sample volume, 13.2.1.4 IC/PCR Analytical Sensitivity. stack gas sample volume, and the digestion The minimum detection limit for IC/PCR concentration factor for the GFAAS analysis with a preconcentrator, as reported in Meth- (500 mL,1.7 dscm, and 1/2, respectively), the ods 0061 and 7199 of SW–846 (Reference 1), is recommended minimum stack concentra- μ ∂6 0.05 g Cr /L. tions for optimum sensitivity are 0.0068 mg 1.3.2.1.5 Determination of Detection Lim- Cr/dscm to 0.0103 mg Cr/dscm for ICP, 0.00074 its. The laboratory performing the Cr∂6 mg Cr/dscm for GFAAS, and 0.000074 mg Cr∂6/ measurements must determine the method dscm for IC/PCR with preconcentration. If detection limit on a quarterly basis using a required, the in-stack detection limits can suitable procedure such as that found in 40 be improved by either increasing the stack CFR, Part 136, Appendix B. The determination should be made on samples in the appro- gas sample volume, further reducing the vol- priate alkaline matrix. Normally this in- ume of the digested sample for GFAAS, im- volves the preparation (if applicable) and proving the analytical detection limits, or consecutive measurement of seven (7) sepa- any combination of the three. rate aliquots of a sample with a concentra- 13.3 Precision.

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13.3.1 The following precision data have with use to minimize the disposal of exces- been reported for the three analytical meth- sive volumes of acid. ods. In each case, when the sampling preci- 14.3 To the extent possible, the con- sion is combined with the reported analyt- tainers/vessels used to collect and prepare ical precision, the resulting overall precision samples should be cleaned and reused to min- may decrease. imize the generation of solid waste. 13.3.2 Bias data is also reported for GFAAS. 15.0 Waste Management 13.4 ICP Precision. 15.1 It is the responsibility of the labora- 13.4.1 As reported in Method 6010B of SW– tory and the sampling team to comply with 846 (Reference 1), in an EPA round-robin all federal, state, and local regulations gov- Phase 1 study, seven laboratories applied the erning waste management, particularly the ICP technique to acid/distilled water mat- discharge regulations, hazardous waste iden- rices that had been spiked with various tification rules, and land disposal restric- metal concentrates. For true values of 10, 50, tions; and to protect the air, water, and land and 150 μg Cr/L; the mean reported values by minimizing and controlling all releases were 10, 50, and 149 μg Cr/L; and the mean from field operations. percent relative standard deviations were 18, 15.2 For further information on waste 3.3, and 3.8 percent, respectively. management, consult The Waste Manage- 13.4.2 In another multi laboratory study ment Manual for Laboratory Personnel and cited in Method 6010B, a mean relative stand- Less is Better—Laboratory Chemical Man- ard of 8.2 percent was reported for an aque- agement for Waste Reduction, available from ous sample concentration of approximately the American Chemical Society’s Depart- 3750 μg Cr/L. ment of Government Relations and Science Policy, 1155 16th Street NW, Washington, DC 13.5 GFAAS Precision. As reported in 20036. Method 7191 of SW–846 (Reference 1), in a single laboratory (EMSL), using Cincinnati, 16.0 References Ohio tap water spiked at concentrations of 19, 48, and 77 μg Cr/L, the standard deviations 1. ‘‘Test Methods for Evaluating Solid were ±0.1, ±0.2, and ±0.8, respectively. Recov- Waste, Physical/Chemical Methods, SW–846, eries at these levels were 97 percent, 101 per- Third Edition,’’ as amended by Updates I, II, cent, and 102 percent, respectively. IIA, IIB, and III. Document No. 955–001– 13.6 IC/PCR Precision. As reported in 000001. Available from Superintendent of Methods 0061 and 7199 of SW–846 (Reference Documents, U.S. Government Printing Of- 1), the precision of IC/PCR with sample fice, Washington, DC, November 1986. preconcentration is 5 to 10 percent. The over- 2. Cox, X.B., R.W. Linton, and F.E. Butler. all precision for sewage sludge incinerators Determination of Chromium Speciation in emitting 120 ng/dscm of Cr∂6 and 3.5 μg/dscm Environmental Particles—A Multi-technique of total Cr was 25 percent and 9 percent, re- Study of Ferrochrome Smelter Dust. Accept- spectively; and for hazardous waste inciner- ed for publication in Environmental Science ators emitting 300 ng/dscm of C∂6 the preci- and Technology. sion was 20 percent. 3. Same as Section 17.0 of Method 5, Ref- erences 2, 3, 4, 5, and 7. 14.0 Pollution Prevention 4. California Air Resources Board, ‘‘Deter- mination of Total Chromium and Hexavalent 14.1 The only materials used in this meth- Chromium Emissions from Stationary od that could be considered pollutants are Sources.’’ Method 425, September 12, 1990. the chromium standards used for instrument 5. The Merck Index. Eleventh Edition. calibration and acids used in the cleaning of Merck & Co., Inc., 1989. the collection and measurement containers/ 6. Walpole, R.E., and R.H. Myers. ‘‘Prob- labware, in the preparation of standards, and ability and Statistics for Scientists and En- in the acid digestion of samples. Both re- gineering.’’ 3rd Edition. MacMillan Pub- agents can be stored in the same waste con- lishing Co., NewYork, N.Y., 1985. tainer. 14.2 Cleaning solutions containing acids 17.0 Tables, Diagrams, Flowcharts, and should be prepared in volumes consistent Validation Data

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METHOD 306A—DETERMINATION OF CHROMIUM other methods in 40 CFR Part 60, Appendix A EMISSIONS FROM DECORATIVE AND HARD and in this part. Therefore, to obtain reliable CHROMIUM ELECTROPLATING AND CHROMIUM results, persons using this method should ANODIZING OPERATIONS have a thorough knowledge of at least Meth- ods 5 and 306. NOTE: This method does not include all of the specifications (e.g., equipment and sup- 1.0 Scope and Application plies) and procedures (e.g., sampling and ana- 1.1 Analyte. Chromium. CAS Number lytical) essential to its performance. Some (7440–47–3). material is incorporated by reference from 1.2 Applicability.

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1.2.1 This method applies to the deter- procedures described in Method 306: induc- mination of chromium (Cr) in emissions tively-coupled plasma emission spectrom- from decorative and hard chromium electro- etry (ICP), graphite furnace atomic absorp- plating facilities, chromium anodizing oper- tion spectrometry (GFAAS), or ion chroma- ations, and continuous chromium plating at tography with a post-column reactor (IC/ iron and steel facilities. The method is less PCR). expensive and less complex to conduct than 2.1.2.1 Total chromium samples with high Method 306. Correctly applied, the precision chromium concentrations (≥35 μg/L) may be and bias of the sample results should be com- analyzed using inductively coupled plasma parable to those obtained with the isokinetic emission spectrometry (ICP) at 267.72 nm. Method 306. This method is applicable for the NOTE: The ICP analysis is applicable for determination of air emissions under nomi- this method only when the solution analyzed nal ambient moisture, temperature, and has a Cr concentration greater than or equal pressure conditions. to 35 μg/L or five times the method detection 1.2.2 The method is also applicable to limit as determined according to Appendix B electroplating and anodizing sources con- in 40 CFR Part 136. trolled by wet scrubbers. 2.1.2.2 Alternatively, when lower total 1.3 Data Quality Objectives. chromium concentrations (<35 μg/L) are en- 1.3.1 Pretest Protocol. countered, a portion of the alkaline sample 1.3.1.1 The pretest protocol should define solution may be digested with nitric acid and and address the test data quality objectives analyzed by graphite furnace atomic absorp- (DQOs), with all assumptions, that will be re- tion spectroscopy (GFAAS) at 357.9 nm. quired by the end user (enforcement author- 2.1.2.3 If it is desirable to determine ity); what data are needed? why are the data hexavalent chromium (Cr∂6) emissions, the needed? how will data be used? what are samples may be analyzed using an ion chro- method detection limits? and what are esti- matograph equipped with a post-column re- mated target analyte levels for the following actor (IC/PCR) and a visible wavelength de- test parameters. tector. To increase sensitivity for trace lev- 1.3.1.1.1 Estimated source concentration els of Cr∂6, a preconcentration system may for total chromium and/or Cr∂6. be used in conjunction with the IC/PCR. 1.3.1.1.2 Estimated minimum sampling time and/or volume required to meet method 3.0 Definitions detection limit requirements (Appendix B 40 CFR Part 136) for measurement of total chro- 3.1 Total Chromium—measured chromium mium and/or Cr∂6. content that includes both major chromium 1.3.1.1.3 Demonstrate that planned sam- oxidation states (Cr + 3, Cr + 6). pling parameters will meet DQOs. The pro- 3.2 May—Implies an optional operation. tocol must demonstrate that the planned 3.3 Digestion—The analytical operation in- sampling parameters calculated by the test- volving the complete (or nearly complete) er will meet the needs of the source and the dissolution of the sample in order to ensure enforcement authority. the complete solubilization of the element 1.3.1.2 The pre-test protocol should in- (analyte) to be measured. clude information on equipment, logistics, 3.4 Interferences—Physical, chemical, or personnel, process operation, and other re- spectral phenomena that may produce a high sources necessary for an efficient and coordi- or low bias in the analytical result. nated performance test. 3.5 Analytical System—All components of 1.3.1.3 At a minimum, the pre-test pro- the analytical process including the sample tocol should identify and be approved by the digestion and measurement apparatus. source, the tester, the analytical laboratory, 3.6 Sample Recovery—The quantitative and the regulatory enforcement authority. transfer of sample from the collection appa- The tester should not proceed with the com- ratus to the sample preparation (digestion, pliance testing before obtaining approval etc.) apparatus. This term should not be con- from the enforcement authority. fused with analytical recovery. 2.0 Summary of Method 4.0 Interferences 2.1 Sampling. 4.1 Same as in Method 306, Section 4.0. 2.1.1 An emission sample is extracted 5.0 Safety from the source at a constant sampling rate determined by a critical orifice and collected 5.1 Disclaimer. This method may involve in a sampling train composed of a probe and hazardous materials, operations, and equip- impingers. The proportional sampling time ment. This test method does not purport to at the cross sectional traverse points is var- address all of the safety issues associated ied according to the stack gas velocity at with its use. It is the responsibility of the each point. The total sample time must be at user to establish appropriate safety and least two hours. health practices and to determine the appli- 2.1.2 The chromium emission concentra- cability of regulatory limitations prior to tion is determined by the same analytical performing this test method.

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5.2 Chromium and some chromium com- 6.1.5.2 Canning Jar Connectors. The jar pounds have been listed as carcinogens al- containers are connected by leak-tight inlet though Chromium (III) compounds show lit- and outlet tubes installed in the lids of each tle or no toxicity. Chromium is a skin and container for assembly with the train. The respiratory irritant. tubes may be made of ∼ 6.4 mm (1⁄4-in.) ID glass or rigid plastic tubing. For the inlet 6.0 Equipment and Supplies tube of the first impinger, heat the glass or NOTE: Mention of trade names or specific plastic tubing and draw until the tubing sep- products does not constitute endorsement by arates. Fabricate the necked tip to form an 3 the Environmental Protection Agency. orifice tip that is approximately 2.4 mm ( ⁄32- in.) ID. 6.1 Sampling Train. A schematic of the 6.1.5.2.1 When assembling the first con- sampling train is shown in Figure 306A–1. tainer, place the orifice tip end of the tube The individual components of the train are approximately 4.8 mm (3⁄16-in.) above the in- available commercially, however, some fab- side bottom of the jar. rication and assembly are required. 6.1.5.2.2 For the second container, the 6.1.1 Probe Nozzle/Tubing and Sheath. inlet tube need not be drawn and sized, but 1 6.1.1.1 Use approximately 6.4-mm ( ⁄4-in.) the tip should be approximately 25 mm (1 in.) inside diameter (ID) glass or rigid plastic above the bottom of the jar. tubing approximately 20 cm (8 in.) in length 6.1.5.2.3 The inlet tube of the third con- with a short 90 degree bend at one end to tainer should extend to approximately 12.7 form the sampling nozzle. Grind a slight mm (1⁄2-in.) above the bottom of the jar. taper on the nozzle end before making the 6.1.5.2.4 Extend the outlet tube for each bend. Attach the nozzle to flexible tubing of container approximately 50 mm (2 in.) above sufficient length to enable collection of a the jar lid and downward through the lid, ap- sample from the stack. proximately 12.7 mm (1⁄2-in.) beneath the bot- 6.1.1.2 Use a straight piece of larger di- tom of the lid. ameter rigid tubing (such as metal conduit 6.1.5.3 Greenburg-Smith Impingers. Three or plastic water pipe) to form a sheath that separate impingers of the Greenburg-Smith begins about 2.5 cm (1 in.) from the 90 ° bend (GS) design as described in Section 6.0 of on the nozzle and encases and supports the Method 5 are required. The first GS impinger flexible tubing. shall have a standard tip (orifice/plate), and 6.1.2 Type S Pitot Tube. Same as Method 2, the second and third GS impingers shall be Section 6.1 (40 CFR Part 60, Appendix A). modified by replacing the orifice/plate tube 6.1.3 Temperature Sensor. with a 13 mm (1⁄2-in.) ID glass tube, having an 6.1.3.1 A thermocouple, liquid-filled bulb unrestricted opening located 13 mm (1⁄2-in.) thermometer, bimetallic thermometer, mer- from the bottom of the outer flask. cury-in-glass thermometer, or other sensor 6.1.5.4 Greenburg-Smith Connectors. The capable of measuring temperature to within GS impingers shall be connected by leak-free 1.5 percent of the minimum absolute stack ground glass ‘‘U’’ tube connectors or by leak- temperature. free non-contaminating flexible tubing. The 6.1.3.2 The temperature sensor shall ei- first impinger shall contain the absorbing so- ther be positioned near the center of the lution, the second is empty and the third stack, or be attached to the pitot tube as di- contains the desiccant drying agent. rected in Section 6.3 of Method 2. 6.1.6 Manometer. Inclined/vertical type, 6.1.4 Sample Train Connectors. or equivalent device, as described in Section 6.1.4.1 Use thick wall flexible plastic tub- 6.2 of Method 2 (40 CFR Part 60, Appendix A). ing (polyethylene, polypropylene, or poly- 6.1.7 Critical Orifice. The critical orifice vinyl chloride) ∼ 6.4-mm (1⁄4-in.) to 9.5-mm is a small restriction in the sample line that (3⁄8-in.) ID to connect the train components. is located upstream of the vacuum pump. 6.1.4.2 A combination of rigid plastic tub- The orifice produces a constant sampling ing and thin wall flexible tubing may be used flow rate that is approximately 0.021 cubic as long as tubing walls do not collapse when meters per minute (m3/min) or 0.75 cubic feet leak-checking the train. Metal tubing can- per minute (cfm). not be used. 6.1.7.1 The critical orifice can be con- 6.1.5 Impingers. Three, one-quart capac- structed by sealing a 2.4-mm (3⁄32-in.) ID ity, glass canning jars with vacuum seal lids, brass tube approximately 14.3 mm (9⁄16-in.) in or three Greenburg-Smith (GS) design length inside a second brass tube that is ap- impingers connected in series, or equivalent, proximately 8 mm (5⁄16-in.) ID and 14.3-mm may be used. (9⁄16-in.) in length . 6.1.5.1 One-quart glass canning jar. Three 6.1.7.2 Materials other than brass can be separate jar containers are required: (1) the used to construct the critical orifice as long first jar contains the absorbing solution; (2) as the flow through the sampling train can the second is empty and is used to collect be maintained at approximately 0.021 cubic any reagent carried over from the first con- meter per minute (0.75) cfm. tainer; and (3) the third contains the des- 6.1.8 Connecting Hardware. Standard pipe iccant drying agent. and fittings, 9.5-mm (3⁄8-in.), 6.4-mm (1⁄4-in.)

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or 3.2-mm (1⁄8-in.) ID, may be used to assem- 6.2.2 Tester may elect to obtain the abso- ble the vacuum pump, dry gas meter and lute barometric pressure from a nearby Na- other sampling train components. tional Weather Service station. 6.1.9 Vacuum Gauge. Capable of meas- 6.2.2.1 The station value (which is the ab- uring approximately 760 mm Hg (30 in. Hg) solute barometric pressure) must be adjusted vacuum in 25.4 mm HG (1 in. Hg) increments. for elevation differences between the weath- Locate vacuum gauge between the critical er station and the sampling location. Either orifice and the vacuum pump. subtract 2.5 mm Hg (0.1 in. Hg) from the sta- 6.1.10 Pump Oiler. A glass oil reservoir tion value per 30 m (100 ft) of elevation in- with a wick mounted at the vacuum pump crease or add the same for an elevation de- inlet that lubricates the pump vanes. The crease. oiler should be an in-line type and not vent- 6.2.2.2 If the field barometer cannot be ad- ed to the atmosphere. See EMTIC Guideline justed to agree within 0.1 in. Hg of the ref- Document No. GD-041.WPD for additional in- erence barometric, repair or discard the unit. formation. The barometer pressure measurement shall 6.1.11 Vacuum Pump. Gast Model 0522– be recorded on the sampling data sheet. V103–G18DX, or equivalent, capable of deliv- 6.3 Sample Recovery. Same as Method 5, Section 6.2 (40 CFR Part 60, Appendix A), ering at least 1.5 cfm at 15 in. Hg vacuum. 6.1.12 Oil Trap/Muffler. An empty glass oil with the following exceptions: reservoir without wick mounted at the pump 6.3.1 Probe-Liner and Probe-Nozzle Brush- outlet to control the pump noise and prevent es. Brushes are not necessary for sample re- oil from reaching the dry gas meter. covery. If a probe brush is used, it must be 6.1.13 By-pass Fine Adjust Valve (Op- non-metallic. tional). Needle valve assembly 6.4-mm (1⁄4- 6.3.2 Wash Bottles. Polyethylene wash in.), Whitey 1 RF 4–A, or equivalent, that al- bottle, for sample recovery absorbing solu- lows for adjustment of the train vacuum. tion. 6.1.13.1 A fine-adjustment valve is posi- 6.3.3 Sample Recovery Solution. Use 0.1 N tioned in the optional pump by-pass system NaOH or 0.1 N NaHCO3, whichever is used as that allows the gas flow to recirculate the impinger absorbing solution, to replace through the pump. This by-pass system al- the acetone. lows the tester to control/reduce the max- 6.3.4 Sample Storage Containers. imum leak-check vacuum pressure produced 6.3.4.1 Glass Canning Jar. The first can- by the pump. ning jar container of the sampling train may 6.1.13.1.1 The tester must conduct the post serve as the sample shipping container. A new lid and sealing plastic wrap shall be sub- test leak check at a vacuum equal to or stituted for the container lid assembly. greater than the maximum vacuum encoun- 6.3.4.2 Polyethylene or Glass Containers. tered during the sampling run. Transfer the Greenburg-Smith impinger con- 6.1.13.1.2 The pump by-pass assembly is tents to precleaned polyethylene or glass not required, but is recommended if the test- containers. The samples shall be stored and er intends to leak-check the 306A train at shipped in 250-mL, 500-mL or 1000-mL poly- the vacuum experienced during a run. ethylene or glass containers with leak-free, 6.1.14 Dry Gas Meter. An Equimeter non metal screw caps. Model 110 test meter or, equivalent with 6.3.5 pH Indicator Strip, for Cr ∂6 Sam- temperature sensor(s) installed (inlet/outlet) ples. pH indicator strips, or equivalent, capa- to monitor the meter temperature. If only ble of determining the pH of solutions be- one temperature sensor is installed, locate tween the range of 7 and 12, at 0.5 pH incre- the sensor at the outlet side of the meter. ments. The dry gas meter must be capable of meas- 6.3.6 Plastic Storage Containers. Air tight ± uring the gaseous volume to within 2% of containers to store silica gel. the true volume. 6.4 Analysis. Same as Method 306, Section NOTE: The Method 306 sampling train is 6.3. also commercially available and may be used to perform the Method 306A tests. The sam- 7.0 Reagents and Standards. pling train may be assembled as specified in NOTE: Unless otherwise indicated, all re- Method 306A with the sampling rate being agents shall conform to the specifications es- operated at the delta H@ specified for the tablished by the Committee on Analytical calibrated orifice located in the meter box. Reagents of the American Chemical Society The Method 306 train is then operated as de- (ACS reagent grade). Where such specifica- scribed in Method 306A. tions are not available, use the best avail- 6.2 Barometer. Mercury aneroid barom- able grade. It is recommended, but not re- eter, or other barometer equivalent, capable quired, that reagents be checked by the ap- of measuring atmospheric pressure to within propriate analysis prior to field use to assure ±2.5 mm Hg (0.1 in. Hg). that contamination is below the analytical 6.2.1 A preliminary check of the barom- detection limit for the ICP or GFAAS total eter shall be made against a mercury-in- chromium analysis; and that contamination glass reference barometer or its equivalent. is below the analytical detection limit for

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Cr∂6 using IC/PCR for direct injection or, if Part 60, Appendix A). Use a total of 24 sam- selected, preconcentration. pling points for round ducts and 24 or 25 7.1 Sampling. points for rectangular ducts. Mark the pitot 7.1.1 Water. Reagent water that conforms and sampling probe to identify the sample to ASTM Specification D1193 Type II (incor- traversing points. porated by reference see § 63.14). All ref- 8.1.1.2.2 For round ducts less than 12 erences to water in the method refer to rea- inches in diameter, use a total of 16 points. gent water unless otherwise specified. It is 8.1.1.3 Velocity Pressure Traverse. Per- recommended that water blanks be checked form an initial velocity traverse before ob- prior to preparing the sampling reagents to taining samples. The Figure 306A–2 data ensure that the Cr content is less than three sheet may be used to record velocity tra- (3) times the anticipated detection limit of verse data. the analytical method. 8.1.1.3.1 To demonstrate that the flow rate 7.1.2 Sodium Hydroxide (NaOH) Absorbing is constant over several days of testing, per- Solution, 0.1 N. Dissolve 4.0 g of sodium hy- form complete traverses at the beginning droxide in 1 liter of water to obtain a pH of and end of each day’s test effort, and cal- approximately 8.5. culate the deviation of the flow rate for each daily period. The beginning and end flow 7.1.3 Sodium Bicarbonate (NaHCO3) Ab- sorbing Solution, 0.1 N. Dissolve approxi- rates are considered constant if the devi- mately 8.5 g of sodium bicarbonate in 1 liter ation does not exceed 10 percent. If the flow of water to obtain a pH of approximately 8.3. rate exceeds the 10 percent criteria, either 7.1.4 Chromium Contamination. correct the inconsistent flow rate problem, 7.1.4.1 The absorbing solution shall not or obtain the Administrator’s approval for exceed the QC criteria noted in Method 306, the test results. Section 7.1.1 (≤3 times the instrument detec- 8.1.1.3.2 Perform traverses as specified in tion limit). Section 8.0 of Method 2, but record only the 7.1.4.2 When the Cr∂6 content in the field Dp (velocity pressure) values for each sam- samples exceeds the blank concentration by pling point. If a mass emission rate is de- at least a factor of ten (10), Cr∂6 blank levels sired, stack velocity pressures shall be re- ≤10 times the detection limit will be allowed. corded before and after each test, and an average stack velocity pressure determined for NOTE: At sources with high concentrations the testing period. of acids and/or SO , the concentration of 2 8.1.1.4 Verification of Absence of Cyclonic NaOH or NaHCO should be ≥0.5 N to insure 3 Flow. Check for cyclonic flow during the ini- that the pH of the solution remains at or tial traverse to verify that it does not exist. above 8.5 for NaOH and 8.0 for NaHCO3 during and after sampling. Perform the cyclonic flow check as specified in Section 11.4 of Method 1 (40 CFR Part 60, 7.1.3 Desiccant. Silica Gel, 6–16 mesh, in- Appendix A). dicating type. Alternatively, other types of 8.1.1.4.1 If cyclonic flow is present, verify desiccants may be used, subject to the ap- that the absolute average angle of the tan- proval of the Administrator. gential flow does not exceed 20 degrees. If the 7.2 Sample Recovery. Same as Method 306, average value exceeds 20 degrees at the sam- Section 7.2. pling location, the flow condition in the 7.3 Sample Preparation and Analysis. stack is unacceptable for testing. Same as Method 306, Section 7.3. 8.1.1.4.2 Alternative procedures, subject to 7.4 Glassware Cleaning Reagents. Same as approval of the Administrator, e.g., install- Method 306, Section 7.4. ing straightening vanes to eliminate the cy- 8.0 Sample Collection, Recovery, Preservation, clonic flow, must be implemented prior to Holding Times, Storage, and Transport conducting the testing. 8.1.1.5 Stack Gas Moisture Measurements. NOTE: Prior to sample collection, consider- Not required. Measuring the moisture content ation should be given as to the type of anal- is optional when a mass emission rate is to ∂ ysis (Cr 6 or total Cr) that will be per- be calculated. formed. Deciding which analysis will be per- 8.1.1.5.1 The tester may elect to either formed will enable the tester to determine measure the actual stack gas moisture dur- which appropriate sample recovery and storing the sampling run or utilize a nominal age procedures will be required to process moisture value of 2 percent. the sample. 8.1.1.5.2 For additional information on de- 8.1 Sample Collection. termining sampling train moisture, please 8.1.1 Pretest Preparation. refer to Method 4 (40 CFR Part 60, Appendix 8.1.1.1 Selection of Measurement Site. Lo- A). cate the sampling ports as specified in Sec- 8.1.1.6 Stack Temperature Measurements. tion 11.0 of Method 1 (40 CFR Part 60, Appen- If a mass emission rate is to be calculated, a dix A). temperature sensor must be placed either 8.1.1.2 Location of Traverse Points. near the center of the stack, or attached to 8.1.1.2.1 Locate the traverse points as the pitot tube as described in Section 8.3 of specified in Section 11.0 of Method 1 (40 CFR Method 2. Stack temperature measurements,

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shall be recorded before and after each test, 8.1.1.7.2 If the sampling period is to occur and an average stack temperature deter- over several days, the sampling times must mined for the testing period. be calculated daily using the initial velocity 8.1.1.7 Point Sampling Times. Since the pressure data recorded for that day. Deter- sampling rate of the train (0.75 cfm) is main- mine the average of the Dp values obtained tained constant by the critical orifice, it is during the velocity traverse (Figure 306A–2). necessary to calculate specific sampling 8.1.1.7.3 If the stack diameter is less than times for each traverse point in order to ob- 12 inches, use 7.5 minutes in place of 5 min- tain a proportional sample. utes in the equation and 16 sampling points 8.1.1.7.1 If the sampling period (3 runs) is instead of 24 or 25 points. Calculate the sam- to be completed in a single day, the point sampling times shall be calculated only pling times for each traverse point using the once. following equation:

Δp at Point n Minutes at point n = × 5 min. Eq. 306A -1 ()Δp avg

Where: mesh indicating silica gel, or equivalent des- n = Sampling point number. iccant into the third jar/impinger until the Dp = Average pressure differential across container is half full (∼ 300 to 400 g). pitot tube, mm H2O (in. H2O). 8.1.1.9.2 Place a small cotton ball in the DPavg = Average of Dp values, mm H2O (in. outlet exit tube of the third jar to collect H2O). small silica gel particles that may dislodge NOTE: Convert the decimal fractions for and impair the pump and/or gas meter. minutes to seconds. 8.1.1.10 Pretest Leak-Check. A pretest 8.1.1.8 Pretest Preparation. It is rec- leak-check is recommended, but not re- ommended, but not required, that all items quired. If the tester opts to conduct the pre- which will be in contact with the sample be test leak-check, the following procedures cleaned prior to performing the testing to shall be performed: (1) Place the jar/impinger avoid possible sample contamination (posi- containers into an ice bath and wait 10 min- tive chromium bias). These items include, utes for the ice to cool the containers before but are not limited to: Sampling probe, con- performing the leak check and/or start sam- necting tubing, impingers, and jar con- pling; (2) to perform the leak check, seal the tainers. nozzle using a piece of clear plastic wrap 8.1.1.8.1 Sample train components should placed over the end of a finger and switch on be: (1) Rinsed with hot tap water; (2) washed the pump; and (3) the train system leak rate with hot soapy water; (3) rinsed with tap should not exceed 0.02 cfm at a vacuum of 380 water; (4) rinsed with reagent water; (5) mm Hg (15 in. Hg) or greater. If the leak rate soaked in a 10 percent (v/v) nitric acid solu- does exceed the 0.02 cfm requirement, iden- tion for at least four hours; and (6) rinsed tify and repair the leak area and perform the throughly with reagent water before use. leak check again. 8.1.1.8.2 At a minimum, the tester should, NOTE: Use caution when releasing the vac- rinse the probe, connecting tubing, and first uum following the leak check. Always allow and second impingers twice with either 0.1 N air to slowly flow through the nozzle end of sodium hydroxide (NaOH) or 0.1 N sodium bi- the train system while the pump is still op- carbonate (NaHCO3) and discard the rinse so- erating. Switching off the pump with vacu- lution. um on the system may result in the silica 8.1.1.8.3 If separate sample shipping con- gel being pulled into the second jar containers are to be used, these also should be tainer. precleaned using the specified cleaning procedures. 8.1.1.11 Leak-Checks During Sample Run. 8.1.1.9 Preparation of Sampling Train. As- If, during the sampling run, a component semble the sampling train as shown in Fig- (e.g., jar container) exchange becomes nec- ure 306A–1. Secure the nozzle-liner assembly essary, a leak-check shall be conducted im- to the outer sheath to prevent movement mediately before the component exchange is when sampling. made. The leak-check shall be performed ac- 8.1.1.9.1 Place 250 mL of 0.1 N NaOH or 0.1 cording to the procedure outlined in Section N NaHCO3 absorbing solution into the first 8.1.1.10 of this method. If the leakage rate is jar container or impinger. The second jar/im- found to be ≤0.02 cfm at the maximum oper- pinger is to remain empty. Place 6 to 16 ating vacuum, the results are acceptable. If,

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however, a higher leak rate is obtained, ei- the sampling train to the next sampling port ther record the leakage rate and correct the and repeat the sequence. Be sure to record sample volume as shown in Section 12.3 of the final dry gas meter reading after com- Method 5 or void the sample and initiate a pleting the test run. After performing the replacement run. Following the component post test leak check, disconnect the jar/im- change, leak-checks are optional, but are pinger containers from the pump and meter recommended as are the pretest leak-checks. assembly and transport the probe, con- 8.1.1.12 Post Test Leak Check. Remove necting tubing, and containers to the sample the probe assembly and flexible tubing from recovery area. the first jar/impinger container. Seal the 8.1.2.4.2 Rectangle Stacks. Complete each inlet tube of the first container using clear port traverse as per the instructions pro- plastic wrap and switch on the pump. The vided in 8.1.2.4.1. vacuum in the line between the pump and NOTE: If an approximate mass emission the critical orifice must be ≥15 in. Hg. Record rate is to be calculated, measure and record the vacuum gauge measurement along with the stack velocity pressure and temperature the leak rate observed on the train system. before and after the test run. 8.1.1.12.1 If the leak rate does not exceed 8.2 Sample Recovery. After the train has 0.02 cfm, the results are acceptable and no been transferred to the sample recovery sample volume correction is necessary. area, disconnect the tubing that connects 8.1.1.12.2 If, however, a higher leak rate is the jar/impingers. The tester shall select ei- obtained (>0.02 cfm), the tester shall either ther the total Cr or Cr∂6 sample recovery op- record the leakage rate and correct the sam- tion. Samples to be analyzed for both total ple volume as shown in Section 12.3 of Meth- Cr and Cr∂6 shall be recovered using the Cr∂6 od 5, or void the sampling run and initiate a sample option (Section 8.2.2). replacement run. After completing the NOTE: Collect a reagent blank sample for leak-check, slowly release the vacuum at the each of the total Cr or the Cr∂6 analytical first container while the pump is still oper- options. If both analyses (Cr and Cr∂6) are to ating. Afterwards, switch-off the pump. be conducted on the samples, collect sepa- 8.1.2 Sample Train Operation. rate reagent blanks for each analysis. Also, 8.1.2.1 Data Recording. Record all perti- since particulate matter is not usually nent process and sampling data on the data present at chromium electroplating and/or sheet (see Figure 306A–3). Ensure that the chromium anodizing operations, it is not process operation is suitable for sample col- necessary to filter the Cr∂6 samples unless lection. there is observed sediment in the collected 8.1.2.2 Starting the Test. Place the probe/ solutions. If it is necessary to filter the Cr∂6 nozzle into the duct at the first sampling solutions, please refer to Method 0061, Deter- point and switch on the pump. Start the mination of Hexavalent Chromium Emis- sampling using the time interval calculated sions from Stationary Sources, Section 7.4, for the first point. When the first point sam- Sample Preparation in SW–846 (see Reference pling time has been completed, move to the 1). second point and continue to sample for the time interval calculated for that point; sam- 8.2.1 Total Cr Sample Option. 8.2.1.1 Shipping Container No. 1. The first ple each point on the traverse in this man- jar container may either be used to store and ner. Maintain ice around the sample con- transport the sample, or if GS impingers are tainers during the run. used, samples may be stored and shipped in 8.1.2.3 Critical Flow. The sample line be- precleaned 250-mL, 500-mL or 1000-mL poly- tween the critical orifice and the pump must ethylene or glass bottles with leak-free, non- operate at a vacuum of ≥380 mm Hg (≥15 in. metal screw caps. Hg) in order for critical flow to be main- 8.2.1.1.1 Unscrew the lid from the first jar/ tained. This vacuum must be monitored and impinger container. documented using the vacuum gauge located 8.2.1.1.2 Lift the inner tube assembly al- between the critical orifice and the pump. most out of the container, and using the NOTE: Theoretically, critical flow for air wash bottle containing fresh absorbing solu- occurs when the ratio of the orifice outlet tion, rinse the outside of the tube that was absolute pressure to the orifice inlet abso- immersed in the container solution; rinse lute pressure is less than a factor of 0.53. the inside of the tube as well, by rinsing This means that the system vacuum should twice from the top of the tube down through be at least ≥356 mm Hg (≥14 in. Hg) at sea the inner tube into the container. level and ∼ 305 mm Hg (∼ 12 in. Hg) at higher 8.2.1.2 Recover the contents of the second elevations. jar/impinger container by removing the lid 8.1.2.4 Completion of Test. and pouring any contents into the first ship- 8.1.2.4.1 Circular Stacks. Complete the ping container. first port traverse and switch off the pump. 8.2.1.2.1 Rinse twice, using fresh absorbing Testers may opt to perform a leak-check be- solution, the inner walls of the second con- tween the port changes to verify the leak tainer including the inside and outside of the rate however, this is not mandatory. Move inner tube.

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8.2.1.2.2 Rinse the connecting tubing be- 0061, Determination of Hexavalent Chro- tween the first and second sample containers mium Emissions from Stationary Sources, with absorbing solution and place the rinses Section 7.4, Sample Preparation in SW–846 into the first container. (see Reference 5) for procedure. 8.2.1.3 Position the nozzle, probe and con- 8.2.3 Silica Gel Container. Observe the necting plastic tubing in a vertical position color of the indicating silica gel to deter- so that the tubing forms a ‘‘U’’. mine if it has been completely spent and 8.2.1.3.1 Using the wash bottle, partially make a notation of its condition/color on the fill the tubing with fresh absorbing solution. field data sheet. Do not use water or other Raise and lower the end of the plastic tubing liquids to remove and transfer the silica gel. several times to allow the solution to con- 8.2.4 Total Cr and/or Cr∂6 Reagent Blank. tact the internal surfaces. Do not allow the solution to overflow or part of the sample 8.2.4.1 Shipping Container No. 2. Place ap- will be lost. Place the nozzle end of the probe proximately 500 mL of the 0.1 N NaOH or 0.1 over the mouth of the first container and N NaHCO3 absorbing solution in a elevate the plastic tubing so that the solu- precleaned, labeled sample container and in- tion flows into the sample container. clude with the field samples for analysis. 8.2.1.3.2 Repeat the probe/tubing sample 8.3 Sample Preservation, Storage, and recovery procedure but allow the solution to Transport. flow out the opposite end of the plastic tub- 8.3.1 Total Cr Option. Samples that are to ing into the sample container. Repeat the be analyzed for total Cr need not be refrig- entire sample recovery procedure once again. erated. 8.2.1.4 Use approximately 200 to 300 mL of 8.3.2 Cr∂6 Option. Samples that are to be ∂6 the 0.1 N NaOH or 0.1 N NaHCO3 absorbing analyzed for Cr must be shipped and stored solution during the rinsing of the probe noz- at 4 °C (∼40 °F). zle, probe liner, sample containers, and con- NOTE: Allow Cr∂6 samples to return to am- necting tubing. bient temperature prior to analysis. 8.2.1.5 Place a piece of clear plastic wrap 8.4 Sample Holding Times. over the mouth of the sample jar to seal the shipping container. Use a standard lid and 8.4.1 Total Cr Option. Samples that are to band assembly to seal and secure the sample be analyzed for total chromium must be ana- in the jar. lyzed within 60 days of collection. ∂ 8.2.1.5.1 Label the jar clearly to identify 8.4.2 Cr 6 Option. Samples that are to be ∂ its contents, sample number and date. analyzed for Cr 6 must be analyzed within 14 8.2.1.5.2 Mark the height of the liquid days of collection. level on the container to identify any losses during shipping and handling. 9.0 Quality Control 8.2.1.5.3 Prepare a chain-of-custody sheet 9.1 Same as Method 306, Section 9.0. to accompany the sample to the laboratory. 8.2.2 Cr∂6 Sample Option. 10.0 Calibration and Standardization 8.2.2.1 Shipping Container No. 1. The first jar container may either be used to store and NOTE: Tester shall maintain a performance transport the sample, or if GS impingers are log of all calibration results. used, samples may be stored and shipped in 10.1 Pitot Tube. The Type S pitot tube as- precleaned 250-mL, 500-mL or 1000-mL poly- sembly shall be calibrated according to the ethylene or glass bottles with leak-free non- procedures outlined in Section 10.1 of Method metal screw caps. 2. 8.2.2.1.1 Unscrew and remove the lid from 10.2 Temperature Sensor. Use the proce- the first jar container. dure in Section 10.3 of Method 2 to calibrate 8.2.2.1.2 Measure and record the pH of the the in-stack temperature sensor. solution in the first container by using a pH 10.3 Metering System. indicator strip. The pH of the solution must 10.3.1 Sample Train Dry Gas Meter Cali- be ≥8.5 for NaOH and ≥8.0 for NaHCO3. If not, bration. Calibrations may be performed as discard the collected sample, increase the described in Section 16.2 of Method 5 by ei- concentration of the NaOH or NaHCO3 ab- ther the manufacturer, a firm who provides sorbing solution to 0.5 M and collect another calibration services, or the tester. air emission sample. 10.3.2 Dry Gas Meter Calibration Coeffi- 8.2.2.2 After measuring the pH of the first cient (Ym). The meter calibration coefficient container, follow sample recovery procedures (Ym) must be determined prior to the initial described in Sections 8.2.1.1 through 8.2.1.5. use of the meter, and following each field NOTE: Since particulate matter is not usu- test program. If the dry gas meter is new, ally present at chromium electroplating and/ the manufacturer will have specified the Ym or chromium anodizing facilities, it is not value for the meter. This Ym value can be necessary to filter the Cr∂6 samples unless used as the pretest value for the first test. there is observed sediment in the collected For subsequent tests, the tester must use the ∂6 solutions. If it is necessary to filter the Cr Ym value established during the pretest cali- solutions, please refer to the EPA Method bration.

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10.3.3 Calibration Orifice. The manufac- not to be reconnected to the sample train turer may have included a calibration orifice during the calibration procedure. and a summary spreadsheet with the meter 10.3.4.2 If the vacuum pump is cold, switch that may be used for calibration purposes. on the pump and allow it to operate (become The spreadsheet will provide data necessary warm) for several minutes prior to starting to determine the calibration for the orifice the calibration. After stopping the pump, and meter (standard cubic feet volume, sam- record the initial dry gas meter volume and ple time, etc.). These data were produced meter temperature. when the initial Y value was determined for m 10.3.4.3 Perform the calibration for the the meter. number of minutes specified by the manufac- 10.3.4 Ym Meter Value Verification or Meter Calibration. turer’s data sheet (usually 5 minutes). Stop the pump and record the final dry gas meter 10.3.4.1 The Ym meter value may be determined by replacing the sampling train crit- volume and temperature. Subtract the start ical orifice with the calibration orifice. Re- volume from the stop volume to obtain the place the critical orifice assembly by install- Vm and average the meter temperatures (tm). ing the calibration orifice in the same loca- 10.3.5 Ym Value Calculation. Ym is the cal- tion. The inlet side of the calibration orifice culated value for the dry gas meter. Cal- is to be left open to the atmosphere and is culate Ym using the following equation:

V () Y = m std ,mfg m ⎛ ⎞⎛ ⎞ Tstd Pbar Vm ⎜ ⎟⎜ ⎟ ⎝ Pstd ⎠⎝ Tm ⎠ V T = m() std ,mfg m Ym Eq. 306A - 2 17.64 Vm P bar

Where: English = 528 °R. V = Volume of gas sample as measured (ac- Pbar = Barometric pressure at meter, mm Hg, m (in. Hg). tual) by dry gas meter, dcm,(dcf). V ( ) = Volume of gas sample measured Pstd = Standard absolute pressure, m std ,mfg Metric = 760 mm Hg. by manufacture’s calibrated orifice and English = 29.92 in. Hg. dry gas meter, corrected to standard conditions (pressure/temperature) dscm tm = Average dry gas meter temperature, °C, (°F). (dscf). Y = Dry gas meter calibration factor, Tm = Absolute average dry gas meter tem- m perature, (dimensionless). Metric °K = 273 + tm (°C). 10.3.6 Ym Comparison. Compare the Ym English °R = 460 + tm (°F). value provided by the manufacturer (Section Tstd = Standard absolute temperature, 10.3.3) or the pretest Ym value to the post Metric = 293 °K. test Ym value using the following equation:

Y ()manufacturer' s or pretest value m Eq. 306A -3 Ym ()post - test value

10.3.6.1 If this ratio is between 0.95 and or post test Ym value) produces the lowest 1.05, the designated Ym value for the meter is sample volume. acceptable for use in later calculations. 10.3.6.1.2 If the post test dry gas meter Ym 10.3.6.1.1 If the value is outside the speci- value differs by more than 5% as compared fied range, the test series shall either be: 1) to the pretest value, either perform the cali- voided and the samples discarded; or 2) cal- bration again to determine acceptability or culations for the test series shall be con- return the meter to the manufacturer for re- ducted using whichever meter coefficient calibration.

value (i.e., manufacturers’s/pretest Ym value

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10.3.6.1.3 The calibration may also be con- Ms = Molecular weight of wet stack gas, wet ducted as specified in Section 10.3 or Section basis, g/g-mole, (lb/lb-mole); in a nominal 16.0 of Method 5 (40 CFR Part 60, Appendix gas stream at 2% moisture the value is A), except that it is only necessary to check 28.62. the calibration at one flow rate of ∼ 0.75 cfm. Pbar = Barometric pressure at sampling site, 10.3.6.1.4 The calibration of the dry gas mm Hg (in. Hg). meter must be verified after each field test Ps = Absolute stack gas pressure; in this program using the same procedures. case, usually the same value as the barometric pressure, mm Hg (in. Hg). NOTE: The tester may elect to use the Ym post test value for the next pretest Ym value; Pstd = Standard absolute pressure: e.g., Test 1 post test Ym value and Test 2 pre- Metric = 760 mm Hg. test Ym value would be the same. English = 29.92 in. Hg. 10.4 Barometer. Calibrate against a mer- Qstd = Average stack gas volumetric flow, cury barometer that has been corrected for dry, corrected to standard conditions, temperature and elevation. dscm/hr (dscf/hr). ° 10.5 ICP Spectrometer Calibration. Same tm = Average dry gas meter temperature, C ° as Method 306, Section 10.2. ( F). 10.6 GFAA Spectrometer Calibration. Tm = Absolute average dry gas meter tem- Same as Method 306, Section 10.3. perature: ° ° 10.7 IC/PCR Calibration. Same as Method Metric K = 273 + tm ( C). ° ° 306, Section 10.4. English R = 460 + tm ( F). ts = Average stack temperature, °C (°F). 11.0 Analytical Procedures Ts = Absolute average stack gas temperature: Metric °K = 273 + t (°C). English °R NOTE: The method determines the chro- s = 460 + t (°F). mium concentration in μg Cr/mL. It is im- s T = Standard absolute temperature: Metric portant that the analyst measure the volume std = 293 °K. English = 528 °R. of the field sample prior to analyzing the V = Volume of sample aliquot after diges- sample. This will allow for conversion of μg ad tion (mL). Cr/mL to μg Cr/sample. Vaf = Volume of sample aliquot after dilution 11.1 Analysis. Refer to Method 306 for (mL). sample preparation and analysis procedures. Vbd = Volume of sample aliquot submitted to digestion (mL). 12.0 Data Analysis and Calculations Vbf = Volume of sample aliquot before dilu- 12.1 Calculations. Perform the calculation (mL). tions, retaining one extra decimal point be- Vm = Volume of gas sample as measured (ac- yond that of the acquired data. When report- tual, dry) by dry gas meter, dcm (dcf). ing final results, round number of figures VmL = Volume of impinger contents plus consistent with the original data. rinses (mL). 12.2 Nomenclature. Vm(std) = Volume of gas sample measured by the dry gas meter, corrected to standard A = Cross-sectional area of stack, m2 (ft2). conditions (temperature/pressure), dscm Bws = Water vapor in gas stream, proportion by volume, dimensionless (assume 2 per- (dscf). cent moisture = 0.02). vs = Stack gas average velocity, calculated by Method 2, Equation 2–9, m/sec (ft/sec). Cp = Pitot tube coefficient; ‘‘S’’ type pitot coefficient usually 0.840, dimensionless. W = Width of a square or rectangular duct, m (ft). CS = Concentration of Cr in sample solution, μg Cr/mL. Ym = Dry gas meter calibration factor, (dimensionless). CCr = Concentration of Cr in stack gas, dry basis, corrected to standard conditions Dp = Velocity head measured by the Type S μg/dscm (gr/dscf). pitot tube, cm H2O (in. H2O). d = Diameter of stack, m (ft). Dpavg = Average of Dp values, mm H2O (in. D = Digestion factor, dimensionless. H2O). ER = Approximate mass emission rate, mg/hr 12.3 Dilution Factor. The dilution factor (lb/hr). is the ratio of the volume of sample aliquot F = Dilution factor, dimensionless. after dilution to the volume before dilution. L = Length of a square or rectangular duct, The dilution factor is usually calculated by m (ft). the laboratory. This ratio is derived by the MCr = Total Cr in each sample, μg (gr). following equation:

V F = af Eq. 306A - 4 Vbf

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12.4 Digestion Factor. The digestion fac- gestion. The digestion factor is usually cal- tor is the ratio of the volume of sample ali- culated by the laboratory. This ratio is de- quot after digestion to the volume before di- rived by the following equation.

V D = ad Eq. 306A - 5 Vbd

12.5 Total Cr in Sample. Calculate MCr, the total μg Cr in each sample, using the following equation:

=××× MVCFDCr mL S Eq. 306A - 6

12.6 Dry Gas Volume. Correct the sample standard conditions (20 °C, 760 mm Hg or 68 volume measured by the dry gas meter to °F, 29.92 in. Hg) using the following equation:

⎛ ⎞⎛ ⎞ ⎛ ⎞ = Tstd Pbar = Pbar VVYm() std mm⎜ ⎟⎜ ⎟ KVlmm Y ⎜ ⎟ Eq. 306A - 7 ⎝ Tm ⎠⎝ Pstd ⎠ ⎝ Tm ⎠

Where: 12.7 Cr Emission Concentration (CCr). Cal- K = Metric units—0.3855 °K/mm Hg. culate CCr, the Cr concentration in the stack 1 gas, in μg/dscm (μg/dscf) on a dry basis, cor- English units—17.64 °R/in. Hg. rected to standard conditions, using the following equation:

= MCr CCr Eq. 306A -8 Vm() std

NOTE: To convert μg/dscm (μg/dscf) to mg/ 12.8.1 Kp = Velocity equation constant: dscm (mg/dscf), divide by 1000. 12.8 Stack Gas Velocity.

⎡ ⎤12/ m ()()g/ g- mole mm Hg Metric K = 34. 97 ⎢ ⎥ p sec ⎢ ° ()⎥ ⎣ ()K mm H2 O ⎦

⎡ ⎤12/ ft ()()lb/ lb- mole in. Hg English K = 85.49 ⎢ ⎥ p sec ⎢ ° ()⎥ ⎣ ()R in. H 2 O ⎦

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12.8.2 Average Stack Gas Velocity.

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Ts() avg vKCp= ()Δ spp avg PMss

Ts() avg = 34. 97 C()Δp Eq. 306A-9 p avg PMss

12.9 Cross sectional area of stack.

Πd2 A = or A = LW Eq. 306A-10 4

12.10 Average Stack Gas Dry Volumetric tester may elect to use either the nominal Flow Rate. stack gas moisture value or the actual stack NOTE: The emission rate may be based on a gas moisture collected during the sampling nominal stack moisture content of 2 percent run. (0.02). To calculate an emission rate, the Volumetric Flow Rate Equation:

⎛ ⎞ ⎛ ⎞ =− Tstd Ps QlBvAstd3600() ws s ⎜ ⎟ ⎜ ⎟ Eq. 306A-11 ⎝ Ts() avg ⎠ ⎝ Pstd ⎠

Where: 3600 = Conversion factor, sec/hr.

⎛ ⎞ P = ⎜ s ⎟ QAstd 62,234 vs ⎜ ⎟ Eq. 306A-12 ⎝ Ts() avg ⎠

NOTE: To convert Qstd from dscm/hr (dscf/ 12.11 Mass emission rate, mg/hr (lb/hr): hr) to dscm/min (dscf/min), divide Qstd by 60.

=× ×−3 ER Ccr Qstd 10() mg / hr Eq. 306A-13 =× × ×−4 () ER Ccr Qstd 1.43 10 lb/ hr Eq. 306A-14

13.0 Method Performance niques can be extended indefinitely by appropriate dilution. 13.1 Range. The recommended working 13.2 Sensitivity. range for all of the three analytical tech- 13.2.1 Analytical Sensitivity. The esti- niques starts at five times the analytical de- mated instrumental detection limits listed tection limit (see also Method 306, Section are provided as a guide for an instrumental 13.2.2). The upper limit of all three tech- limit. The actual method detection limits

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are sample and instrument dependent and were 10, 50, and 149 μg Cr/L; and the mean may vary as the sample matrix varies. percent relative standard deviations were 18, 13.2.1.1 ICP Analytical Sensitivity. The 3.3, and 3.8 percent, respectively. minimum estimated detection limits for 13.4.2 In another multilaboratory study ICP, as reported in Method 6010A and the re- cited in Method 6010B, a mean relative stand- cently revised Method 6010B of SW–846 (Ref- ard of 8.2 percent was reported for an aque- erence 1), are 7.0 μg Cr/L and 4.7 μg Cr/L, re- ous sample concentration of approximately spectively. 3750 μg Cr/L. 13.2.1.2 GFAAS Analytical Sensitivity. 13.5 GFAAS Precision. As reported in The minimum estimated detection limit for Method 7191 of SW–846 (Reference 1), in a sin- GFAAS, as reported in Methods 7000A and gle laboratory (EMSL), using Cincinnati, 7191 of SW–846 (Reference 1), is 1.0 μg Cr/L. Ohio tap water spiked at concentrations of 13.2.1.3 IC/PCR Analytical Sensitivity. 19, 48, and 77 μg Cr/L, the standard deviations The minimum detection limit for IC/PCR were ±0.1, ±0.2, and ±0.8, respectively. Recov- with a preconcentrator, as reported in Meth- eries at these levels were 97 percent, 101 per- ods 0061 and 7199 of SW–846 (Reference 1), is cent, and 102 percent, respectively. ∂ 0.05 μg Cr 6/L. 13.6 IC/PCR Precision. As reported in 13.2.2 In-stack Sensitivity. The in-stack Methods 0061 and 7199 of SW–846 (Reference sensitivity depends upon the analytical de- 1), the precision of IC/PCR with sample tection limit, the volume of stack gas sam- preconcentration is 5 to 10 percent; the over- pled, and the total volume of the impinger all precision for sewage sludge incinerators absorbing solution plus the rinses. Using the emitting 120 ng/dscm of Cr∂6 and 3.5 μg/dscm analytical detection limits given in Sections of total Cr is 25 percent and 9 percent, re- 13.2.1.1, 13.2.1.2, and 13.2.1.3; a stack gas sam- spectively; and for hazardous waste inciner- ple volume of 1.7 dscm; and a total liquid ators emitting 300 ng/dscm of Cr∂6 the preci- sample volume of 500 mL; the corresponding sion is 20 percent. in-stack detection limits are 0.0014 mg Cr/ dscm to 0.0021 mg Cr/dscm for ICP, 0.00029 mg 14.0 Pollution Prevention Cr/dscm for GFAAS, and 0.000015 mg Cr∂36/ dscm for IC/PCR with preconcentration. 14.1 The only materials used in this method that could be considered pollutants are NOTE: It is recommended that the con- the chromium standards used for instrument centration of Cr in the analytical solutions calibration and acids used in the cleaning of be at least five times the analytical detec- the collection and measurement containers/ tion limit to optimize sensitivity in the labware, in the preparation of standards, and analyses. Using this guideline and the same in the acid digestion of samples. Both re- assumptions for impinger sample volume and agents can be stored in the same waste con- stack gas sample volume (500 mL and 1.7 tainer. dscm, respectively), the recommended minimum stack concentrations for optimum 14.2 Cleaning solutions containing acids sensitivity are 0.0068 mg Cr/dscm to 0.0103 mg should be prepared in volumes consistent Cr/dscm for ICP, 0.0015 mg Cr/dscm for with use to minimize the disposal of excessive volumes of acid. GFAAS, and 0.000074 mg Cr∂6 dscm for IC/ PCR with preconcentration. If required, the 14.3 To the extent possible, the con- in-stack detection limits can be improved by tainers/vessels used to collect and prepare either increasing the sampling time, the samples should be cleaned and reused to min- stack gas sample volume, reducing the vol- imize the generation of solid waste. ume of the digested sample for GFAAS, im- 15.0 Waste Management proving the analytical detection limits, or any combination of the three. 15.1 It is the responsibility of the labora- 13.3 Precision. tory and the sampling team to comply with 13.3.1 The following precision data have all federal, state, and local regulations gov- been reported for the three analytical meth- erning waste management, particularly the ods. In each case, when the sampling preci- discharge regulations, hazardous waste iden- sion is combined with the reported analyt- tification rules, and land disposal restric- ical precision, the resulting overall precision tions; and to protect the air, water, and land may decrease. by minimizing and controlling all releases 13.3.2 Bias data is also reported for from field operations. GFAAS. 15.2 For further information on waste 13.4 ICP Precision. management, consult The Waste Manage- 13.4.1 As reported in Method 6010B of SW– ment Manual for Laboratory Personnel and 846 (Reference 1), in an EPA round-robin Less is Better-Laboratory Chemical Manage- Phase 1 study, seven laboratories applied the ment for Waste Reduction, available from ICP technique to acid/distilled water mat- the American Chemical Society’s Depart- rices that had been spiked with various ment of Government Relations and Science metal concentrates. For true values of 10, 50, Policy, 1155 16th Street NW, Washington, DC and 150 μg Cr/L; the mean reported values 20036.

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16.0 References 4. Clay, F.R., Proposed Sampling Method 306A for the Determination of Hexavalent 1. F.R. Clay, Memo, Impinger Collection Efficiency—Mason Jars vs. Greenburg-Smith Chromium Emissions from Electroplating Impingers, Dec. 1989. and Anodizing Facilities. In: Proceedings of 2. Segall, R.R., W.G. DeWees, F.R. Clay, the 1992 EPA/A&WMA International Sympo- and J.W. Brown. Development of Screening sium-Measurement of Toxic and Related Air Methods for Use in Chromium Emissions Pollutants, A&WMA Publication VIP–25, Measurement and Regulations Enforcement. EPA Report No. 600/R–92/131, p. 209. In: Proceedings of the 1989 EPA/A&WMA 5. Test Methods for Evaluating Solid International Symposium-Measurement of Waste, Physical/Chemical Methods, SW–846, Toxic and Related Air Pollutants, A&WMA Third Edition as amended by Updates I, II, Publication VIP–13, EPA Report No. 600/9–89– IIA, IIB, and III. Document No. 955–001– 060, p. 785. 000001. Available from Superintendent of 3. Clay, F.R., Chromium Sampling Method. Documents, U.S. Government Printing Of- In: Proceedings of the 1990 EPA/A&WMA fice, Washington, DC, November 1986. International Symposium-Measurement of Toxic and Related Air Pollutants, A&WMA 17.0 Tables, Diagrams, Flowcharts, and Publication VIP–17, EPA Report No. 600/9–90– Validation Data 026, p. 576.

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METHOD 306B—SURFACE TENSION MEASURE- other methods in 40 CFR Part 60, Appendix A MENT FOR TANKS USED AT DECORATIVE and in this part. Therefore, to obtain reliable CHROMIUM ELECTROPLATING AND CHROMIUM results, persons using this method should ANODIZING FACILITIES have a thorough knowledge of at least Meth- ods 5 and 306. NOTE: This method does not include all of the specifications (e.g., equipment and sup- 1.0 Scope and Application plies) and procedures (e.g., sampling and analytical) essential to its performance. Some 1.1 Analyte. Not applicable. material is incorporated by reference from

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1.2 Applicability. This method is applica- 7.0 Reagents and Standards [Reserved] ble to all chromium electroplating and chromium anodizing operations, and continuous 8.0 Sample Collection, Sample Recovery, Sam- chromium plating at iron and steel facilities ple Preservation, Sample Holding Times, Stor- where a wetting agent is used in the tank as age, and Transport [Reserved] the primary mechanism for reducing emis- 9.0 Quality Control [Reserved] sions from the surface of the plating solution. 10.0 Calibration and Standardization [Reserved] 2.0 Summary of Method 11.0 Analytical Procedure 2.1 During an electroplating or anodizing operation, gas bubbles generated during the 11.1 Procedure. The surface tension of the process rise to the surface of the liquid and tank bath may be measured using a tensiom- burst. Upon bursting, tiny droplets of chro- eter, stalagmometer, or any other equivalent mic acid become entrained in ambient air. surface tension measuring device for meas- The addition of a wetting agent to the tank uring surface tension in dynes per centi- bath reduces the surface tension of the liquid meter. and diminishes the formation of these drop- 11.1.1 If a tensiometer is used, the proce- lets. dures specified in ASTM Method D 1331–89 2.2 This method determines the surface must be followed. tension of the bath using a stalagmometer or 11.1.2 If a stalagmometer is used, the procedures specified in Sections 11.1.2.1 through a tensiometer to confirm that there is suffi- 11.1.2.3 must be followed. cient wetting agent present. 11.1.2.1 Check the stalagmometer for vis- 3.0 Definitions [Reserved] ual signs of damage. If the stalagmometer appears to be chipped, cracked, or otherwise 4.0 Interferences [Reserved] in disrepair, the instrument shall not be used. 5.0 Safety 11.1.2.2 Using distilled or deionized water and following the procedures provided by the 5.1 Disclaimer. This method may involve manufacturer, count the number of drops hazardous materials, operations, and equip- corresponding to the distilled/deionized ment. This test method may not address all water liquid volume between the upper and of the safety problems associated with its lower etched marks on the stalagmometer. If use. It is the responsibility of the user to es- the number of drops for the distilled/deion- tablish appropriate safety and health prac- ized water is not within ±1 drop of the num- tices and to determine the applicability of ber indicated on the instrument, the stal- regulatory limitations prior to performing agmometer must be cleaned, using the proce- this test method. dures specified in Section 11.1.3 of this method, before using the instrument to measure 6.0 Equipment and Supplies the surface tension of the tank liquid. 6.1 Stalagmometer. Any commercially 11.1.2.2.1 If the stalagmometer must be available stalagmometer or equivalent sur- cleaned, as indicated in Section 11.1.2.2, re- face tension measuring device may be used peat the procedure specified in Section 11.1.2.2 before proceeding. to measure the surface tension of the plating 11.1.2.2.2 If, after cleaning and performing or anodizing tank liquid provided the proce- the procedure in Section 11.1.2.2, the number dures specified in Section 11.1.2 are followed. of drops indicated for the distilled/deionized 6.2 Tensiometer. A tensiometer may be water is not within ±1 drop of the number in- used to measure the surface tension of the dicated on the instrument, either use the tank liquid provided the procedures specified number of drops corresponding to the dis- in ASTM Method D 1331–89, Standard Test tilled/deionized water volume as the ref- Methods for Surface and Interfacial Tension erence number of drops, or replace the in- of Solutions of Surface Active Agents (incor- strument. porated by reference—see § 63.14) are fol- 11.1.2.3 Determine the surface tension of lowed. the tank liquid using the procedures specified by the manufacturer of the stalagmometer. 11.1.3 Stalagmometer cleaning procedures. The procedures specified in Sections 11.1.3.1 through 11.1.3.10 shall be used for cleaning a stalagmometer, as required by Section 11.1.2.2. 11.1.3.1 Set up the stalagmometer on its stand in a fume hood.

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11.1.3.2 Place a clean 150 (mL) beaker un- 12.0 Data Analysis and Calculations derneath the stalagmometer and fill the beaker with reagent grade concentrated ni- 12.1 Log Book of Surface Tension Meas- tric acid. urements and Fume Suppressant Additions. 11.1.3.3 Immerse the bottom tip of the 12.1.1 The surface tension of the plating stalagmometer (approximately 1 centimeter or anodizing tank bath must be measured as (0.5 inches)) into the beaker. specified in Section 11.2. 11.1.3.4 Squeeze the rubber bulb and pinch 12.1.2 The measurements must be re- at the arrow up (1) position to collapse. corded in the log book. In addition to the record of surface tension measurements, the 11.1.3.5 Place the bulb end securely on top frequency of fume suppressant maintenance end of stalagmometer and carefully draw the additions and the amount of fume suppres- nitric acid by pinching the arrow up (1) posi- sant added during each maintenance addition until the level is above the top etched tion must be recorded in the log book. line. 12.1.3 The log book will be readily avail- 11.1.3.6 Allow the nitric acid to remain in able for inspection by regulatory personnel. stalagmometer for 5 minutes, then carefully 12.2 Instructions for Apparatus Used in remove the bulb, allowing the acid to com- Measuring Surface Tension. pletely drain. 12.2.1 Included with the log book must be 11.1.3.7 Fill a clean 150 mL beaker with a copy of the instructions for the apparatus distilled or deionized water. used for measuring the surface tension of the 11.1.3.8 Using the rubber bulb per the in- plating or anodizing bath. structions in Sections 11.1.3.4 and 11.1.3.5, 12.2.2 If a tensiometer is used, a copy of rinse and drain stalagmometer with deion- ASTM Method D 1331–89 must be included ized or distilled water. with the log book. 11.1.3.9 Fill a clean 150 mL beaker with isopropyl alcohol. 13.0 Method Performance [Reserved] 11.1.3.10 Again using the rubber bulb per the instructions in Sections 11.1.3.4 and 14.0 Pollution Prevention [Reserved] 11.1.3.5, rinse and drain stalagmometer twice with isopropyl alcohol and allow the stal- 15.0 Waste Management [Reserved] agmometer to dry completely. 11.2 Frequency of Measurements. 16.0 References [Reserved] 11.2.1 Measurements of the bath surface 17.0 Tables, Diagrams, Flowcharts, and tension are performed using a progressive Validation Data [Reserved] system which decreases the frequency of surface tension measurements required when METHOD 307—DETERMINATION OF EMISSIONS the proper surface tension is maintained. FROM HALOGENATED SOLVENT VAPOR 11.2.1.1 Initially, following the compliance CLEANING MACHINES USING A LIQUID LEVEL date, surface tension measurements must be PROCEDURE conducted once every 4 hours of tank operation for the first 40 hours of tank operation. 1. Applicability and Principle 11.2.1.2 Once there are no exceedances 1.1 Applicability. This method is applica- during a period of 40 hours of tank operation, ble to the determination of the halogenated measurements may be conducted once every solvent emissions from solvent vapor clean- 8 hours of tank operation. ers in the idling mode. 11.2.1.3 Once there are no exceedances 1.2 Principle. The solvent level in the sol- during a second period of 40 consecutive vent cleaning machine is measured using in- hours of tank operation, measurements may clined liquid level indicators. The change in be conducted once every 40 hours of tank op- liquid level corresponds directly to the eration on an on-going basis, until an ex- amount of solvent lost from the solvent ceedance occurs. The maximum time inter- cleaning machine. val for measurements is once every 40 hours of tank operation. 2. Apparatus 11.2.2 If a measurement of the surface tension of the solution is above the 40 dynes per NOTE: Mention of trade names or specific centimeter limit when measured using a products does not constitute endorsement by stalagmometer, above 33 dynes per centi- the Environmental Protection Agency. meter when measured using a tensiometer, 2.1 Inclined Liquid Level Indicator. A or above an alternate surface tension limit schematic of the inclined liquid level indica- established during the performance test, the tors used in this method is shown in figure time interval shall revert back to the origi- 307–1; two inclined liquid level indicators nal monitoring schedule of once every 4 having 0.05 centimeters divisions or smaller hours. A subsequent decrease in frequency shall be used. The liquid level indicators would then be allowed according to Section shall be made of glass, Teflon, or any similar 11.2.1. material that will not react with the solvent

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being used. A 6-inch by 1-inch slope is rec- NOTE: It is important that the inclined liq- ommended; however the slope may vary de- uid level indicators be constructed with ease pending on the size and design of the solvent of reading in mind. The inclined liquid level cleaning machine. indicators should also be mounted so that they can be raised or lowered if necessary to suit the solvent cleaning machine size.

2.2 Horizontal Indicator. Device to check 3. Procedure the inclined liquid level indicators orienta- 3.1 Connection of the Inclined Liquid tion relative to horizontal. Level Indicator. Connect one of the inclined 2.3 Velocity Meter. Hotwire and vane liquid level indicators to the boiling sump anemometers, or other devices capable of drain and the other inclined liquid level indi- measuring the flow rates ranging from 0 to cator to the immersion sump drain using 15.2 meters per minute across the solvent Teflon tubing and the appropriate fittings. A cleaning machine. schematic diagram is shown in figure 307–2.

3.2 Positioning of Velocity Meter. Posi- Date lllllllllllllllllllll tion the velocity meter so that it measures Run lllllllllllllllllllll the flow rate of the air passing directly across the solvent cleaning machine. Solvent type llllllllllllllll 3.3 Level the Inclined Liquid Level Indi- Solvent density, g/m 3 (lb/ft 3) llllllll cators. Length of boiling sump (SB), m (ft) lllll 3.4 Initial Inclined Liquid Level Indicator Readings. Open the sump drainage valves. Width of boiling sump (WB), m (ft) lllll Allow the solvent cleaning machine to oper- Length of immersion sump (SI), m (ft) lll ate long enough for the vapor zone to form Width of immersion sump (W ), m (ft) lll and the system to stabilize (check with man- I ufacturer). Record the inclined liquid level Length of solvent vapor/air interface (SV), m indicators readings and the starting time on (ft) llllll the data sheet. A sample data sheet is pro- Width of solvent vapor/air interface (WV), m vided in figure 307–3. (ft) llllll

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check to make sure the inclined liquid level Boiling Immer- sion Flow rate indicators are level; if not, make the nec- Clock time sump sump reading reading reading essary adjustments. Record the final inclined liquid level indicators readings and time. 3.6 Determination of Solvent Vapor/Air Interface Area for Each Sump. Determine the area of the solvent/air interface of the individual sumps. Whenever possible, physically measure these dimensions, rather than using factory specifications. A schematic of Figure 307–3. Data sheet. the dimensions of a solvent cleaning ma- 3.5 Final Inclined Liquid Level Indicator chine is provided in figure 307–4. Readings. At the end of the 16-hour test run,

4. Calculations 4.3 Area of Solvent/Air Interface. Cal- culate the area of the solvent vapor/air inter- 4.1 Nomenclature. face as follows: A = area of boiling sump interface, m2 (ft2). B A = S W Eq. 307–3 A = area of immersion sump interface, m2 V V V I 4.4 Emission Rate. Calculate the emission (ft2). 2 2 rate as follows: AV = area of solvent/air interface, m (ft ). E = emission rate, kg/m2-hr (lb/ft2-hr). K = 100,000 cm . g/m . kg for metric units. ()LLALLA− ρρ+−() BBBIIfi fi I = 12 in./ft for English units. E = LBF = final boiling sump inclined liquid level KA θ indicators reading, cm (in.). V

LBi = initial boiling sump inclined liquid level indicators reading, cm (in.). Eq. 307- 4

LIf = final immersion sump inclined liquid level indicators reading, cm (in.). METHOD 308—PROCEDURE FOR DETERMINATION OF METHANOL EMISSION FROM STATIONARY L = initial immersion sump inclined liquid Ii SOURCES level indicators reading, cm (in.). SB = length of the boiling sump, m (ft). 1.0 Scope and Application S = length of the immersion sump, m (ft). I 1.1 Analyte. Methanol. Chemical Abstract SV = length of the solvent vapor/air interface, m (ft). Service (CAS) No. 67–56–1. 1.2 Applicability. This method applies to W = width of the boiling sump, m (ft). B the measurement of methanol emissions W = width of the immersion sump, m (ft). I from specified stationary sources. WV = width of the solvent vapor/air interface, m (ft). 2.0 Summary of Method r = density of solvent, g/m3 (lb/ft3). A gas sample is extracted from the sam- q = test time, hr. pling point in the stack. The methanol is 4.2 Area of Sump Interfaces. Calculate the collected in deionized distilled water and ad- areas of the boiling and immersion sump sorbed on silica gel. The sample is returned interfaces as follows: to the laboratory where the methanol in the AB = SB WB Eq. 307–1 water fraction is separated from other or- AI = SI WI Eq. 307–2 ganic compounds with a gas chromatograph 729

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(GC) and is then measured by a flame ioniza- mospheric pressure to within 2.5 mm (0.1 tion detector (FID). The fraction adsorbed on inch) Hg. See the NOTE in Method 5 (40 CFR silica gel is extracted with deionized dis- part 60, appendix A), section 6.1.2. tilled water and is then separated and meas- 6.1.1.9 Vacuum Gauge and Rotameter. At ured by GC/FID. least 760-mm (30-inch) Hg gauge and 0- to 40- ml/min rotameter, to be used for leak-check 3.0 Definitions [Reserved] of the sampling train. 4.0 Interferences [Reserved] 6.2 Sample Recovery. The following items are required for sample recovery: 5.0 Safety 6.2.1 Wash Bottles. Polyethylene or glass, 5.1 Disclaimer. This method may involve 500-ml, two. hazardous materials, operations, and equip- 6.2.2 Sample Vials. Glass, 40-ml, with Tef- ment. This test method does not purport to lon ®-lined septa, to store impinger samples address all of the safety problems associated (one per sample). with its use. It is the responsibility of the 6.2.3 Graduated Cylinder. 100-ml size. user of this test method to establish appro- 6.3 Analysis. The following are required priate safety and health practices and to de- for analysis: termine the applicability of regulatory limi- 6.3.1 Gas Chromatograph. GC with an FID, tations before performing this test method. programmable temperature control, and 5.2 Methanol Characteristics. Methanol is heated liquid injection port. flammable and a dangerous fire and explo- 6.3.2 Pump. Capable of pumping 100 ml/ sion risk. It is moderately toxic by ingestion min. For flushing sample loop. and inhalation. 6.3.3 Flow Meter. To monitor accurately 6.0 Equipment and Supplies sample loop flow rate of 100 ml/min. 6.3.4 Regulators. Two-stage regulators 6.1 Sample Collection. The following used on gas cylinders for GC and for cylinder items are required for sample collection: standards. 6.1.1 Sampling Train. The sampling train 6.3.5 Recorder. To record, integrate, and is shown in Figure 308–1 and component parts store chromatograms. are discussed below. 6.3.6 Syringes. 1.0- and 10-microliter (l) 6.1.1.1 Probe. Teflon ®, approximately 6- size, calibrated, for injecting samples. millimeter (mm) (0.24 inch) outside diameter. 6.3.7 Tubing Fittings. Stainless steel, to 6.1.1.2 Impinger. A 30-milliliter (ml) midg- plumb GC and gas cylinders. et impinger. The impinger must be con- 6.3.8 Vials. Two 5.0-ml glass vials with ® nected with leak-free glass connectors. Sili- screw caps fitted with Teflon -lined septa cone grease may not be used to lubricate the for each sample. connectors. 6.3.9 Pipettes. Volumetric type, assorted 6.1.1.3 Adsorbent Tube. Glass tubes sizes for preparing calibration standards. packed with the required amount of the spec- 6.3.10 Volumetric Flasks. Assorted sizes ified adsorbent. for preparing calibration standards. 6.1.1.4 Valve. Needle valve, to regulate 6.3.11 Vials. Glass 40-ml with Teflon ®- sample gas flow rate. lined septa, to store calibration standards 6.1.1.5 Pump. Leak-free diaphragm pump, (one per standard). or equivalent, to pull gas through the sampling train. Install a small surge tank be- 7.0 Reagents and Standards tween the pump and rate meter to eliminate NOTE: Unless otherwise indicated, all re- the pulsation effect of the diaphragm pump agents must conform to the specifications on the rotameter. established by the Committee on Analytical 6.1.1.6 Rate Meter. Rotameter, or equiva- Reagents of the American Chemical Society. lent, capable of measuring flow rate to with- Where such specifications are not available, in 2 percent of the selected flow rate of up to use the best available grade. 1000 milliliter per minute (ml/min). Alter- natively, the tester may use a critical orifice 7.1 Sampling. The following are required to set the flow rate. for sampling: 6.1.1.7 Volume Meter. Dry gas meter 7.1.1 Water. Deionized distilled to conform (DGM), sufficiently accurate to measure the to the American Society for Testing and Ma- sample volume to within 2 percent, cali- terials (ASTM) Specification D 1193–77, Type brated at the selected flow rate and condi- 3. At the option of the analyst, the potas- tions actually encountered during sampling, sium permanganate (KMnO4) test for oxidiz- and equipped with a temperature sensor (dial able organic matter may be omitted when thermometer, or equivalent) capable of high concentrations of organic matter are measuring temperature accurately to within not expected to be present. 3 °C (5.4 °F). 7.1.2 Silica Gel. Deactivated 6.1.1.8 Barometer. Mercury (Hg), aneroid, chromatographic grade 20/40 mesh silica gel or other barometer capable of measuring at- packed in glass adsorbent tubes. The silica

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gel is packed in two sections. The front sec- anol. Pipette 5, 15, and 25 ml of this standard, tion contains 520 milligrams (mg) of silica respectively, into three 50-ml volumetric gel, and the back section contains 260 mg. flasks. Dilute each solution to 50 ml with de- 7.2 Analysis. The following are required ionized distilled water. These standards will for analysis: have 1, 3, and 5 μg/ml of methanol, respec- 7.2.1 Water. Same as specified in section tively. Transfer all four standards into 40-ml 7.1.1. glass vials capped with Teflon®-lined septa 7.2.2 [Reserved] and store under refrigeration. Discard any 7.2.3 Methanol Stock Standard. Prepare a excess solution. methanol stock standard by weighing 1 gram 7.2.4 GC Column. Capillary column, 30 me- of methanol into a 100-ml volumetric flask. ters (100 feet) long with an inside diameter Dilute to 100 ml with water. (ID) of 0.53 mm (0.02 inch), coated with DB 7.2.3.1 Methanol Working Standard. Pre- 624 to a film thickness of 3.0 micrometers, pare a methanol working standard by (μm) or an equivalent column. Alternatively, pipetting 1 ml of the methanol stock stand- a 30-meter capillary column coated with pol- ard into a 100-ml volumetric flask. Dilute the yethylene glycol to a film thickness of 1 μm solution to 100 ml with water. such as AT-WAX or its equivalent. 7.2.3.2 Methanol Standards For Impinger 7.2.5 Helium. Ultra high purity. Samples. Prepare a series of methanol stand- 7.2.6 Hydrogen. Zero grade. ards by pipetting 1, 2, 5, 10, and 25 ml of 7.2.7 Oxygen. Zero grade. methanol working standard solution respectively into five 50-ml volumetric flasks. Di- 8.0 Procedure lute the solutions to 50 ml with water. These standards will have 2, 4, 10, 20, and 50 μg/ml 8.1 Sampling. The following items are re- of methanol, respectively. After preparation, quired for sampling: transfer the solutions to 40-ml glass vials 8.1.1 Preparation of Collection Train. capped with Teflon ® septa and store the Measure 20 ml of water into the midget im- vials under refrigeration. Discard any excess pinger. The adsorbent tube must contain 520 solution. mg of silica gel in the front section and 260 7.2.3.3 Methanol Standards for Adsorbent mg of silica gel in the backup section. As- Tube Samples. Prepare a series of methanol semble the train as shown in Figure 308–1. An standards by first pipetting 10 ml of the optional, second impinger that is left empty methanol working standard into a 100-ml may be placed in front of the water-con- volumetric flask and diluting the contents to taining impinger to act as a condensate trap. exactly 100 ml with deionized distilled water. Place crushed ice and water around the im- This standard will contain 10 μg/ml of meth- pinger.

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8.1.2 Leak Check. A leak check before and 8.1.3 Sample Collection. Record the initial after the sampling run is mandatory. The DGM reading and barometric pressure. To leak-check procedure is as follows: begin sampling, position the tip of the Tef- Temporarily attach a suitable (e.g., 0- to lon ® tubing at the sampling point, connect 40-ml/min) rotameter to the outlet of the the tubing to the impinger, and start the DGM, and place a vacuum gauge at or near pump. Adjust the sample flow to a constant the probe inlet. Plug the probe inlet, pull a rate between 200 and 1000 ml/min as indicated vacuum of at least 250 mm (10 inch) Hg or by the rotameter. Maintain this constant the highest vacuum experienced during the rate (±10 percent) during the entire sampling sampling run, and note the flow rate as indi- run. Take readings (DGM, temperatures at cated by the rotameter. A leakage rate in ex- DGM and at impinger outlet, and rate meter) cess of 2 percent of the average sampling at least every 5 minutes. Add more ice dur- rate is acceptable. ing the run to keep the temperature of the NOTE: Carefully release the probe inlet gases leaving the last impinger at 20 °C (68 plug before turning off the pump. °F) or less. At the conclusion of each run,

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turn off the pump, remove the Teflon ® tub- cylinder. Record the sample volume. Trans- ing from the stack, and record the final read- fer the sample to a glass vial and cap with a ings. Conduct a leak check as in section 8.1.2. Teflon ® septum. Discard any excess sample. (This leak check is mandatory.) If a leak is Place the samples in an ice chest for ship- found, void the test run or use procedures ac- ment to the laboratory. ceptable to the Administrator to adjust the 8.2.2. Adsorbent Tubes. Seal the silica gel sample volume for the leakage. adsorbent tubes and place them in an ice 8.2 Sample Recovery. The following items chest for shipment to the laboratory. are required for sample recovery: 8.2.1 Impinger. Disconnect the impinger. 9.0 Quality Control Pour the contents of the midget impinger into a graduated cylinder. Rinse the midget 9.1 Miscellaneous Quality Control Meas- impinger and the connecting tubes with ures. The following quality control measures water, and add the rinses to the graduated are required:

Section Quality control measure Effect

8.1.2, 8.1.3, 10.1 ...... Sampling equipment leak check and calibration .. Ensures accurate measurement of sample volume. 10.2 ...... GC calibration ...... Ensures precision of GC analysis. 13.0 ...... Methanol spike recovery check ...... Verifies all methanol in stack gas is being captured in impinge/adsorbent tube setup.

10.0 Calibration and Standardization then the DGM volumes obtained during the test series are acceptable. If the calibration 10.1 Metering System. The following items are required for the metering system: factor deviates by more than 5 percent, re- 10.1.1 Initial Calibration. calibrate the metering system as in section 10.1.1.1 Before its initial use in the field, 10.1.1, and for the calculations, use the cali- first leak-check the metering system (drying bration factor (initial or recalibration) that tube, needle valve, pump, rotameter, and yields the lower gas volume for each test DGM) as follows: Place a vacuum gauge at run. the inlet to the drying tube, and pull a vacu- 10.1.3 Temperature Sensors. Calibrate um of 250 mm (10 inch) Hg; plug or pinch off against mercury-in-glass thermometers. An the outlet of the flow meter, and then turn alternative mercury-free thermometer may off the pump. The vacuum shall remain sta- be used if the thermometer is, at a min- ble for at least 30 seconds. Carefully release imum, equivalent in terms of performance or the vacuum gauge before releasing the flow suitably effective for the specific tempera- meter end. ture measurement application. 10.1.1.2 Next, remove the drying tube, and 10.1.4 Rotameter. The rotameter need not calibrate the metering system (at the sam- be calibrated, but should be cleaned and pling flow rate specified by the method) as maintained according to the manufacturer’s follows: Connect an appropriately sized wet instruction. test meter (e.g., 1 liter per revolution (0.035 10.1.5 Barometer. Calibrate against a mer- cubic feet per revolution)) to the inlet of the cury barometer. drying tube. Make three independent cali- 10.2 Gas Chromatograph. The following brations runs, using at least five revolutions procedures are required for the gas chro- of the DGM per run. Calculate the calibra- matograph: tion factor, Y (wet test meter calibration μ volume divided by the DGM volume, both 10.2.1 Initial Calibration. Inject 1 l of volumes adjusted to the same reference tem- each of the standards prepared in sections perature and pressure), for each run, and av- 7.2.3.3 and 7.2.3.4 into the GC and record the erage the results. If any Y-value deviates by response. Repeat the injections for each more than 2 percent from the average, the standard until two successive injections metering system is unacceptable for use. agree within 5 percent. Using the mean re- Otherwise, use the average as the calibration sponse for each calibration standard, prepare factor for subsequent test runs. a linear least squares equation relating the 10.1.2 Posttest Calibration Check. After response to the mass of methanol in the sam- each field test series, conduct a calibration ple. Perform the calibration before analyzing check as in section 10.1.1 above, except for each set of samples. the following variations: (a) The leak check 10.2.2 Continuing Calibration. At the be- is not to be conducted, (b) three, or more ginning of each day, analyze the mid level revolutions of the DGM may be used, and (c) calibration standard as described in section only two independent runs need be made. If 10.5.1. The response from the daily analysis the calibration factor does not deviate by must agree with the response from the ini- more than 5 percent from the initial calibra- tial calibration within 10 percent. If it does tion factor (determined in section 10.1.1), not, the initial calibration must be repeated.

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11.0 Analytical Procedure bracket the response of the sample. These standards should produce approximately 50 11.1 Gas Chromatograph Operating Condi- percent and 150 percent of the response of the tions. The following operating conditions are sample. required for the GC: 11.1.1 Injector. Configured for capillary 12.0 Data Analysis and Calculations column, splitless, 200 °C (392 °F). 11.1.2 Carrier. Helium at 10 ml/min. 12.1 Nomenclature. 11.1.3 Oven. Initially at 45 °C for 3 min- Caf = Concentration of methanol in the front utes; then raise by 10 °C to 70 °C; then raise of the adsorbent tube, μg/ml. ° ° by 70 C/min to 200 C. C = Concentration of methanol in the back μ ab 11.2 Impinger Sample. Inject 1 l of the of the adsorbent tube, μg/ml. stored sample into the GC. Repeat the injec- C = Concentration of methanol in the im- tion and average the results. If the sample i pinger portion of the sample train,μg/ml. response is above that of the highest calibra- E = Mass emission rate of methanol, μg/hr tion standard, either dilute the sample until (lb/hr). it is in the measurement range of the calibration line or prepare additional calibration ms = Total mass of compound measured in standards. If the sample response is below impinger and on adsorbent with spiked that of the lowest calibration standard, pre- train (mg). pare additional calibration standards. If ad- mu = Total mass of compound measured in ditional calibration standards are prepared, impinger and on adsorbent with unspiked there shall be at least two that bracket the train (mg). response of the sample. These standards mv = Mass per volume of spiked compound should produce approximately 50 percent and measured (mg/L). 150 percent of the response of the sample. Mtot = Total mass of methanol collected in 11.3 Silica Gel Adsorbent Sample. The fol- the sample train, μg. lowing items are required for the silica gel Pbar = Barometric pressure at the exit orifice adsorbent samples: of the DGM, mm Hg (in. Hg). 11.3.1 Preparation of Samples. Extract the Pstd = Standard absolute pressure, 760 mm Hg front and backup sections of the adsorbent (29.92 in. Hg).

tube separately. With a file, score the glass Qstd = Dry volumetric stack gas flow rate cor- adsorbent tube in front of the first section of rected to standard conditions, dscm/hr silica gel. Break the tube open. Remove and (dscf/hr). discard the glass wool. Transfer the first sec- R = fraction of spiked compound recovered tion of the silica gel to a 5-ml glass vial and s = theoretical concentration (ppm) of spiked stopper the vial. Remove the spacer between target compound the first and second section of the adsorbent Tm = Average DGM absolute temperature, de- tube and discard it. Transfer the second sec- grees K (°R). tion of silica gel to a separate 5-ml glass vial Tstd = Standard absolute temperature, 293 de- and stopper the vial. grees K (528 °R). 11.3.2 Desorption of Samples. Add 3 ml of V = Volume of front half adsorbent sample, deionized distilled water to each of the af ml. stoppered vials and shake or vibrate the V = Volume of back half adsorbent sample, vials for 30 minutes. ab ml. 11.3.3 Inject a 1-μl aliquot of the diluted sample from each vial into the GC. Repeat Vi = Volume of impinger sample, ml. the injection and average the results. If the Vm = Dry gas volume as measured by the sample response is above that of the highest DGM, dry cubic meters (dcm), dry cubic calibration standard, either dilute the sam- feet (dcf). ple until it is in the measurement range of Vm(std) = Dry gas volume measured by the the calibration line or prepare additional DGM, corrected to standard conditions, calibration standards. If the sample response dry standard cubic meters (dscm), dry is below that of the lowest calibration stand- standard cubic feet (dscf). ard, prepare additional calibration stand- 12.2 Mass of Methanol. Calculate the total ards. If additional calibration standards are mass of methanol collected in the sampling prepared, there shall be at least two that train using Equation 308–1.

=+ + MVCVCVCtot i i af af ab ab Equation 308-1

12.3 Dry Sample Gas Volume, Corrected ume of gas sampled at standard conditions to Standard Conditions. Calculate the vol- using Equation 308–2.

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= VYTPm std bar Vm () std Equation 308- 2 TPm std

12.4 Mass Emission Rate of Methanol. Cal- culate the mass emission rate of methanol using Equation 308–3.

MQ E = tot sd Equation 308- 3 Vm() std

12.5 Recovery Fraction (R)

13.0 Method Performance cedures and instrumentation. Determine the Since a potential sample may contain a va- fraction of spiked methanol recovered (R) by riety of compounds from various sources, a combining the amount recovered in the im- specific precision limit for the analysis of pinger and in the adsorbent tube, using the field samples is impractical. Precision in the equations in section 12.5. Recovery values range of 5 to 10 percent relative standard de- must fall in the range: 0.70 ≤ R ≤ 1.30. Report viation (RSD) is typical for gas the R value in the test report. chromatographic techniques, but an experi- ii. [Reserved] enced GC operator with a reliable instrument can readily achieve 5 percent RSD. For 14.0 Pollution Prevention [Reserved] this method, the following combined GC/operator values are required. 15.0 Waste Management [Reserved] (a) Precision. Calibration standards must meet the requirements in section 10.2.1 or 16.0 Bibliography 10.2.2 as applicable. 1. Rom, J.J. ‘‘Maintenance, Calibration, (b) Recovery. After developing an appro- and Operation of Isokinetic Source Sampling priate sampling and analytical system for Equipment.’’ Office of Air Programs, Envi- the pollutants of interest, conduct the fol- ronmental Protection Agency. Research Tri- lowing spike recovery procedure at each angle Park, NC. APTD–0576 March 1972. sampling point where the method is being applied. 2. Annual Book of ASTM Standards. Part i. Methanol Spike. Set up two identical 31; Water, Atmospheric Analysis. American sampling trains. Collocate the two sampling Society for Testing and Materials. Philadel- probes in the stack. The probes shall be phia, PA. 1974. pp. 40–42. placed in the same horizontal plane, where 3. Westlin, P.R. and R.T. Shigehara. ‘‘Pro- the first probe tip is 2.5 cm from the outside cedure for Calibrating and Using Dry Gas edge of the other. One of the sampling trains Volume Meters as Calibration Standards.’’ shall be designated the spiked train and the Source Evaluation Society Newsletter. 3 (1) other the unspiked train. Spike methanol :17–30. February 1978. into the impinger, and onto the adsorbent 4. Yu, K.K. ‘‘Evaluation of Moisture Effect tube in the spiked train prior to sampling. on Dry Gas Meter Calibration.’’ Source Eval- The total mass of methanol shall be 40 to 60 uation Society Newsletter. 5 (1) :24–28. Feb- percent of the mass expected to be collected ruary 1980. with the unspiked train. Sample the stack gas into the two trains simultaneously. Ana- 5. NIOSH Manual of Analytical Methods, lyze the impingers and adsorbents from the Volume 2. U.S. Department of Health and two trains utilizing identical analytical pro-

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Human Services National Institute for Occu- 7.0 Reagents and Standards pational Safety and Health. Center for Dis- 7.1 Chloroform, 99.9 + %, A.S.C. HPLC ease Control. 4676 Columbia Parkway, Cin- grade cinnati, OH 45226. (available from the Super- intendent of Documents, Government Print- 8.0 Sample Collection, Preservation, and ing Office, Washington, DC 20402.) Storage 6. Pinkerton, J.E. ‘‘Method for Measuring Methanol in Pulp Mill Vent Gases.’’ National 8.1 A representative sample should be Council of the Pulp and Paper Industry for caught in a clean 8 oz. container with a se- Air and Stream Improvement, Inc., New cure lid. York, NY. 8.2 The container should be labeled with sample identification, date and time. 17.0 Tables, Diagrams, Flowcharts, and Validation Data [Reserved] 9.0 Quality Control 9.1 The instrument is calibrated by inject- METHOD 310A—DETERMINATION OF RESIDUAL ing calibration solution (Section 10.2 of this HEXANE THROUGH GAS CHROMATOGRAPHY method) five times. 1.0 Scope and Application 9.2 The retention time for components of interest and relative response of monomer to 1.1 This method is used to analyze any the internal standard is determined. crumb rubber or water samples for residual 9.3 Recovery efficiency must be deter- hexane content. mined once for each sample type and when- 1.2 The sample is heated in a sealed bottle ever modifications are made to the method. with an internal standard and the vapor is 9.3.1 Determine the percent hexane in analyzed by gas chromatography. three separate dried rubber crumb samples. 9.3.2 Weigh a portion of each crumb sam- 2.0 Summary of Method ple into separate sample bottles and add a 2.1 This method, utilizing a capillary col- known amount of hexane (10 microliters) by umn gas chromatograph with a flame ioniza- microliter syringe and 20 microliters of in- tion detector, determines the concentration ternal standard. Analyze each by the de- of residual hexane in rubber crumb samples. scribed procedure and calculate the percent recovery of the known added hexane. 3.0 Definitions 9.3.3 Repeat the previous step using twice 3.1 The definitions are included in the the hexane level (20 microliters), analyze and text as needed. calculate the percent recovery of the known added hexane. 4.0 Interferences 9.3.4 Set up two additional sets of samples using 10 microliters and 20 microliters of 4.1 There are no known interferences. hexane as before, but add an amount of 5.0 Safety water equal to the dry crumb used. Analyze and calculate percent recovery to show the 5.1 It is the responsibility of the user of effect of free water on the results obtained. this procedure to establish safety and health 9.3.5 A value of R between 0.70 and 1.30 is practices applicable to their specific oper- acceptable. ation. 9.3.6 R shall be used to correct all reported results for each compound by dividing 6.0 Equipment and Supplies the measured results of each compound by 6.1 Gas Chromatograph with a flame ion- the R for that compound for the same sample ization detector and data handling station type. equipped with a capillary column 30 meters long. 10.0 Calibration and Instrument Settings 6.2 Chromatograph conditions for Sigma 10.1 Calibrate the chromatograph using a 1: standard made by injecting 10 μl of fresh 6.2.1 Helium pressure: 50# inlet A, 14# aux hexane and 20 μl of chloroform into a sealed 6.2.2 Carrier flow: 25 cc/min septum bottle. This standard will be 0.6 wt.% 6.2.3 Range switch: 100x total hexane based on 1 gram of dry rubber. 6.2.4 DB: 1 capillary column 10.2 Analyze the hexane used and cal- 6.3 Chromatograph conditions for Hew- culate the percentage of each hexane isomer lett-Packard GC: (2-methylpentane, 3-methylpentane, n- 6.3.1 Initial temperature: 40 °C hexane, and methylcyclo-pentane). Enter 6.3.2 Initial time: 8 min these percentages into the method calibra- 6.3.3 Rate: 0 tion table. 6.3.4 Range: 2 10.3 Heat the standard bottle for 30 min- 6.3.5 DB: 1705 capillary column utes in a 105 °C oven. 6.4 Septum bottles and stoppers 10.4 Inject about 0.25 cc of vapor into the 6.5 Gas Syringe—0.5 cc gas chromatograph and after the analysis is

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finished, calibrate according to the proce- ppmhexane = (Ahexane × Rhexane)/(Ais × Ris) dures described by the instrument manufac- Where: turer. Ahexane = area of hexane 11.0 Procedure Rhexane = response of hexane A = area of the internal standard 11.1 Using a cold mill set at a wide roller is gap (125–150 mm), mill about 250 grams of Ris = response of the internal standard crumb two times to homogenize the sample. % hexane in crumb = (ppmhexane/sample 11.2 Weigh about 2 grams of wet crumb amount)100 into a septum bottle and cap with a septum 12.3 Correct the results by the value of R ring. Add 20 μl of chloroform with a syringe (as determined in sections 9.3.4, 9.3.5, and and place in a 105 °C oven for 45 minutes. 9.3.6 of this method). 11.3 Run the moisture content on a separate portion of the sample and calculate the 13.0 Method Performance grams of dry rubber put into the septum bot- 13.1 The test has a standard deviation of tle. 0.14 wt% at 0.66 wt% hexane. Spike recovery 11.4 Set up the data station on the required method and enter the dry rubber of 12 samples at two levels of hexane aver- weight in the sample weight field. aged 102.3%. Note: Recovery must be deter- 11.5 Inject a 0.25 cc vapor sample into the mined for each type of sample. The values chromatograph and push the start button. given here are meant to be examples of 11.6 At the end of the analysis, the data method performance. station will print a report listing the concentration of each identified component. 14.0 Pollution Prevention 11.7 To analyze water samples, pipet 5 ml 14.1 Waste generation should be mini- of sample into the septum bottle, cap and mized where possible. Sample size should be μ ° add 20 l of chloroform. Place in a 105 C oven an amount necessary to adequately run the for 30 minutes. analysis. 11.8 Enter 5 grams into the sample weight field. 15.0 Waste Management 11.9 Inject a 0.25 cc vapor sample into the chromatograph and push the start button. 15.1 All waste shall be handled in accord- 11.10 At the end of the analysis, the data ance with federal and state environmental station will print a report listing the con- regulations. centration of each identified component. 16.0 References and Publications 12.0 Data Analysis and Calculation 16.1 DSM Copolymer Test Method T–3380. 12.1 For samples that are prepared as in section 11 of this method, ppm n-hexane is METHOD 310B—DETERMINATION OF RESIDUAL read directly from the computer. HEXANE THROUGH GAS CHROMATOGRAPHY 12.2 The formulas for calculation of the results are as follows: 1.0 Scope and Application

Method sensitivity Analyte CAS No. Matrix (5.5g sample size)

Hexane ...... 110–54–3 Rubber crumb...... 01 wt%. Applicable Termonomer ...... Rubber crumb ...... 001 wt%.

1.1 Data Quality Objectives: added to this solution to precipitate the In the production of ethylene-propylene crumb, and the supernatant is analyzed for terpolymer crumb rubber, the polymer is re- hexane and diene by a gas chromatograph covered from solution by flashing off the sol- equipped with a flame ionization detector vent with steam and hot water. The result- (FID). ing water-crumb slurry is then pumped to the finishing units. Certain amounts of sol- 3.0 Definitions vent (hexane being the most commonly used 3.1 Included in text as needed. solvent) and diene monomer remain in the crumb. The analyst uses the following proce- 4.0 Interferences dure to determine those amounts. 4.1 None known. 2.0 Summary of Method 4.2 Benzene, introduced as a contaminant in the toluene solvent, elutes between meth- 2.1 The crumb rubber sample is dissolved in toluene to which heptane has been added yl cyclopentane and cyclohexane. However, as an internal standard. Acetone is then the benzene peak is completely resolved.

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4.3 2,2-dimethyl pentane, a minor compo- 6.2 100-ml volumetric pipette nent of the hexane used in our process, 6.3 1000-ml volumetric flask elutes just prior to methyl cyclopentane. It 6.4 8-oz. French Square sample bottles is included as ‘‘hexane’’ in the analysis with plastic-lined caps whether it is integrated separately or in- 6.5 Top-loading balance cluded in the methyl cyclopentane peak. 6.6 Laboratory shaker 5.0 Safety 6.7 Laboratory oven set at 110 °C (steam oven) 5.1 This procedure does not purport to ad- 6.8 Gas chromatograph, Hewlett-Packard dress all of the safety concerns associated with its use. It is the responsibility of the 5890A, or equivalent, interfaced with HP user of this procedure to establish appro- 7673A (or equivalent) autosampler (equipped priate safety and health practices and deter- with nanoliter adapter and robotic arm), and mine the applicability of regulatory limita- HP 3396 series II or 3392A (or equivalent) in- tions prior to use. tegrator/controller. 5.2 Chemicals used in this analysis are 6.9 GC column, capillary type, 50m × flammable and hazardous (see specific tox- 0.53mm, methyl silicone, 5 micron film icity information below). Avoid contact with thickness, Quadrex, or equivalent. sources of ignition during sample prep. All 6.10 Computerized data acquisition sys- handling should be done beneath a hood. tem, such as CIS/CALS Playtex or nitrile gloves recommended. 6.11 Crimp-top sample vials and HP p/n 5.3 Hexane is toxic by ingestion and inha- 5181–1211 crimp caps, or screw-top lation. Vapor inhalation causes irritation of autosampler vials and screw tops. nasal and respiratory passages, headache, 6.12 Glass syringes, 5-ml, with ‘‘Luer- dizziness, nausea, central nervous system de- lock’’ fitting pression. Chronic overexposure can cause se- μ vere nerve damage. May cause irritation on 6.13 Filters, PTFE, .45 m pore size, contact with skin or eyes. May cause damage Gelman Acrodisc or equivalent, to fit on to kidneys. Luer-lock syringes (in 6.12, above). 5.4 Termonomer may be harmful by inha- 7.0 Reagents and Standards lation, ingestion, or skin absorption. Vapor or mist is irritating to the eyes, mucous 7.1 Reagent toluene, EM Science membranes, and upper respiratory tract. Omnisolv (or equivalent) Causes skin irritation. Purity Check: Prior to using any bottle of 5.5 Toluene is harmful or fatal if swal- reagent toluene, analyze it according to sec- lowed. Vapor harmful if inhaled. Symptoms: tion 11.2 of this method. Use the bottle only headache, dizziness, hallucinations, distorted if hexane, heptane, and termonomer peak perceptions, changes in motor activity, nau- areas are less than 15 each (note that an area sea, diarrhea, respiratory irritation, central of 15 is equivalent to less than 0.01 wt% in a nervous system depression, unconsciousness, liver, kidney and lung damage. Contact can 10g sample). cause severe eye irritation. May cause skin 7.2 Reagent acetone, EM Science irritation. Causes irritation of eyes, nose, Omnisolv HR-GC (or equivalent) and throat. Purity Check: Prior to using any bottle of 5.6 Acetone, at high concentrations or reagent acetone, analyze it according to sec- prolonged overexposure, may cause head- tion 11.2 of this method. Use the bottle only ache, dizziness, irritation of eyes and res- if hexane, heptane, and termonomer peak piratory tract, loss of strength, and narcosis. areas are less than 15 each. Eye contact causes severe irritation; skin 7.3 Reagent heptane, Aldrich Chemical contact may cause mild irritation. Con- Gold Label, Cat #15,487–3 (or equivalent) centrations of 20,000 ppm are immediately Purity Check: Prior to using any bottle of dangerous to life and health. reagent heptane, analyze it according to sec- 5.7 Heptane is harmful if inhaled or swal- tion 11.2 of this method. Use the bottle only lowed. May be harmful if absorbed through if hexane and termonomer peak areas are the skin. Vapor or mist is irritating to the less than 5 each. eyes, mucous membranes, and upper respiratory tract. Prolonged or repeated expo- 7.4 Internal standard solution—used as a sure to skin causes defatting and dermatitis. concentrate for preparation of the more di- 5.8 The steam oven used to dry the poly- lute Polymer Dissolving Solution. It con- mer in this procedure is set at 110 °C. Wear tains 12.00g heptane/100ml of solution which leather gloves when removing bottles from is 120.0g per liter. the oven. Preparation of internal standard solution (polymer dissolving stock solution): 6.0 Equipment and Supplies 6.1 4000-ml volumetric flask

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Action Notes

7.4.1 Tare a clean, dry 1-liter volumetric flask on the balance. If the 1-liter volumetric flask is too tall to fit in the balance Record the weight to three places. case, you can shield the flask from drafts by inverting a paint bucket with a hole cut in the bottom over the balance cover. Allow the neck of the flask to project through the hole in the bucket. 7.4.2 Weigh 120.00 g of n-heptane into the flask. Record the Use 99 + % n-heptane from Aldrich or Janssen Chimica. total weight of the flask and heptane as well as the weight of heptane added. 7.4.3 Fill the flask close to the mark with toluene, about 1 to Use EM Science Omnisolve toluene, Grade TX0737–1, or 2″ below the mark. equivalent. 7.4.4 Shake the flask vigorously to mix the contents ...... Allow any bubbles to clear before proceeding to the next step. 7.4.5 Top off the flask to the mark with toluene. Shake vigorously, as in section 7.4.4 of this method, to mix well. 7.4.6 Weigh the flask containing the solution on the three place balance record the weight 7.4.7 Transfer the contents of the flask to a 1 qt Boston round Discard any excess solution bottle. 7.4.8 Label the bottle with the identity of the contents, the Be sure to include the words ‘‘Hexane in Crumb Polymer Dis- weights of heptane and toluene used, the date of preparation solving Stock Solution’’ on the label. and the preparer’s name. 7.4.9 Refrigerate the completed blend for the use of the routine Technicians.

7.5 Polymer Dissolving Solution in the same approximate time region as (‘‘PDS’’)—Heptane (as internal standard) in termonomer and is used to quantify in that toluene. This solution contains 0.3g of region because it has a longer shelf life. heptane internal standard per 100 ml of solu- Termonomer, having a high tendency to po- tion. lymerize, is used in the QC solution only to 7.5.1 Preparation of Polymer Dissolving ensure that both termonomer isomers elute Solution. Fill a 4,000-ml volumetric flask at the proper time. about 3⁄4 full with toluene. First, a concentrated stock solution is pre- 7.5.2 Add 100 ml of the internal standard pared; the final QC solution can then be pre- solution (section 7.4 of this method) to the pared by diluting the stock solution. flask using the 100ml pipette. 7.6.1 In preparation of stock solution, fill 7.5.3 Fill the flask to the mark with tol- a 1-liter volumetric flask partially with uene. Discard any excess. polymer dissolving solution (PDS)—see sec- 7.5.4 Add a large magnetic stirring bar to tion 7.5 of this method. Add 20.0 ml barge the flask and mix by stirring. hexane, 5.0 ml n-nonane, and 3 ml 7.5.5 Transfer the polymer solvent solu- termonomer. Finish filling the volumetric to tion to the one-gallon labeled container with the mark with PDS. 50ml volumetric dispenser attached. 7.6.2 In preparation of quality control so- 7.5.6 Purity Check: Analyze according to lution, dilute the quality control stock solu- section 11.2. NOTE: You must ‘‘precipitate’’ tion (above) precisely 1:10 with PDS, i.e. 10 the sample with an equal part of acetone ml of stock solution made up to 100 ml (volu- (thus duplicating actual test conditions—see metric flask) with PDS. Pour the solution section 11.1 of this method, sample prep) be- into a 4 oz. Boston round bottle and store in fore analyzing. Analyze the reagent 3 times the refrigerator. to quantify the C6 and termonomer interferences. Inspect the results to ensure good 8.0 Sample Collection, Preservation and agreement among the three runs (within Storage 10%). 8.1 Line up facility to catch crumb sam- 7.5.7 Tag the bottle with the following in- ples. The facility is a special facility where formation: the sample is drawn. POLYMER DISSOLVING SOLUTION 8.1.1 Ensure that the cock valve beneath FOR C6 IN CRUMB ANALYSIS facility is closed. PREPARER’S NAME 8.1.2 Line up the system from the slurry DATE line cock valve to the cock valve at the noz- CALS FILE ID’S OF THE THREE zle on the stripper. ANALYSES FOR PURITY (from section 8.1.3 Allow the system to flush through 7.5.6 of this method) facility for a period of 30 seconds. 7.6 Quality Control Solution: the quality 8.2 Catch a slurry crumb sample. control solution is prepared by adding spe- 8.2.1 Simultaneously close the cock valves cific amounts of mixed hexanes (barge upstream and downstream of facility. hexane), n-nonane and termonomer to some 8.2.2 Close the cock valve beneath the polymer dissolving solution. Nonane elutes slurry line in service.

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8.2.3 Line up the cooling tower water oil extended samples and whenever modifica- through the sample bomb water jacket to tions are made to the method. Recovery the sewer for a minimum of 30 minutes. shall be between 70 and 130 percent. All test 8.2.4 Place the sample catching basket be- results must be corrected by the recovery ef- neath facility and open the cock valve under- ficiency value (R). neath the bomb to retrieve the rubber 9.3.1 Approximately 10 grams of wet crumb. EPDM crumb (equivalent to about 5 grams of 8.2.5 If no rubber falls by gravity into the dry rubber) shall be added to six sample bot- basket, line up nitrogen to the bleeder up- tles containing 100 ml of hexane in crumb stream of the sample bomb and force the polymer dissolving solution (toluene con- rubber into the basket. taining 0.3 gram n-heptane/100 ml solution). 8.2.6 Close the cock valve underneath the The polymer shall be dissolved by agitating sample bomb. the bottles on a shaker for 4 hours. The poly- 8.3 Fill a plastic ‘‘Whirl-pak’’ sample bag mer shall be precipitated using 100 ml ace- with slurry crumb and send it to the lab im- tone. mediately. 9.3.2 The supernatant liquid shall be de- 8.4 Once the sample reaches the lab, it canted from the polymer. Care shall be taken should be prepped as soon as possible to to remove as much of the liquid phase from avoid hexane loss through evaporation. Sam- the sample as possible to minimize the effect ples which have lain untouched for more of retained liquid phase upon the next cycle than 30 minutes should be discarded. of the analysis. The supernatant liquid shall be analyzed by gas chromatography using an 9.0 Quality Control internal standard quantitation method with Quality control is monitored via a com- heptane as the internal standard. puter program that tracks analyses of a pre- 9.3.3 The precipitated polymer from the pared QC sample (from section 7.6.2 of this steps described above shall be redissolved method). The QC sample result is entered using toluene as the solvent. No heptane daily into the program, which plots the re- shall be added to the sample in the second sult as a data point on a statistical chart. If dissolving step. The toluene solvent and ace- the data point does not satisfy the ‘‘in-con- tone precipitant shall be determined to be trol’’ criteria (as defined by the lab quality free of interfering compounds. facilitator), an ‘‘out-of-control’’ flag appears, 9.3.4 The rubber which was dissolved in mandating corrective action. the toluene shall be precipitated with ace- In addition, the area of the n-heptane peak tone as before, and the supernatant liquid is monitored so that any errors in making up decanted from the precipitated polymer. The the polymer dissolving solution will be liquid shall be analyzed by gas chroma- caught and corrected. Refer to section 12.4 of tography and the rubber phase dried in a this method. steam-oven to determine the final polymer weight. 9.1 Fill an autosampler vial with the qual- 9.3.5 The ratios of the areas of the hexane ity control solution (from section 7.6.2 of peaks and of the heptane internal standard this method) and analyze on the GC as nor- peak shall be calculated for each of the six mal (per section 11 of this method). samples in the two analysis cycles outlined 9.2 Add the concentrations of the 5 hexane above. The area ratios of the total hexane to isomers as they appear on the CALS print- heptane (R1) shall be determined for the two out. Also include the 2,2-dimethyl-pentane analysis cycles of the sample set. The ratio peak just ahead of the methyl cyclopentane of the values of R1 from the second analysis (the fourth major isomer) peak in the event cycle to the first cycle shall be determined that the peak integration split this peak out. to give a second ratio (R2). Do not include the benzene peak in the sum. Note the nonane concentration. Record both 10.0 Calibration and Standardization results (total hexane and nonane) in the QC computer program. If out of control, and GC The procedure for preparing a Quality Con- appears to be functioning within normal pa- trol sample with the internal standard in it rameters, reanalyze a fresh control sample. is outlined in section 7.6 of this method. If the fresh QC is not in control, check stock 10.1 The relative FID response factors for solution for contaminants or make up a new n-heptane, the internal standard, versus the QC sample with the toluene currently in use. various hexane isomers and termonomer are If instrument remains out-of-control, more relatively constant and should seldom need thorough GC troubleshooting may be needed. to be altered. However Baseline construction Also, verify that the instrument has de- is a most critical factor in the production of tected both isomers of termonomer (quan- good data. For this reason, close attention tification not necessary—see section 7.0 of should be paid to peak integration. Proce- this method). dures for handling peak integration will de- 9.3 Recovery efficiency must be deter- pend upon the data system used. mined for high ethylene concentration, low 10.2 If recalibration of the analysis is ethylene concentration, E-P terpolymer, or needed, make up a calibration blend of the

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internal standard and the analytes as de- polymer buildup in the GC. Clean the sy- tailed below and analyze it using the analyt- ringes in toluene. ical method used for the samples. 11.1.9 Decant remaining supernatant into 10.2.1 Weigh 5 g heptane into a tared scin- a hydrocarbon waste sink, being careful not tillation vial to five places. to discard any of the polymer. Place bottle 10.2.2 Add 0.2 ml termonomer to the vial of precipitate into the steam oven and dry and reweigh. for six hours—Some grades of Vistalon 10.2.3 Add 0.5 ml hexane to the vial and reproduce very small particles in the precipi- weigh. tate, thus making complete decanting im- 10.2.4 Cap, and shake vigorously to mix. possible without discarding some polymer. In 10.2.5 Calculate the weights of this case, decant as much as possible and put termonomer and of hexane added and divide into the oven as is, allowing the oven to their weights by the weight of the n-heptane drive off remaining supernatant (this prac- added. The result is the known of given value tice is avoided for environmental reasons). for the calibration. WARNING: OVEN IS HOT—110 °C (230 °F). 10.2.6 Add 0.4 ml of this mixture to a mix- 11.1.10 Cool, weigh and record final weight ture of 100 ml toluene and 100 ml of acetone. of bottle. Cap and shake vigorously to mix. 11.2 GC ANALYSIS 10.2.7 Analyze the sample. 11.2.1 Initiate the CALS computer chan- 10.2.8 Divide the termonomer area and the nel. total areas of the hexane peaks by the n- 11.2.2 Enter the correct instrument meth- heptane area. This result is the ‘‘found’’ od into the GC’s integrator. value for the calibration. 11.2.3 Load sample vial(s) into 10.2.9 Divide the appropriate ‘‘known’’ autosampler. value from 10.2.5 by the found value from 11.2.4 Start the integrator. 10.2.8. The result is the response factor for 11.2.5 When analysis is complete, plot the analyte in question. Previous work has CALS run to check baseline skim. shown that the standard deviation of the 12.0 Data Analysis and Calculations calibration method is about 1% relative. 12.1 Add the concentrations of the hexane 11.0 Procedure peaks as they appear on the CALS printout. 11.1 SAMPLE PREPARATION Do not include the benzene peak in the sum. 11.1.1 Tare an 8oz sample bottle—Tag at- 12.2 Subtract any hexane interferences tached, cap off; record weight and sample ID found in the PDS (see section 7.5.6 of this on tag in pencil. method); record the result. 11.1.2 Place crumb sample in bottle: RLA– 12.3 Note the termonomer concentration 3: 10 g (gives a dry wt. of ∼5.5 g). on the CALS printout. Subtract any 11.1.3 Dispense 100ml of PDS into each termonomer interference found in the PDS bottle. SAMPLE SHOULD BE PLACED and record this result in a ‘‘% termonomer INTO SOLUTION ASAP TO AVOID HEXANE by GC’’ column in a logbook. LOSS—Using ‘‘Dispensette’’ pipettor. Before 12.4 Record the area (from CALS print- dispensing, ‘‘purge’’ the dispensette (25% of its out) of the heptane internal standard peak in volume) into a waste bottle to eliminate any a ‘‘C7 area’’ column in the logbook. This voids. helps track instrument performance over the 11.1.4 Tightly cap bottles and load sam- long term. ples into shaker. 12.5 After obtaining the final dry weight 11.1.5 Insure that ‘‘ON-OFF’’ switch on of polymer used (Section 11.1.10 of this meth- the shaker itself is ‘‘ON.’’ od), record that result in a ‘‘dry wt.’’ column 11.1.6 Locate shaker timer. Insure that of the logbook (for oil extended polymer, the toggle switch atop timer control box is in amount of oil extracted is added to the dry the middle (‘‘off’’) position. If display reads rubber weight). ‘‘04:00’’ (4 hours), move toggle switch to the 12.6 Divide the %C6 by the dry weight to left position. Shaker should begin operating. obtain the total PHR hexane in crumb. Simi- 11.1.7 After shaker stops, add 100 ml ace- larly, divide the % termonomer by the dry tone to each sample to precipitate polymer. weight to obtain the total PHR termonomer Shake minimum of 5 minutes on shaker— in crumb. Note that PHR is an abbreviation Vistalon sample may not have fully dis- for ‘‘parts per hundred’’. Record both the solved; nevertheless, for purposes of consist- hexane and termonomer results in the log- ency, 4 hours is the agreed-upon dissolving book. time. 12.7 Correct all results by the recovery ef- 11.1.8 Using a 5-ml glass Luer-lock syringe ficiency value (R). and Acrodisc filter, filter some of the super- 13.0 Method Performance natant liquid into an autosampler vial; crimp the vial and load it into the GC 13.1 The method has been shown to pro- autosampler for analysis (section 11.2 of this vide 100% recovery of the hexane analyte. method)—The samples are filtered to prevent The method was found to give a 6% relative

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standard deviation when the same six por- 3.2 Heptane—refers to n-heptane tions of the same sample were carried 3.3 MIBK—methyl isobutyl ketone (4 through the procedure. Note: These values methyl 2—Pentanone) are examples; each sample type, as specified in Section 9.3, must be tested for sample re- 4.0 Interferences covery. 4.1 Material eluting at or near the hexane and/or the IS will cause erroneous results. 14.0 Pollution Prevention Prior to extraction, solvent blanks must be 14.1 Dispose of all hydrocarbon liquids in analyzed to confirm the absence of inter- the appropriate disposal sink system; never fering peaks. pour hydrocarbons down a water sink. 14.2 As discussed in section 11.1.9 of this 5.0 Safety method, the analyst can minimize venting 5.1 Review Material Safety Data Sheets of hydrocarbon vapor to the atmosphere by de- the chemicals used in this method. canting as much hydrocarbon liquid as possible before oven drying. 6.0 Equipment and Supplies 15.0 Waste Management 6.1 4 oz round glass jar with a wide mouth screw cap lid. 15.1 The Technician conducting the anal- 6.2 Vacuum oven. ysis should follow the proper waste manage- 6.3 50 ml pipettes. ment practices for their laboratory location. 6.4 A gas chromatograph with an auto 16.0 References sampler and a 50 meter, 0.53 ID, methyl silicone column with 5 micron phase thickness. 16.1 Baton Rouge Chemical Plant Analyt- 6.5 Shaker, large enough to hold 10, 4 oz. ical Procedure no. BRCP 1302 jars. 16.2 Material Safety Data Sheets (from 6.6 1000 and 4000 ml volumetric flasks. chemical vendors) for hexane, ENB, toluene, 6.7 Electronic integrator or equivalent acetone, and heptane data system. 6.8 GC autosampler vials. METHOD 310C—DETERMINATION OF RESIDUAL 6.9 50 uL syringe. N-HEXANE IN EPDM RUBBER THROUGH GAS CHROMATOGRAPHY 7.0 Reagents and Standards 1.0 Scope and Application 7.1 Reagent grade Methyl-Iso-Butyl-Ke- 1.1 This method describes a procedure for tone (MIBK) the determination of residual hexane in 7.2 n-heptane, 99% + purity EPDM wet crumb rubber in the 0.01—2% 7.3 n-hexane, 99% + purity range by solvent extraction of the hexane 8.0 Sample Collection followed by gas chromatographic analysis where the hexane is detected by flame ion- 8.1 Trap a sample of the EPDM crumb ization and quantified via an internal stand- slurry in the sampling apparatus. Allow the ard. crumb slurry to circulate through the sam- 1.2 This method may involve hazardous pling apparatus for 5 minutes; then close off materials operations and equipment. This the values at the bottom and top of the sam- method does not purport to address all the pling apparatus, trapping the crumb slurry. safety problems associated with it use, if Run cooling water through the water jacket any. It is the responsibility of the user to for a minimum of 30 minutes. Expel the consult and establish appropriate safety and cooled crumb slurry into a sample catching health practices and determine the applica- basket. If the crumb does not fall by gravity, bility of regulatory limitations prior to use. force it out with demineralized water or nitrogen. Send the crumb slurry to the lab for 2.0 Summary analysis. 2.1 Residual hexane contained in wet pieces of EPDM polymer is extracted with 9.0 Quality Control MIBK. A known amount of an internal stand- 9.1 The Royalene crumb sample is ex- ard (IS) is added to the extract which is subtracted three times with MIBK containing sequently analyzed via gas chromatography an internal standard. The hexane from each where the hexane and IS are separated and extraction is added together to obtain a detected utilizing a megabore column and total hexane content. The percent hexane in flame ionization detection (FID). From the the first extraction is then calculated and response to the hexane and the IS, the used as the recovery factor for the analysis. amount of hexane in the EPDM polymer is 9.2 Follow this test method through sec- calculated. tion 11.4 of the method. After removing the sample of the first extraction to be run on 3.0 Definitions the gas chromatograph, drain off the remain- 3.1 Hexane—refers to n-hexane der of the extraction solvent, retaining the

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crumb sample in the sample jar. Rinse the 11.0 Procedure crumb with demineralized water to remove any MIBK left on the surface of the crumb. 11.1 Weight 10 grams of wet crumb into a Repeat the extraction procedure with fresh tared (W1), wide mouth 4 oz. jar. MIBK with internal standard two more 11.2 Pipette 50 ml of Solution B into the times. jar with the wet crumb rubber. 9.3 After the third extraction, proceed to 11.3 Screw the cap on tightly and place it section 11.5 of this method and obtain the on a shaker for 4 hours. percent hexane in each extraction. Use the 11.4 Remove the sample from the shaker sample weight obtained in section 12.1 of this and fill an autosampler vial with the MIBK method to calculate the percent hexane in extract. each of the extracts. 11.5 Analyze the sample two times. 9.4 Add the percent hexane obtained from 11.6 Analyze the HS twice, followed by the the three extractions for a total percent samples. Inject the HS twice at the end of hexane in the sample. each 10 samples or at the end of the run. 9.5 Use the following equations to determine the recovery factor (R): 12.0 Calculations % Recovery of the first extraction = (% 12.1 Drain off the remainder of the MIBK hexane in the first extract/total % hexane) × extract from the polymer in the 4 oz. jar. Re- 100 Recovery Factor (R) = (% Hexane Recov- tain all the polymer in the jar. Place the un- ered in the first extract)/100 covered jar and polymer in a heated vacuum oven until the polymer is dry. Reweigh the 10.0 Calibration jar and polymer (W2) and calculate the dried sample weight of the polymer as follows: 10.1 Preparation of Internal Standard (IS) solution: Dried SW = W2—W1 (2) Accuracy weigh 30 grams of n-heptane into 12.2 Should the polymer be oil extended, a 1000 ml volumetric flask. Dilute to the pipette 10 ml of the MIBK extract into a mark with reagent grade MIBK. Label this tared evaporating dish (W1) and evaporate to Solution ‘‘A’’. Pipette 100 mls. of Solution A dryness on a steam plate. into a 4 liter volumetric flask. Fill the flask Reweigh the evaporating dish containing to the mark with reagent MIBK. Label this the extracted oil (W2). Calculate the oil con- Solution ‘‘B’’. Solution ‘‘B’’ will have a content of the polymer as follows: centration of 0.75 mg/ml of heptane. Gram of oil extracted = 5 (W2—W1) (3) 10.2 Preparation of Hexane Standard So- lution (HS): % Hexane in polymer = (As × RF × CIS × PIS)/ Using a 50 uL syringe, weigh by difference, (AIS × SW) (4) 20 mg of n-hexane into a 50 ml volumetric Where: flask containing approximately 40 ml of So- lution B. Fill the flask to the mark with So- As = Area of sample hexane sample peak. lution B and mix well. AIS = Area of IS peak in sample. 10.3 Conditions for GC analysis of stand- CIS = Concentration of IS in 50 ml. ards and samples: PIS = Purity of IS. Temperature: SW = Weight of dried rubber after extrac- Initial = 40 °C tion. (For oil extended polymer, the Final = 150 °C amount of oil extracted is added to the Injector = 160 °C dry rubber weight). Detector = 280 °C % Corrected Hexane = (% Hexane in Poly- Program Rate = 5.0 °C/min mer)/R (5) Initial Time = 5 minutes Final Time = 6 R = Recovery factor determined in section 9 minutes of this method. Flow Rate = 5.0 ml/min Sensitivity = detector response must be ad- 13.0 Method Performance justed to keep the hexane and IS on scale. 13.1 Performance must be determined for 10.4 Fill an autosampler vial with the HS, each sample type by following the proce- analyze it three times and calculate a dures in section 9 of this method. Hexane Relative Response Factor (RF) as follows: 14.0 Waste Generation RF = (AIS × CHS × PHS)/(AHS × CIS × PIS) (1) 14.1 Waste generation should be mini- Where: mized where possible. AIS = Area of IS peak (Heptane) AHS = Area of peak (Hexane Standard) 15.0 Waste Management CHS = Mg of Hexane/50 ml HS CIS = Mg of Heptane/50 ml IS Solution B 15.1 All waste shall be handled in accord- PIS = Purity of the IS n-heptane ance with Federal and State environmental PHS = Purity of the HS n-hexane regulations. 743

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16.0 References [Reserved] for the sample to the responses obtained using known concentrations of the analytes. METHOD 311—ANALYSIS OF HAZARDOUS AIR POLLUTANT COMPOUNDS IN PAINTS AND 3. Definitions [Reserved] COATINGS BY DIRECT INJECTION INTO A GAS CHROMATOGRAPH 4. Interferences 4.1 Coating samples of unknown composi- 1. Scope and Application tion may contain the compound used as the 1.1 Applicability. This method is applica- internal standard. Whether or not this is the ble for determination of most compounds case may be determined by following the designated by the U.S. Environmental Pro- procedures of Section 11 and deleting the ad- tection Agency as volatile hazardous air pol- dition of the internal standard specified in lutants (HAP’s) (See Reference 1) that are Section 11.5.3. If necessary, a different inter- contained in paints and coatings. Styrene, nal standard may be used. ethyl acrylate, and methyl methacrylate can 4.2 The GC column and operating condi- be measured by ASTM D 4827–93 or ASTM D tions developed for one coating formulation 4747–87. Formaldehyde can be measured by may not ensure adequate resolution of target ASTM PS 9–94 or ASTM D 1979–91. Toluene analytes for other coating formulations. diisocyanate can be measured in urethane Some formulations may contain nontarget prepolymers by ASTM D 3432–89. Method 311 analytes that coelute with target analytes. applies only to those volatile HAP’s which If there is any doubt about the identification are added to the coating when it is manufac- or resolution of any gas chromatograph (GC) tured, not to those which may form as the peak, it may be necessary to analyze the coating cures (reaction products or cure sample using a different GC column or dif- volatiles). A separate or modified test proce- ferent GC operating conditions. dure must be used to measure these reaction 4.3 Cross-contamination may occur when- products or cure volatiles in order to deter- ever high-level and low-level samples are analyzed sequentially. The order of sample mine the total volatile HAP emissions from analyses specified in Section 11.7 is designed a coating. Cure volatiles are a significant to minimize this problem. component of the total HAP content of some 4.4 Cross-contamination may also occur if coatings. The term ‘‘coating’’ used in this the devices used to transfer coating during method shall be understood to mean paints the sample preparation process or for inject- and coatings. ing the sample into the GC are not ade- 1.2 Principle. The method uses the prin- quately cleaned between uses. All such de- ciple of gas chromatographic separation and vices should be cleaned with acetone or other quantification using a detector that responds suitable solvent and checked for plugs or to concentration differences. Because there cracks before and after each use. are many potential analytical systems or sets of operating conditions that may rep- 5. Safety resent useable methods for determining the concentrations of the compounds cited in 5.1 Many solvents used in coatings are Section 1.1 in the applicable matrices, all hazardous. Precautions should be taken to systems that employ this principle, but dif- avoid unnecessary inhalation and skin or eye contact. This method may involve hazardous fer only in details of equipment and oper- materials, operations, and equipment. This ation, may be used as alternative methods, test method does not purport to address all provided that the prescribed quality control, of the safety problems associated with its calibration, and method performance reuse. It is the responsibility of the user of this quirements are met. Certified product data test method to establish appropriate safety sheets (CPDS) may also include information and health practices and to determine the relevant to the analysis of the coating sam- applicability of regulatory limitations in re- ple including, but not limited to, separation gards to the performance of this test meth- column, oven temperature, carrier gas, injec- od. tion port temperature, extraction solvent, 5.2 Dimethylformamide is harmful if in- and internal standard. haled or absorbed through the skin. The user 2. Summary of Method should obtain relevant health and safety information from the manufacturer. Whole coating is added to Dimethylformamide should be used only dimethylformamide and a suitable internal with adequate ventilation. Avoid contact standard compound is added. An aliquot of with skin, eyes, and clothing. In case of con- the sample mixture is injected onto a tact, immediately flush skin or eyes with chromatographic column containing a sta- plenty of water for at least 15 minutes. If tionary phase that separates the analytes eyes are affected, consult a physician. Re- from each other and from other volatile move and wash contaminated clothing before compounds contained in the sample. The reuse. concentrations of the analytes are deter- 5.3 User’s manuals for the gas chro- mined by comparing the detector responses matograph and other related equipment

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should be consulted for specific precautions a maximum noise level of ±0.03 percent of to be taken related to their use. full scale. 6.2.3 Column. The column must be con- 6. Equipment and Supplies structed of materials that do not react with components of the sample (e.g., fused silica, NOTE: Certified product data sheets (CPDS) may also include information relevant to the stainless steel, glass). The column should be analysis of the coating sample including, but of appropriate physical dimensions (e.g., not limited to, separation column, oven tem- length, internal diameter) and contain suffi- perature, carrier gas, injection port tempera- cient suitable stationary phase to allow separation of the analytes. DB–5, DB-Wax, and ture, extraction solvent, and internal stand- FFAP columns are commonly used for paint ard. analysis; however, it is the responsibility of 6.1 Sample Collection. each analyst to select appropriate columns 6.1.1 Sampling Containers. Dual-seal sam- and stationary phases. pling containers, four to eight fluid ounce 6.2.4 Tube and Tube Fittings. Supplies to capacity, should be used to collect the sam- connect the GC and gas cylinders. ples. Glass sample bottles or plastic con- 6.2.5 Pressure Regulators. Devices used to tainers with volatile organic compound regulate the pressure between gas cylinders (VOC) impermeable walls must be used for and the GC. corrosive substances (e.g., etch primers and 6.2.6 Flow Meter. A device used to deter- certain coating catalysts such as methyl mine the carrier gas flow rate through the ethyl ketone (MEK) peroxide). Sample con- GC. Either a digital flow meter or a soap tainers, caps, and inner seal liners must be film bubble meter may be used to measure inert to the compounds in the sample and gas flow rates. must be selected on a case-by-case basis. 6.2.7 Septa. Seals on the GC injection port 6.1.1.1 Other routine sampling supplies through which liquid or gas samples can be needed include waterproof marking pens, injected using a syringe. tubing, scrappers/spatulas, clean rags, paper 6.2.8 Liquid Charging Devices. Devices towels, cooler/ice, long handle tongs, and used to inject samples into the GC such as mixing/stirring paddles. clean and graduated 1, 5, and 10 microliter 6.1.2 Personal safety equipment needed in- (μl) capacity syringes. cludes eye protection, respiratory protec- 6.2.9 Vials. Containers that can be sealed tion, a hard hat, gloves, steel toe shoes, etc. with a septum in which samples may be pre- 6.1.3 Shipping supplies needed include pared or stored. The recommended size is 25 ® shipping boxes, packing material, shipping ml capacity. Mininert valves have been labels, strapping tape, etc. found satisfactory and are available from 6.1.4 Data recording forms and labels Pierce Chemical Company, Rockford, Illi- needed include coating data sheets and sam- nois. ple can labels. 6.2.10 Balance. Device used to determine the weights of standards and samples. An an- NOTE: The actual requirements will depend alytical balance capable of accurately weigh- upon the conditions existing at the source ing to 0.0001 g is required. sampled. 6.2 Laboratory Equipment and Supplies. 7. Reagents and Standards 6.2.1 Gas Chromatograph (GC). Any in- 7.1 Purity of Reagents. Reagent grade strument equipped with a flame ionization chemicals shall be used in all tests. Unless detector and capable of being temperature otherwise specified, all reagents shall con- programmed may be used. Optionally, other form to the specifications of the Committee types of detectors (e.g., a mass spectrom- on Analytical Reagents of the American eter), and any necessary interfaces, may be Chemical Society, where such specifications used provided that the detector system are available. Other grades may be used pro- yields an appropriate and reproducible re- vided it is first ascertained that the reagent sponse to the analytes in the injected sam- is of sufficient purity to permit its use with- ple. Autosampler injection may be used, if out lessening the accuracy of determination. available. 7.2 Carrier Gas. Helium carrier gas shall 6.2.2 Recorder. If available, an electronic have a purity of 99.995 percent or higher. data station or integrator may be used to High purity nitrogen may also be used. Other record the gas chromatogram and associated carrier gases that are appropriate for the data. If a strip chart recorder is used, it must column system and analyte may also be meet the following criteria: A 1 to 10 milli- used. Ultra-high purity grade hydrogen gas volt (mV) linear response with a full scale re- and zero-grade air shall be used for the flame sponse time of 2 seconds or less and a max- ionization detector. imum noise level of ±0.03 percent of full 7.3 Dimethylformamide (DMF). Solvent scale. Other types of recorders may be used for all standards and samples. Some other as appropriate to the specific detector in- suitable solvent may be used if DMF is not stalled provided that the recorder has a full compatible with the sample or coelutes with scale response time of 2 seconds or less and a target analyte.

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NOTE: DMF may coelute with ethylbenzene 7.6.2 Transfer the stock reference stand- or p-xylene under the conditions described in ard solution into one or more Teflon-sealed the note under Section 6.2.3. screw-cap bottles. Store, with minimal ¥ ° ° 7.4 Internal Standard Materials. The in- headspace, at 10 C to 0 C and protect from ternal standard material is used in the quan- light. titation of the analytes for this method. It 7.6.3 Prepare fresh stock reference stand- shall be gas chromatography ards every six months, or sooner if analysis spectrophotometric quality or, if this grade results from daily calibration check stand- is not available, the highest quality avail- ards indicate a problem. Fresh stock ref- able. Obtain the assay for the internal stand- erence standards for very volatile HAP’s ard material and maintain at that purity may have to be prepared more frequently. during use. The recommended internal 7.7 Calibration Standards. Calibration standard material is 1-propanol; however, se- standards are used to determine the response lection of an appropriate internal standard of the detector to known amounts of ref- material for the particular coating and GC erence material. Calibration standards must conditions used is the responsibility of each be prepared at a minimum of three concentration levels from the stock reference analyst. standards (see Section 7.6). Prepare the cali- 7.5 Reference Standard Materials. The ref- bration standards in dimethylformamide (see erence standard materials are the chemicals Section 7.3). The lowest concentration stand- cited in Section 1.1 which are of known iden- ard should contain a concentration of tity and purity and which are used to assist analyte equivalent either to a concentration in the identification and quantification of of no more than 0.01% of the analyte in a the analytes of this method. They shall be coating or to a concentration that is lower the highest quality available. Obtain the as- than the actual concentration of the analyte says for the reference standard materials and in the coating, whichever concentration is maintain at those purities during use. higher. The highest concentration standard 7.6 Stock Reference Standards. Stock ref- should contain a concentration of analyte erence standards are dilutions of the ref- equivalent to slightly more than the highest erence standard materials that may be used concentration expected for the analyte in a on a daily basis to prepare calibration stand- coating. The remaining calibration standard ards, calibration check standards, and qual- should contain a concentration of analyte ity control check standards. Stock reference roughly at the midpoint of the range defined standards may be prepared from the ref- by the lowest and highest concentration cali- erence standard materials or purchased as bration standards. The concentration range certified solutions. of the standards should thus correspond to 7.6.1 Stock reference standards should be the expected range of analyte concentrations prepared in dimethylformamide for each in the prepared coating samples (see Section analyte expected in the coating samples to 11.5). Each calibration standard should con- be analyzed. The concentrations of analytes tain each analyte for detection by this meth- in the stock reference standards are not od expected in the actual coating samples specified but must be adequate to prepare (e.g., some or all of the compounds listed in the calibration standards required in the Section 1.1 may be included). Each calibra- method. A stock reference standard may tion standard should also contain an appro- contain more than one analyte provided all priate amount of internal standard material analytes are chemically compatible and no (response for the internal standard material analytes coelute. The actual concentrations is within 25 to 75 percent of full scale on the prepared must be known to within 0.1 per- attenuation setting for the particular ref- cent (e.g., 0.1000 ±0.0001 g/g solution). The fol- erence standard concentration level). Cali- lowing procedure is suggested. Place about 35 bration Standards should be stored for 1 ml of dimethylformamide into a tared week only in sealed vials with minimal ground-glass stoppered 50 ml volumetric headspace. If the stock reference standards flask. Weigh the flask to the nearest 0.1 mg. were prepared as specified in Section 7.6, the Add 12.5 g of the reference standard material calibration standards may be prepared by ei- and reweigh the flask. Dilute to volume with ther weighing each addition of the stock ref- dimethylformamide and reweigh. Stopper erence standard or by adding known volumes the flask and mix the contents by inverting of the stock reference standard and calcu- the flask several times. Calculate the con- lating the mass of the standard reference centration in grams per gram of solution material added. Alternative 1 (Section 7.7.1) from the net gain in weights, correcting for specifies the procedure to be followed when the assayed purity of the reference standard the stock reference standard is added by vol- material. ume. Alternative 2 (Section 7.7.2) specifies NOTE: Although a glass-stoppered volu- the procedure to be followed when the stock metric flask is convenient, any suitable reference standard is added by weight. glass container may be used because stock NOTE: To assist with determining the ap- reference standards are prepared by weight. propriate amount of internal standard to

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add, as required here and in other sections of 8.2 A copy of the blender’s worksheet can this method, the analyst may find it advan- be requested to obtain data on the exact tageous to prepare a curve showing the area coating being sampled. A blank coating data response versus the amount of internal sheet form (see Section 18) may also be used. standard injected into the GC. The manufacturer’s formulation information 7.7.1 Preparation Alternative 1. Deter- from the product data sheet should also be mine the amount of each stock reference obtained. 8.3 Prior to sample collection, thoroughly standard and dimethylformamide solvent mix the coating to ensure that a representa- needed to prepare approximately 25 ml of the tive, homogeneous sample is obtained. It is specific calibration concentration level de- preferred that this be accomplished using a sired. To a tared 25 ml vial that can be sealed coating can shaker or similar device; how- with a crimp-on or Mininert ® valve, add the ever, when necessary, this may be accom- total amount of dimethylformamide cal- plished using mechanical agitation or cir- culated to be needed. As quickly as practical, culation systems. add the calculated amount of each stock ref- 8.3.1 Water-thinned coatings tend to in- erence standard using new pipets (or pipet corporate or entrain air bubbles if stirred too tips) for each stock reference standard. Re- vigorously; mix these types of coatings slow- weigh the vial and seal it. Using the known ly and only as long as necessary to homog- weights of the standard reference materials enize. per ml in the stock reference standards, the 8.3.2 Each component of multicomponent volumes added, and the total weight of all coatings that harden when mixed must be reagents added to the vial, calculate the sampled separately. The component mix ra- weight percent of each standard reference tios must be obtained at the facility at the material in the calibration standard pre- time of sampling and submitted to the ana- pared. Repeat this process for each calibra- lytical laboratory. tion standard to be prepared. 8.4 Sample Collection. Samples must be 7.7.2 Preparation Alternative 2. Deter- collected in a manner that prevents or mini- mine the amount of each stock reference mizes loss of volatile components and that standard and dimethylformamide solvent does not contaminate the coating reservoir. needed to prepare approximately 25 ml of the A suggested procedure is as follows. Select a specific calibration concentration level de- sample collection container which has a ca- sired. To a tared 25 ml vial that can be sealed pacity at least 25 percent greater than the with a crimp-on or Mininert ® valve, add the container in which the sample is to be trans- total amount of dimethylformamide cal- ported. Make sure both sample containers culated to be needed. As quickly as practical, are clean and dry. Using clean, long-handled add the calculated amount of a stock ref- tongs, turn the sample collection container erence standard using a new pipet (or pipet upside down and lower it into the coating tip) and reweigh the vial. Repeat this process reservoir. The mouth of the sample collec- for each stock reference standard to be tion container should be at approximately added. Seal the vial after obtaining the final the midpoint of the reservoir (do not take weight. Using the known weight percents of the sample from the top surface). Turn the the standard reference materials in the stock sample collection container over and slowly reference standards, the weights of the stock bring it to the top of the coating reservoir. reference standards added, and the total Rapidly pour the collected coating into the weight of all reagents added to the vial, cal- sample container, filling it completely. It is culate the weight percent of each standard important to fill the sample container com- reference material in the calibration stand- pletely to avoid any loss of volatiles due to ard prepared. Repeat this process for each volatilization into the headspace. Return calibration standard to be prepared. any unused coating to the reservoir or dispose as appropriate. 8. Sample Collection, Preservation, Transport, NOTE: If a company requests a set of sam- and Storage ples for its own analysis, a separate set of 8.1 Copies of material safety data sheets samples, using new sample containers, (MSDS’s) for each sample should be obtained should be taken at the same time. prior to sampling. The MSDS’s contain infor- 8.5 Once the sample is collected, place the mation on the ingredients, and physical and sample container on a firm surface and in- chemical properties data. The MSDS’s also sert the inner seal in the container by plac- contain recommendations for proper han- ing the seal inside the rim of the container, dling or required safety precautions. Cer- inverting a screw cap, and pressing down on tified product data sheets (CPDS) may also the screw cap which will evenly force the include information relevant to the analysis inner seal into the container for a tight fit. of the coating sample including, but not lim- Using clean towels or rags, remove all resid- ited to, separation column, oven tempera- ual coating material from the outside of the ture, carrier gas, injection port temperature, sample container after inserting the inner extraction solvent, and internal standard. seal. Screw the cap onto the container.

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8.5.1 Affix a sample label (see Section 18) sion, the analyst must perform the following clearly identifying the sample, date col- operations. lected, and person collecting the sample. 9.4.1 Prepare a quality control check 8.5.2 Prepare the sample for transpor- standard (QCCS) containing each analyte ex- tation to the laboratory. The sample should pected in the coating samples at a con- be maintained at the coating’s recommended centration expected to result in a response storage temperature specified on the Mate- between 25 percent and 75 percent of the lim- rial Safety Data Sheet, or, if no temperature its of the calibration curve when the sample is specified, the sample should be maintained is prepared as described in Section 11.5. The within the range of 5 °C to 38 °C. QCCS may be prepared from reference stand- 8.9 The shipping container should adhere ard materials or purchased as certified solu- to U.S. Department of Transportation speci- tions. If prepared in the laboratory, the fication DOT 12–B. Coating samples are con- QCCS must be prepared independently from sidered hazardous materials; appropriate the calibration standards. shipping procedures should be followed. 9.4.2 Analyze three aliquots of the QCCS according to the method beginning in Sec- 9. Quality Control tion 11.5.3 and calculate the weight percent 9.1 Laboratories using this method should of each analyte using Equation 1, Section 12. operate a formal quality control program. 9.4.3 Calculate the mean weight percent ¯ The minimum requirements of the program (X) for each analyte from the three results should consist of an initial demonstration of obtained in Section 9.4.2. laboratory capability and an ongoing anal- 9.4.4 Calculate the percent accuracy for ysis of blanks and quality control samples to each analyte using the known concentra- evaluate and document quality data. The tions (Ti) in the QCCS using Equation 3, Sec- laboratory must maintain records to docu- tion 12. ment the quality of the data generated. 9.4.5 Calculate the percent relative stand- When results indicate atypical method per- ard deviation (percent RSD) for each analyte formance, a quality control check standard using Equation 7, Section 12, substituting (see Section 9.4) must be analyzed to confirm the appropriate values for the relative re- that the measurements were performed in an sponse factors (RRF’s) in said equation. in-control mode of operation. 9.4.6 If the percent accuracy (Section 9.2 Before processing any samples, the an- 9.4.4) for all analytes is within the range 90 alyst must demonstrate, through analysis of percent to 110 percent and the percent RSD a reagent blank, that there are no inter- (Section 9.4.5) for all analytes is ≤20 percent, ferences from the analytical system, glass- system performance is acceptable and sam- ware, and reagents that would bias the sample analysis may begin. If these criteria are ple analysis results. Each time a set of ana- not met for any analyte, then system per- lytical samples is processed or there is a formance is not acceptable for that analyte change in reagents, a reagent blank should and the test must be repeated for those be processed as a safeguard against chronic analytes only. Repeated failures indicate a laboratory contamination. The blank sam- general problem with the measurement sys- ples should be carried through all stages of tem that must be located and corrected. In the sample preparation and measurement this case, the entire test, beginning at Sec- steps. tion 9.4.1, must be repeated after the problem 9.3 Required instrument quality control is corrected. parameters are found in the following sec- 9.5 Great care must be exercised to main- tions: tain the integrity of all standards. It is rec- 9.3.1 Baseline stability must be dem- ommended that all standards be stored at onstrated to be ≤5 percent of full scale using ¥10 °C to 0 °C in screw-cap amber glass bot- the procedures given in Section 10.1. tles with Teflon liners. 9.3.2 The GC calibration is not valid un- 9.6 Unless otherwise specified, all weights less the retention time (RT) for each analyte are to be recorded within 0.1 mg. at each concentration is within ±0.05 min of 10. Calibration and Standardization. the retention time measured for that analyte in the stock standard. 10.1 Column Baseline Drift. Before each 9.3.3 The retention time (RT) of any sam- calibration and series of determinations and ple analyte must be within ±0.05 min of the before the daily calibration check, condition average RT of the analyte in the calibration the column using procedures developed by standards for the analyte to be considered the laboratory or as specified by the column tentatively identified. supplier. Operate the GC at initial (i.e., be- 9.3.4 The GC system must be calibrated as fore sample injection) conditions on the low- specified in Section 10.2. est attenuation to be used during sample 9.3.5 A one-point daily calibration check analysis. Adjust the recorder pen to zero on must be performed as specified in Section the chart and obtain a baseline for at least 10.3. one minute. Initiate the GC operating cycle 9.4 To establish the ability to generate re- that would be used for sample analysis. On sults having acceptable accuracy and preci- the recorder chart, mark the pen position at

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the end of the simulated sample analysis described beginning in Section 11.7. Repeat cycle. Baseline drift is defined as the abso- the procedure for each progressively higher lute difference in the pen positions at the be- concentration level until all calibration ginning and end of the cycle in the direction standards have been analyzed. perpendicular to the chart movement. Cal- 10.2.2.1 Calculate the RT’s for the internal culate the percent baseline drift by dividing standard and for each analyte in the calibra- the baseline drift by the chart width rep- tion standards at each concentration level as resenting full-scale deflection and multiply described in Section 10.2.1. The RT’s for the the result by 100. internal standard must not vary by more 10.2 Calibration of GC. Bring all stock than 0.10 minutes. Identify each analyte by standards and calibration standards to room comparison of the RT’s for peak maxima to temperature while establishing the GC at the the RT’s determined in Section 10.2.1. determined operating conditions. 10.2.2.2 Compare the retention times 10.2.1 Retention Times (RT’s) for Indi- (RT’s) for each potential analyte in the cali- vidual Compounds. bration standards for each concentration NOTE: The procedures of this subsection level to the retention times determined in are required only for the initial calibration. Section 10.2.1. The calibration is not valid However, it is good laboratory practice to unless all RT’s for all analytes meet the cri- follow these procedures for some or all teria given in Section 9.3.2. analytes before each calibration. The proce- 10.2.2.3 Tabulate the area responses and dures were written for chromatograms out- the concentrations for the internal standard put to a strip chart recorder. More modern and each analyte in the calibration stand- instruments (e.g., integrators and electronic ards. Calculate the response factor for the data stations) determine and print out or internal standard (RFis) and the response fac- display retention times automatically. tor for each compound relative to the inter- The RT for each analyte should be deter- nal standard (RRF) for each concentration mined before calibration. This provides a level using Equations 5 and 6, Section 12. positive identification for each peak ob- 10.2.2.4 Using the RRF’s from the calibra- served from the calibration standards. Inject tion, calculate the percent relative standard an appropriate volume (see note in Section deviation (percent RSD) for each analyte in 11.5.2) of one of the stock reference standards the calibration standard using Equation 7, into the gas chromatograph and record on Section 12. The percent RSD for each indi- the chart the pen position at the time of the vidual calibration analyte must be less than injection (see Section 7.6.1). Dilute an ali- 15 percent. This criterion must be met in quot of the stock reference standard as re- order for the calibration to be valid. If the quired in dimethylformamide to achieve a criterion is met, the mean RRF’s determined concentration that will result in an on-scale above are to be used until the next calibra- response. Operate the gas chromatograph action. cording to the determined procedures. Select 10.3 Daily Calibration Checks. The cali- the peak(s) that correspond to the analyte(s) bration curve (Section 10.2.2) must be [and internal standard, if used] and measure checked and verified at least once each day the retention time(s). If a chart recorder is that samples are analyzed. This is accom- used, measure the distance(s) on the chart plished by analyzing a calibration standard from the injection point to the peak maxi- that is at a concentration near the midpoint ma. These distances, divided by the chart of the working range and performing the speed, are defined as the RT’s of the analytes checks in Sections 10.3.1, 10.3.2, and 10.3.3. in question. Repeat this process for each of 10.3.1 For each analyte in the calibration the stock reference standard solutions. standard, calculate the percent difference in NOTE: If gas chromatography with mass the RRF from the last calibration using spectrometer detection (GC-MS) is used, a Equation 8, Section 12. If the percent dif- stock reference standard may contain a ference for each calibration analyte is less group of analytes, provided all analytes are than 10 percent, the last calibration curve is adequately separated during the analysis. assumed to be valid. If the percent difference Mass spectral library matching can be used for any analyte is greater than 5 percent, the to identify the analyte associated with each analyst should consider this a warning limit. peak in the gas chromatogram. The reten- If the percent difference for any one calibration time for the analyte then becomes the tion analyte exceeds 10 percent, corrective retention time of its peak in the chromato- action must be taken. If no source of the gram. problem can be determined after corrective 10.2.2 Calibration. The GC must be cali- action has been taken, a new three-point brated using a minimum of three concentra- (minimum) calibration must be generated. tion levels of each potential analyte. (See This criterion must be met before quan- Section 7.7 for instructions on preparation of titative analysis begins. the calibration standards.) Beginning with 10.3.2 If the RFis for the internal standard the lowest concentration level calibration changes by more than ±20 percent from the standard, carry out the analysis procedure as last daily calibration check, the system

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must be inspected for malfunctions and cor- tween 25 percent and 75 percent of the linear rections made as appropriate. range of the calibration curve. 10.3.3 The retention times for the internal 11.5.4 Seal the vials with crimp-on or standard and all calibration check analytes Mininert ® septum seals. must be evaluated. If the retention time for 11.6 Shake the vials containing the pre- the internal standard or for any calibration pared coating samples for 60 seconds. Allow check analyte changes by more than 0.10 min the vials to stand undisturbed for ten min- from the last calibration, the system must utes. If solids have not settled out on the be inspected for malfunctions and correc- bottom after 10 minutes, then centrifuge at tions made as required. 1,000 rpm for 5 minutes. The analyst also has 11. Procedure the option of injecting the sample without allowing the solids to settle. 11.1 All samples and standards must be al- 11.7 Analyses should be conducted in the lowed to warm to room temperature before following order: daily calibration check sam- analysis. Observe the given order of ingre- ple, method blank, up to 10 injections from dient addition to minimize loss of volatiles. sample vials (i.e., one injection each from up 11.2 Bring the GC system to the deter- to five pairs of vials, which corresponds to mined operating conditions and condition analysis of 5 coating samples). the column as described in Section 10.1. 11.8 Inject the prescribed volume of super- NOTE: The temperature of the injection natant from the calibration check sample, port may be an especially critical parameter. the method blank, and the sample vials onto Information about the proper temperature the chromatographic column and record the may be found on the CPDS. chromatograms while operating the system 11.3 Perform the daily calibration checks under the specified operating conditions. as described in Section 10.3. Samples are not NOTE: The analyst has the option of inject- to be analyzed until the criteria in Section ing the unseparated sample. 10.3 are met. 11.4 Place the as-received coating sample 12. Data Analysis and Calculations on a paint shaker, or similar device, and shake the sample for a minimum of 5 min- 12.1 Qualitative Analysis. An analyte (e.g., utes to achieve homogenization. those cited in Section 1.1) is considered ten- 11.5 NOTE: The steps in this section must tatively identified if two criteria are satis- be performed rapidly and without interrup- fied: (1) elution of the sample analyte within tion to avoid loss of volatile organics. These ±0.05 min of the average GC retention time of steps must be performed in a laboratory the same analyte in the calibration stand- hood free from solvent vapors. All weights ard; and (2) either (a) confirmation of the must be recorded to the nearest 0.1 mg. identity of the compound by spectral match- 11.5.1 Add 16 g of dimethylformamide to ing on a gas chromatograph equipped with a each of two tared vials (A and B) capable of mass selective detector or (b) elution of the being septum sealed. sample analyte within ±0.05 min of the aver- 11.5.2 To each vial add a weight of coating age GC retention time of the same analyte in that will result in the response for the major the calibration standard analyzed on a dis- constituent being in the upper half of the similar GC column. linear range of the calibration curve. 12.1.1 The RT of the sample analyte must NOTE: The magnitude of the response obvi- meet the criteria specified in Section 9.3.3. ously depends on the amount of sample in- 12.1.2 When doubt exists as to the identi- jected into the GC as specified in Section fication of a peak or the resolution of two or 11.8. This volume must be the same as used more components possibly comprising one for preparation of the calibration curve, oth- peak, additional confirmatory techniques erwise shifts in compound retention times (listed in Section 12.1) must be used. may occur. If a sample is prepared that re- 12.2 Quantitative Analysis. When an sults in a response outside the limits of the analyte has been identified, the quantifica- calibration curve, new samples must be pre- tion of that compound will be based on the pared; changing the volume injected to bring internal standard technique. the response within the calibration curve 12.2.1 A single analysis consists of one in- limits is not permitted. jection from each of two sample vials (A and 11.5.3 Add a weight of internal standard to B) prepared using the same coating. Cal- each vial (A and B) that will result in the re- culate the concentration of each identified sponse for the internal standard being be- analyte in the sample as follows:

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()AW() =× xis HAPwt% 100Eq.() 1 ()Ais() RRF x() W x where:

HAP= weight percent of the analyte in coating. wt% = Ax Area response of the analyte in the sample. W = Weight of internal standard added to sample, g. is = Ais Area response of the internal standard in the sample. RRF = Mean relative response factor for the analyte in the calibration standards. x = Wx Weight of coating added to the sample solution, g.

12.2.2 Report results for duplicate analysis where Ai and Bi are the measured concentra- (sample vials A and B) without correction. tions of the analyte in vials A and B. 12.3 Precision Data. Calculate the percent 12.4 Calculate the percent accuracy for difference between the measured concentra- analytes in the QCCS (See Section 9.4) as fol- tions of each analyte in vials A and B as follows: lows. X 12.3.1 Calculate the weight percent of the =×x () analyte in each of the two sample vials as % Accuracyx 100 Eq. 3 described in Section 12.2.1. Tx 12.3.2 Calculate the percent difference for where Xx is the mean measured value and Tx each analyte as: is the known true value of the analyte in the QCCS. − 12.5 Obtain retention times (RT’s) from ABii %Dif =×100 Eq. (2) data station or integrator or, for i + chromatograms from a chart recorder, cal- ()ABii culate the RT’s for analytes in the calibra- 2 tion standards (See Section 10.2.2.2) as follows:

Distance from injection to peak maximum RT = Eq. ()4 Recorder chart speed

12.6 Calculate the response factor for the A internal standard (See Section 10.2.2.3) as fol- = x lows: RRFx Eq. (6) RFis C x A = is () RRF = Relative response factor for an in- RFis Eq. 5 x dividual analyte. Cis Ax = Area response of the analyte being where: measured. A = Area response of the internal stand- is Cx = Weight percent of the analyte being ard. measured. Cis = Weight percent of the internal stand- 12.8 Calculate the percent relative standard ard. deviation of the relative response factors for 12.7 Calculate the relative response factors analytes in the calibration standards (See for analytes in the calibration standards Section 10.2.2.4) as follows: (See Section 10.2.2.3) as follows: where:

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n − 2 ∑ ()RRFxx RRF i=1 n −1 %RSD =×100 Eq. (7) RRFx where:

n = Number of calibration concentration levels used for an analyte. = RRFx Individual RRF for an analyte. = ′ RRFx Mean of all RRF s for an analyte.

12.9 Calculate the percent difference in the bration curve and the daily calibration relative response factors between the cali- checks (See Section 10.3) as follows:

− RRFxc RRF % Difference = ×100 Eq. (8) RRFx where:

RRF= mean relative response factor from last calibration. RRF= relative response factor from calibration check standard.

13. Measurement of Reaction Byproducts That tory. It is recommended that unused or ex- are HAP [Reserved] cess samples and reagents be placed in a solvent-resistant plastic or metal container 14. Method Performance [Reserved] with a lid or cover designed for flammable liquids. This container should not be stored 15. Pollution Prevention [Reserved] in the area where analytical work is performed. It is recommended that a record be 16. Waste Management kept of all compounds placed in the con- 16.1 The coating samples and laboratory tainer for identification of the contents upon standards and reagents may contain com- disposal. pounds which require management as hazardous waste. It is the laboratory’s responsi- 17. References bility to ensure all wastes are managed in 1. Clean Air Act Amendments, Public Law accordance with all applicable laws and reg- 101–549, Titles I–XI, November, 1990. ulations. 2. Standard Test Method for Water Content 16.2 To avoid excessive laboratory waste, of Water-Reducible Paints by Direct Injec- obtain only enough sample for laboratory tion into a Gas Chromatograph. ASTM Des- analysis. ignation D3792–79. 16.3 It is recommended that discarded 3. Standard Practice for Sampling Liquid waste coating solids, used rags, used paper Paints and Related Pigment Coatings. ASTM towels, and other nonglass or nonsharp waste Designation D3925–81. materials be placed in a plastic bag before 4. Standard Test Method for Determination disposal. A separate container, designated of Dichloromethane and 1,1,1-Trichloro- ‘‘For Sharp Objects Only,’’ is recommended ethane in Paints and Coatings by Direct In- for collection of discarded glassware and jection into a Gas Chromatograph. ASTM other sharp-edge items used in the labora- Designation D4457–85.

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5. Standard Test Method for Determining 18. Tables, Diagrams, Flowcharts, and the Unreacted Monomer Content of Latexes Validation Data Using Capillary Column Gas Chroma- tography. ASTM Designation D4827–93. Agency: lllllllllllllllllll 6. Standard Test Method for Determining Inspector: llllllllllllllllll Unreacted Monomer Content of Latexes Date/Time: lllllllllllllllll Using Gas-Liquid Chromatography. ASTM Sample ID#: lllllllllllllllll Designation D 4747–87. Source ID: llllllllllllllllll 7. Method 301—‘‘Field Validation of Pollut- Coating Name/Type: llllllllllll ant Measurement Methods from Various Plant Witness: lllllllllllllll Waste Media,’’ 40 CFR 63, Appendix A. Type Analysis Required: llllllllll 8. ‘‘Reagent Chemicals, American Chem- Special Handling: llllllllllllll ical Society Specifications,’’ American Chemical Society, Washington, DC. For sug- Sample Container Label gestions on the testing of reagents not listed by the American Chemical Society, see ‘‘Re- Coating Data agent Chemicals and Standards’’ by Joseph Rosin, D. Van Nostrand Co., Inc., New York, Date: llllllllllllllllllll NY and the ‘‘United States Pharmacopeia.’’ Source: lllllllllllllllllll

Data Sample ID No. Sample ID No.

Coating: Supplier Name ...... Name and Color of Coating ...... Type of Coating (primer, clearcoat, etc.) ...... Identification Number for Coating ...... Coating Density (lbs/gal) ...... Total Volatiles Content (wt percent) ...... Water Content (wt percent) ...... Exempt Solvents Content (wt percent) ...... VOC Content (wt percent) ...... Solids Content (vol percent) ...... Diluent Properties: Name. Identification Number ...... Diluent Solvent Density (lbs/gal) ...... VOC Content (wt percent) ...... Water Content (wt percent) ...... Exempt Solvent Content (wt percent) ...... Diluent/Solvent Ratio (gal diluent solvent/gal coating) ......

Stock Reference Standard PREPARATION INFORMATION—Continued Name of Reference Material: llllllll 5. Weight DMF (lines 2–1 llll,g Supplier Name: lllllllllllllll + 3–4). 6. Weight Ref. Material llll,g Lot Number: llllllllllllllll (lines 3–2). Purity: lllllllllllllllllll 7. Corrected Weight of Ref- llll,g Name of Solvent Material: erence Material (line 6 Dimethylformamide lllllllllllll times purity). Supplier Name: lllllllllllllll 8. Fraction Reference Ma- llll,g/g Lot Number: llllllllllllllll terial in Standard (Line 7 Purity: lllllllllllllllllll ÷ Line 5) soln. Date Prepared: lllllllllllllll 9. Total Volume of Stand- llll, ml Prepared By: llllllllllllllll ard Solution. 10. Weight Reference Ma- llll,g/ml Notebook/page no.: lllllllllllll terial per ml of Solution ÷ PREPARATION INFORMATION (Line 7 Line 9). Laboratory ID No. for this llll 1. Weight Empty Flask ...... llll,g Standard. 2. Weight Plus DMF ...... llll,g Expiration Date for this llll 3. Weight Plus Reference llll,g Standard. Material. 4. Weight After Made to llll,g CALIBRATION STANDARD Volume. Date Prepared: lllllllllllllll 753

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Date Expires: llllllllllllllll PREPARATION INFORMATION Prepared By: llllllllllllllll Final Weight Flask Plus Re- llll, g Notebook/page: lllllllllllllll agents. Calibration Standard Identification No.: Weight Empty Flask ...... llll, g llllllllllllllllllllllll Total Weight Of Reagents ...... llll, g

Amount of stock reference standard added (by volume or Stock ref- by weight) Calculated Weight per- erence weight cent analyte Analyte name a in calibra- standard ID Volume Amount in Weight Amount in analyte tion stand- No. standard, g/ standard, g/ added, g b added, ml ml added, g g soln ard

...... a Include internal standard(s). b Weight percent = weight analyte added ÷ total weight of reagents.

Quality Control Check Standard llllllllllllllllllllllll Date Prepared: lllllllllllllll PREPARATION INFORMATION Date Expires: llllllllllllllll Prepared By: llllllllllllllll Final Weight Flask Plus Re- llll,g Notebook/page: lllllllllllllll agents. Weight Empty Flask ...... llll,g Quality Control Check Standard Identifica- Total Weight Of Reagents ...... llll,g tion No.:

Amount of stock reference standard added (by volume or Stock ref- by weight) Calculated Weight per- erence weight cent analyte Analyte name a standard ID Volume Amount in Weight Amount in analyte in QCC No. standard, g/ standard, g/ added, g standard b added, ml ml added, g g soln

...... a Include internal Standard(s). b Weight percent = weight analyte added ÷ total weight of reagents.

Quality Control Check Standard Analysis OCCS Identification No. llllllllll Date OCCS Analyzed: llllllllllll Analyst: lllllllllllllllllll QCC Expiration Date: llllllllllll

ANALYSIS RESULTS

Weight percent determined Meets criteria in Sec- tion 9.4.6 Analyte Mean Wt Percent Percent Run 1 Run 2 Run 3 percent accuracx RSD Percent Percent accuracy RSD

. . .

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ANALYSIS RESULTS—Continued

Weight percent determined Meets criteria in Sec- tion 9.4.6 Analyte Mean Wt Percent Percent Run 1 Run 2 Run 3 percent accuracx RSD Percent Percent accuracy RSD

......

Calibration of Gas Chromatograph Calibrated By: llllllllllllllll Calibration Date: llllllllllllll

PART 1—RETENTION TIMES FOR INDIVIDUAL ANALYTES

Recorder chart speed Distance from injection point to Analyte Stock stand- peak maximum Retention ard. ID No. time, minutes a Inches/min. cm/min. Inches Centimeters

...... a Retention time = distance to peak maxima ÷ chart speed.

CALIBRATION OF GAS CHROMATOGRAPH Calibrated By: llllllllllllllll Calibration Date: llllllllllllll

PART 2—ANALYSIS OF CALIBRATION STANDARDS

Calib. STD ID Calib. STD ID Calib. STD ID Analyte No. No. No.

Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ......

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PART 2—ANALYSIS OF CALIBRATION STANDARDS—Continued

Calib. STD ID Calib. STD ID Calib. STD ID Analyte No. No. No.

Name: Conc. in STD ...... Area Response ...... RT ...... Name: Conc. in STD ...... Area Response ...... RT ...... Internal Standard Name: Conc. in STD ...... Area Response ...... RT ......

Calibration of Gas Chromatograph Calibrated By: llllllllllllllll Calibration Date: llllllllllllll

PART 3—DATA ANALYSIS FOR CALIBRATION STANDARDS

Is RT within Calib. STD Calib. STD Calib. STD percent ±0.05 min of Is percent Analyte ID ID ID Mean RSD of RF RT for RSD <30% stock? (Y/N) (Y/N)

Name: RT ...... RF ...... Name: RT ...... RF ...... Name: RT ...... RF ...... Name: RT ...... RF ...... Name: RT ...... RF ...... Name: RT ...... RF ...... Name: RT ...... RF ......

Daily Calibration Check Analyst: lllllllllllllllllll Calibration Check Standard ID No.: Date: llllllllllllllllllll Expiration Date: llllllllllllll

Retention Time (RT) Response Factor (RF) Analyte Last This Difference a Last This Difference b

...... a Retention time (RT) change (difference) must be less than ±0.10 minutes.

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b Response factor (RF) change (difference) must be less than 20 percent for each analyte and for the internal standard.

Sample Analysis Vial B ID No.: llllllllllllllll Vial A ID No.: llllllllllllllll Analyzed By: llllllllllllllll Date: llllllllllllllllllll

Sample preparation information Vial A (g) Vial B (g)

Measured: wt empty via. wt plus DMF. wt plus sample. wt plus internal. standard. Calculated: wt DMF. wt sample. wt internal standard.

ANALYSIS RESULTS: DUPLICATE SAMPLES

Area response Wt percent in sample Analyte RF Vial A Vial B Vial A Vial B Average

...... Internal Standard.

METHOD 312A—DETERMINATION OF STYRENE IN 4.0 Interferences LATEX STYRENE-BUTADIENE RUBBER, 4.1 In order to reduce matrix effects and THROUGH GAS CHROMATOGRAPHY emulsify the styrene, similar styrene free 1. Scope and Application latex is added to the internal standard. There are no known interferences. 1.1 This method describes a procedure for 4.2 The operating parameters are selected determining parts per million (ppm) styrene to obtain resolution necessary to determine monomer (CAS No. 100–42–5) in aqueous sam- styrene monomer concentrations in latex. ples, including latex samples and styrene stripper water. 5.0 Safety 1.2 The sample is separated in a gas chro- 5.1 It is the responsibility of the user of matograph equipped with a packed column this procedure to establish appropriate safe- and a flame ionization detector. ty and health practices. 2.0 Summary of Method 6.0 Equipment and Supplies 2.1 This method utilizes a packed column 6.1 Adjustable bottle-top dispenser, set to gas chromatograph with a flame ionization deliver 3 ml. (for internal standard), detector to determine the concentration of Brinkmann Dispensette, or equivalent. residual styrene in styrene butadiene rubber 6.2 Pipettor, set to 10 ml., Oxford Macro- (SBR) latex samples. set, or equivalent. 3.0 Definitions 6.3 Volumetric flask, 100-ml, with stopper. 6.4 Hewlett Packard Model 5710A dual 3.1 The definitions are included in the text channel gas chromatograph equipped with as needed. flame ionization detector.

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6.4.1 11 ft. × 1⁄8 in. stainless steel column where: packed with 10% TCEP on 100/120 mesh R=S(Rn)/6 Chromosorb P, or equivalent. where: 6.4.2 Perkin Elmer Model 023 strip chart re- Rn = (cns¥cv)/Sn corder, or equivalent. n = sample number 6.5 Helium carrier gas, zero grade. μ cns = concentration of compound measured in 6.6 Liquid syringe, 25- l. spiked sample number n. 6.7 Digital MicroVAX 3100 computer with cnu = concentration of compound measured in VG Multichrom software, or equivalent data unspiked sample number n. handling system. Sn = theoretical concentration of compound 6.6 Wire Screens, circular, 70-mm, 80-mesh spiked into sample n. diamond weave. 9.3.4 A value of R between 0.70 and 1.30 is 6.7 DEHA—(N,N-Diethyl hydroxylamine), acceptable. 97 + % purity, CAS No. 3710–84–7 9.3.5 R is used to correct all reported re- 6.8 p-Dioxane, CAS No. 123–91–1 sults for each compound by dividing the 7.0 Reagents and Standards measured results of each compound by the R for that compound for the same sample type. 7.1 Internal standard preparation. 7.1.1 Pipette 5 ml p-dioxane into a 1000-ml 10.0 Calibration and Instrument Settings volumetric flask and fill to the mark with 10.1 Injection port temperature, 250 °C. distilled water and mix thoroughly. 10.2 Oven temperature, 110 °C, isothermal. 7.2 Calibration solution preparation. 10.3 Carrier gas flow, 25 cc/min. 7.2.1 Pipette 10 ml styrene-free latex (eg: 10.4 Detector temperature, 250 °C. NBR latex) into a 100-ml volumetric flask. 10.5 Range, 1X. 7.2.2 Add 3 ml internal standard (section 7.1.1 of this method). 11.0 Procedure 7.2.3 Weigh exactly 10 μl fresh styrene and record the weight. 11.1 Turn on recorder and adjust baseline 7.2.4 Inject the styrene into the flask and to zero. mix well. 11.2 Prepare sample. 7.2.5 Add 2 drops of DEHA, fill to the mark 11.2.1 For latex samples, add 3 ml Internal with water and mix well again. Standard (section 7.1 of this method) to a 7.2.6 Calculate concentration of the cali- 100-ml volumetric flask. Pipet 10 ml sample bration solution as follows: into the flask using the Oxford pipettor, dilute to the 100-ml mark with water, and mg/l styrene = (mg styrene added)/0.1 L shake well. 8.0 Sample Collection, Preservation, and Storage 11.2.2 For water samples, add 3 ml Internal Standard (section 7.1 of this method) to a 8.1 A representative SBR emulsion sample 100-ml volumetric flask and fill to the mark should be caught in a clean, dry 6-oz. teflon with sample. Shake well. lined glass container. Close it properly to as- 11.3 Flush syringe with sample. sure no sample leakage. 11.4 Carefully inject 2 μl of sample into the 8.2 The container should be labeled with gas chromatograph column injection port sample identification, date and time. and press the start button. 11.5 When the run is complete the com- 9.0 Quality Control puter will print a report of the analysis. 9.1 The instrument is calibrated by injecting calibration solution (Section 7.2 of this 12.0 Data Analysis and Calculation method) five times. 12.1 For samples that are prepared as in 9.2 The retention time for components of section 11.2.1 of this method: interest and relative response of monomer to ppm styrene = A × D the internal standard is determined. 9.3 Recovery efficiency must be determined Where: A = ‘‘ppm’’ readout from computer once for each sample type and whenever D = dilution factor (10 for latex samples) modifications are made to the method. 9.3.1 A set of six latex samples shall be col- 12.2 For samples that are prepared as in lected. Two samples shall be prepared for section 11.2.2 of this method, ppm styrene is analysis from each sample. Each sample read directly from the computer. shall be analyzed in duplicate. 13.0 Method Performance 9.3.2 The second set of six latex samples shall be analyzed in duplicate before spiking 13.1 This test has a standard deviation (1) each sample with approximately 1000 ppm of 3.3 ppm at 100 ppm styrene. The average styrene. The spiked samples shall be ana- Spike Recovery from six samples at 1000 ppm lyzed in duplicate. Styrene was 96.7 percent. The test method 9.3.3 For each hydrocarbon, calculate the was validated using 926 ppm styrene stand- average recovery efficiency (R) using the fol- ard. Six analysis of the same standard pro- lowing equations: vided average 97.7 percent recovery. Note:

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These are example recoveries and do not re- 6.0 Equipment and Supplies place quality assurance procedures in this 6.1 Analytical balance, 160 g capacity, and method. 0.1 mg resolution 6.2 Bottles, 2-oz capacity, with poly-cap 14.0 Pollution Prevention screw lids 14.1 Waste generation should be minimized 6.3 Mechanical shaker where possible. Sample size should be an 6.4 Syringe, 10-ul capacity amount necessary to adequately run the 6.5 Gas chromatograph, Hewlett Packard analysis. model 5890A, or equivalent, configured with FID with a megabore jet, splitless injector 15.0 Waste Management packed with silanized glass wool. 6.5.1 Establish the following gas 15.1 All waste shall be handled in accord- chromatographic conditions, and allow the ance with Federal and State environmental system to thoroughly equilibrate before use. regulations. Injection technique = Splitless Injector temperature = 225 deg C 16.0 References and Publications Oven temperature = 70 deg C (isothermal) 16.1 40 CFR 63 Appendix A—Method 301 Detector: temperature = 300 deg C Test Methods Field Validation of Pollutant range = 5 Measurement attenuation = 0 16.2 DSM Copolymer Test Method T–3060, Carrier gas: helium = 47 ml/min Detector gases: hydrogen = 30 ml/min dated October 19, 1995, entitled: Determination air = 270 ml/min of Residual Styrene in Latex, Leonard, C.D., make-up = 0 ml/min Vora, N.M.et al Analysis time: = 3.2 min at the specified carrier gas flow rate and column tempera- METHOD 312B—DETERMINATION OF RESIDUAL ture. STYRENE IN STYRENE-BUTADIENE (SBR) 6.6 Gas chromatographic column, DB–1, 30 RUBBER LATEX BY CAPILLARY GAS CHROMA- M X 0.53 ID, or equivalent, with a 1.5 micron TOGRAPHY film thickness. 6.7 Data collection system, Perkin-Elmer/ 1.0 Scope Nelson Series Turbochrom 4 Series 900 Inter- 1.1 This method is applicable to SBR latex face, or equivalent. solutions. 6.8 Pipet, automatic dispensing, 50-ml ca- 1.2 This method quantitatively determines pacity, and 2-liter reservoir. residual styrene concentrations in SBR latex 6.9 Flasks, volumetric, class A, 100-ml and solutions at levels from 80 to 1200 ppm. 1000-ml capacity. 6.10 Pipet, volumetric delivery, 10-ml ca- 2.0 Principle of Method pacity, class A. 2.1 A weighed sample of a latex solution is 7.0 Chemicals and Reagents coagulated with an ethyl alcohol (EtOH) so- CHEMICALS: lution containing a specific amount of alpha- 7.1 Styrene, C8H8, 99 + %, CAS 100–42–5 methyl styrene (AMS) as the internal stand- 7.2 Alpha methyl styrene, C9H10, 99%, CAS ard. The extract of this coagulation is then 98–83–9 injected into a gas chromatograph and sepa- 7.3 Ethyl alcohol, C2H5OH, denatured for- rated into individual components. Quan- mula 2B, CAS 64–17–5 tification is achieved by the method of inter- REAGENTS: nal standardization. 7.4 Internal Standard Stock Solution: 5.0 mg/ml AMS in ethyl alcohol. 3.0 Definitions 7.4.1 Into a 100-ml volumetric flask, weigh 3.1 The definitions are included in the text 0.50 g of AMS to the nearest 0.1 mg. as needed. 7.4.2 Dilute to the mark with ethyl alcohol. This solution will contain 5.0 mg/ml AMS in 4.0 Interferences [Reserved] ethyl alcohol and will be labeled the AMS STOCK SOLUTION. 5.0 Safety 7.5 Internal Standard Working Solution: 2500 ug/50 ml of AMS in ethyl alcohol. 5.1 This method may involve hazardous 7.5.1 Using a 10 ml volumetric pipet, quan- materials, operations, and equipment. This titatively transfer 10.0 ml of the AMS method does not purport to address all of the STOCK SOLUTION into a 1000-ml volumetric safety problems associated with its use. It is flask. the responsibility of the user of this method 7.5.2 Dilute to the mark with ethyl alcohol. to establish appropriate safety and health This solution will contain 2500 ug/50ml of practices and determine the applicability of AMS in ethyl alcohol and will be labeled the regulatory limitations prior to use. AMS WORKING SOLUTION.

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7.5.3 Transfer the AMS WORKING SOLU- R = Mr/S TION to the automatic dispensing pipet res- where: ervoir. Mu = Mean value of styrene in the unspiked 7.6 Styrene Stock Solution: 5.0 mg/ml sty- sample rene in ethyl alcohol. Ms = Measured amount of styrene in the 7.6.1 Into a 100-ml volumetric flask, weigh spiked sample 0.50 g of styrene to the nearest 0.1 mg. Mr = Measured amount of the spiked com- 7.6.2 Dilute to the mark with ethyl alcohol. pound This solution will contain 5.0 mg/ml styrene S = Amount of styrene added to the spiked in ethyl alcohol and will be labeled the STY- sample RENE STOCK SOLUTION. R = Fraction of spiked styrene recovered 7.7 Styrene Working Solution: 5000 ug/10 ml 9.6 A value of R between 0.70 and 1.30 is ac- of styrene in ethyl alcohol. ceptable. 7.7.1 Using a 10-ml volumetric pipet, quan- 9.7 R is used to correct all reported results titatively transfer 10.0 ml of the STYRENE for each compound by dividing the measured STOCK SOLUTION into a 100-ml volumetric results of each compound by the R for that flask. compound for the same sample type. 7.7.2 Dilute to the mark with ethyl alcohol. This solution will contain 5000 ug/10 ml of 10.0 Calibration styrene in ethyl alcohol and will be labeled the STYRENE WORKING SOLUTION. 10.1 Using a 10-ml volumetric pipet, quantitatively transfer 10.0 ml of the STYRENE 8.0 Sample Collection, Preservation and Storage WORKING SOLUTION (section 7.7.2 of this method) into a 2-oz bottle. 8.1 Label a 2-oz sample poly-cap lid with 10.2 Using the AMS WORKING SOLUTION the identity, date and time of the sample to equipped with the automatic dispensing be obtained. pipet (section 7.5.3 of this method), transfer 8.2 At the sample location, open sample 50.0 ml of the internal standard solution into valve for at least 15 seconds to ensure that the 2-oz bottle. the sampling pipe has been properly flushed 10.3 Cap the 2-oz bottle and swirl. This is with fresh sample. the calibration standard, which contains 5000 8.3 Fill the sample jar to the top (no μg of styrene and 2500 μg of AMS. headspace) with sample, then cap it tightly. 10.4 Using the conditions prescribed (sec- 8.4 Deliver sample to the Laboratory for tion 6.5 of this method), chromatograph 1 μl testing within one hour of sampling. of the calibration standard. 8.5 Laboratory testing will be done within 10.5 Obtain the peak areas and calculate two hours of the sampling time. the relative response factor as described in 8.6 No special storage conditions are re- the calculations section (section 12.1 of this quired unless the storage time exceeds 2 method). hours in which case refrigeration of the sample is recommended. 11.0 Procedure 9.0 Quality Control 11.1 Into a tared 2-oz bottle, weigh 10.0 g of latex to the nearest 0.1 g. 9.1 For each sample type, 12 samples of 11.2 Using the AMS WORKING SOLUTION SBR latex shall be obtained from the process equipped with the automatic dispensing for the recovery study. Half the vials and pipet (section 7.5.3 of this method), transfer caps shall be tared, labeled ‘‘spiked’’, and 50.0 ml of the internal standard solution into numbered 1 through 6. The other vials are la- the 2-oz bottle. beled ‘‘unspiked’’ and need not be tared, but 11.3 Cap the bottle. Using a mechanical are also numbered 1 through 6. shaker, shake the bottle for at least one 9.2 The six vials labeled ‘‘spiked’’ shall be minute or until coagulation of the latex is spiked with an amount of styrene to approxi- complete as indicated by a clear solvent. mate 50% of the solution’s expected residual 11.4 Using the conditions prescribed (sec- styrene level. tion 6.5 of this method), chromatograph 1 ul 9.3 The spiked samples shall be shaken for of the liquor. several hours and allowed to cool to room 11.5 Obtain the peak areas and calculate temperature before analysis. the concentration of styrene in the latex as 9.4 The six samples of unspiked solution described in the calculations section (Sec- shall be coagulated and a mean styrene value tion 12.2 of this method). shall be determined, along with the standard deviation, and the percent relative standard 12.0 Calculations deviation. 9.5 The six samples of the spiked solution 12.1 Calibration: shall be coagulated and the results of the RF = (Wx × Ais) / (Wis × Ax) analyses shall be determined using the fol- where: lowing equations: RF = the relative response factor for styrene Mr = Ms¥Mu Wx = the weight (ug) of styrene 760

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Ais = the area of AMS Percent styrene is calculated by relating the Wis = the weight (ug) of AMS area of the styrene peak to the area of the Ax = the area of styrene Internal Standard peak of known concentra- 12.2 Procedure: tion. ppm = (A RF × W ) / (A × W ) styrene x is is s 3.0 Definitions where: ppmstyrene = parts per million of styrene in the 3.1 The definitions are included in the text latex as needed. Ax = the area of styrene RF = the response factor for styrene 4.0 Interferences [Reserved] W = the weight (ug) of AMS is 5.0 Safety Ais = the area of AMS Ws = the weight (g) of the latex sample 5.1 When using solvents, avoid contact 12.3 Correct for recovery (R) as determined with skin and eyes. Wear hand and eye pro- by section 9.0 of this method. tection. Wash thoroughly after use. 5.2 Avoid overexposure to solvent vapors. 13.0 Precision Handle only in well ventilated areas. 13.1 Precision for the method was deter- 6.0 Equipment and Supplies mined at the 80, 144, 590, and 1160 ppm levels. The standard deviations were 0.8, 1.5, 5 and 9 6.1 Gas Chromatograph—Hewlett Packard ppm respectively. The percent relative 5890, Series II with flame ionization detector, standard deviations (%RSD) were 1% or less or equivalent. at all levels. Five degrees of freedom were Column—HP 19095F–123, 30m × 0.53mm, or used for all precision data except at the 80 equivalent. Substrate HP FFAP (cross- ppm level, where nine degrees of freedom linked) film thickness 1 micrometer. Glass were used. Note: These are example results injector port liners with silanized glass wool and do not replace quality assurance proce- plug. dures in this method. Integrator—HP 3396, Series II, or equivalent. 14.0 Pollution Prevention 6.2 Wrist action shaker 14.1 Waste generation should be minimized 6.3 Automatic dispenser where possible. Sample size should be an 6.4 Automatic pipet, calibrated to deliver amount necessary to adequately run the 5.0 ±0.01 grams of latex analysis. 6.5 Four-ounce wide-mouth bottles with foil lined lids 15.0 Waste Management 6.6 Crimp cap vials, 2ml, teflon lined septa 15.1 Discard liquid chemical waste into the 6.7 Disposable pipets chemical waste drum. 6.8 Qualitative filter paper 15.2 Discard latex sample waste into the 6.9 Cap crimper latex waste drum. 6.10 Analytical balance 15.3 Discard polymer waste into the poly- 6.11 10ml pipette mer waste container. 6.12 Two-inch funnel 16.0 References 7.0 Reagents and Standards 16.1 This method is based on Goodyear 7.1 2-Propanol (HP2C grade) Chemical Division Test Method E–889. 7.2 Alpha methyl styrene (99 + % purity) 7.3 Styrene (99 + % purity) METHOD 312C—DETERMINATION OF RESIDUAL 7.4 Zero air STYRENE IN SBR LATEX PRODUCED BY 7.5 Hydrogen (chromatographic grade) EMULSION POLYMERIZATION 7.6 Helium 7.7 Internal Standard preparation 1.0 Scope 7.7.1 Weigh 5.000–5.005 grams of alpha-meth- 1.1 This method is applicable for deter- yl styrene into a 100ml volumetric flask and mining the amount of residual styrene in bring to mark with 2-propanol to make SBR latex as produced in the emulsion po- Stock ‘‘A’’ Solution. lymerization process. NOTE: Shelf life—6 months. 7.7.2 Pipette 10ml of Stock ‘‘A’’ Solution 2.0 Principle of Method into a 100ml volumetric flask and bring to 2.1 A weighed sample of latex is coagulated mark with 2-propanol to prepare Stock ‘‘B’’ in 2-propanol which contains alpha-methyl Solution. styrene as an Internal Standard. The extract 7.7.3 Pipette 10ml of the Stock ‘‘B’’ solu- from the coagulation will contain the alpha- tion to a 1000ml volumetric flask and bring methyl styrene as the Internal Standard and to the mark with 2-propanol. This will be the the residual styrene from the latex. The ex- Internal Standard Solution (0.00005 grams/ tract is analyzed by a Gas Chromatograph. ml).

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7.8 Certification of Internal Standard— 9.1.2 If new types of samples are being ana- Each batch of Stock ‘‘B’’ Solution will be lyzed, then recovery efficiency for each new certified to confirm concentration. type of sample must be determined. New 7.8.1 Prepare a Standard Styrene Control type includes any change, such as polymer Solution in 2-propanol by the following type, physical form or a significant change method: in the composition of the matrix. ± 7.8.1.1 Weigh 5.000 .005g of styrene to a 9.2 Recovery efficiency must be determined 100ml volumetric flask and fill to mark with once for each sample type and whenever 2-propanol to make Styrene Stock ‘‘A’’ Solu- modifications are made to the method. tion. 9.2.1 In determining the recovery effi- 7.8.1.2 Pipette 10ml of Styrene Stock ‘‘A’’ Solution to a 100ml volumetric flask and fill ciency, the quadruplet sampling system shall to mark with 2-propanol to make Styrene be used. Six sets of samples (for a total of 24) Stock ‘‘B’’ Solution. shall be taken. In each quadruplet set, half 7.8.1.3 Pipette 10ml of Styrene Stock ‘‘B’’ of the samples (two out of the four) shall be soluion to a 250ml volumtric flask and fill to spiked with styrene. mark wtih 2-propanol to make the Certifi- 9.2.2 Prepare the samples as described in cation Solution. section 8 of this method. To the vials labeled 7.8.2 Certify Alpha-Methyl Styrene Stock ‘‘spiked’’, add a known amount of styrene ‘‘B’’ Solution. that is expected to be present in the latex. 7.8.2.1 Pipette 5ml of the Certification So- 9.2.3 Run the spiked and unspiked samples lution and 25ml of the Alpha Methyl Styrene in the normal manner. Record the concentra- Internal Standard Solution to a 4-oz. bottle, tions of styrene reported for each pair of cap and shake well. spiked and unspiked samples with the same 7.8.2.2 Analyze the resulting mixture by GC vial number. using the residual styrene method. (11.4–11.6 9.2.4 For each hydrocarbon, calculate the of this method) average recovery efficiency (R) using the fol- 7.8.2.3 Calculate the weight of alpha meth- lowing equation: yl styrene present in the 25ml aliquat of the new Alpha Methyl Styrene Standard by the R=S(Rn)/12 following equation: Where: n = sample number ¥ Wx = Fx xWis(Ax/Ais) Rn = (Ms Mu)/S Where Ms = total mass of compound (styrene) measured in spiked sample (μg) Ax = Peak area of alpha methyl styrene Ais = Peak area of styrene Mu = total mass of compound (styrene) meas- μ Wx = Weight of alpha methyl styrene ured in unspiked sample ( g) Wis = Weight of styrene (.00100) S = theoretical mass of compound (styrene) Fx = Analyzed response factor = 1 spiked into sample (μg) The Alpha Methyl Styrene Stock Solution R = fraction of spiked compound (styrene) used to prepare the Internal Standard Solu- recovered tion may be considered certified if the 9.2.5 A different R value should be obtained weight of alpha methyl styrene analyzed by for each sample type. A value of R between this method is within the range of .00121g to 0.70 and 1.30 is acceptable. .00129g. 9.2.6 R is used to correct all reported re- 8.0 Sampling sults for each compound by dividing the measured results of each compound by the R 8.1 Collect a latex sample in a capped con- for that compound for the same sample type. tainer. Cap the bottle and identify the sample as to location and time. 10.0 Calibration 8.2 Deliver sample to Laboratory for testing within one hour. A styrene control sample will be tested 8.3 Laboratory will test within two hours. weekly to confirm the FID response and cali- 8.4 No special storage conditions are re- bration. quired. 10.1 Using the Styrene Certification Solu- tion prepared in 7.8.1, perform test analysis 9.0 Quality Control as described in 7.8.2 using the equation in 9.1 The laboratory is required to operate a 7.8.2.3 to calculate results. formal quality control program. This con- 10.2 Calculate the weight of styrene in the sists of an initial demonstration of the capa- styrene control sample using the following bility of the method as well as ongoing anal- equation: ysis of standards, blanks, and spiked samples to demonstrate continued performance. Wsty = (Fx xAsty xWis)Ais 9.1.1 When the method is first set up, a The instrument can be considered cali- calibration is run and the recovery efficiency brated if the weight of the styrene analyzed for each type of sample must be determined. is within range of 0.00097–0.00103gms.

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11.0 Procedure 15.0 Waste Management 11.1 Using an auto pipet, add 25ml of Inter- 15.1 All waste shall be handled in accord- nal Standard Solution to a 4 oz. wide-mouth ance with Federal and State environmental bottle. regulations. 11.2 Using a calibrated auto pipet, add 5.0 ±0.01g latex to the bottle containing the 25ml 16.0 References [Reserved] of Internal Standard Solution. METHOD 313A—DETERMINATION OF RESIDUAL 11.3 Cap the bottle and place on the wrist HYDROCARBONS IN RUBBER CRUMB action shaker. Shake the sample for a minimum of five minutes using the timer on the 1.0 Scope and Application shaker. Remove from shaker. 11.4 Using a disposable pipet, fill the 2ml 1.1 This method determines residual tol- sample vial with the clear alcohol extract. uene and styrene in stripper crumb of the of (If the extract is not clear, it should be fil- the following types of rubber: polybutadiene tered using a funnel and filter paper.) Cap (PBR) and styrene/butadiene rubber (SBR), and seal the vial. both derived from solution polymerization 11.5 Place the sample in the autosampler processes that utilize toluene as the polym- tray and start the GC and Integrator. The erization solvent. sample will be injected into the GC by the 1.2 The method is applicable to a wide auto-injector, and the Integrator will print range of concentrations of toluene and sty- the results. rene provided that calibration standards 11.6 Gas Chromatograph Conditions cover the desired range. It is applicable at least over the range of 0.01 to 10.0 % residual ° Oven Temp—70 C toluene and from 0.1 to 3.0 % residual sty- Injector Temp—225 °C ° rene. It is probably applicable over a wider Detector Temp—275 C range, but this must be verified prior to use. Helium Pressure—500 KPA 1.3 The method may also be applicable to Column Head Pressure—70 KPA other process samples as long as they are of Makeup Gas—30 ml/min. a similar composition to stripper crumb. See Column—HP 19095F—123, 30m × 0.53mm Sub- section 3.1 of this method for a description of strate: HP—FFAP (cross-linked) 1 microm- stripper crumb. eter film thickness 2.0 Summary of Method 12.0 Calculations 2.1 The wet crumb is placed in a sealed vial 12.1 The integrator is programmed to do and run on a headspace sampler which heats the following calculation at the end of the the vial to a specified temperature for a spe- analysis: cific time and then injects a known volume %ResidualStyrene = (Ax XWis)/(Ais XWx)XFx of vapor into a capillary GC. The concentra- X100 tion of each component in the vapor is pro- Where: portional to the level of that component in Ax = Peak area of styrene the crumb sample and does not depend on Ais = Peak area of internal standard water content of the crumb. Wx = Weight of sample = 5g 2.2 Identification of each component is per- Wis = Weight of internal std. = 0.00125g formed by comparing the retention times to Fx = Analyzed response factor = 1.0 those of known standards. 12.2 The response factor is determined by 2.3 Results are calculated by the external analyzing a solution of 0.02g of styrene and standard method since injections are all per- 0.02g of alpha methyl styrene in 100ml of 2- formed in an identical manner. The response propanol. Calculate the factor by the fol- for each component is compared with that lowing equation: obtained from dosed samples of crumb. 2.4 Measured results of each compound are F = (W xA )/(W xA ) x x is is x corrected by dividing each by the average re- Where: covery efficiency determined for the same Wx = Weight of styrene compound in the same sample type. Ax = Peak area of styrene Wis = Weight of alpha methyl styrene 3.0 Definitions A = Peak area of alpha methyl styrene is 3.1 Stripper crumb refers to pieces of rub- 13.0 Method Performance ber resulting from the steam stripping of a toluene solution of the same polymer in a 13.1 Performance must be determined for water slurry. The primary component of this each sample type by following the proce- will be polymer with lesser amounts of en- dures in section 9 of this method. trained water and residual toluene and other hydrocarbons. The amounts of hydrocarbons 14.0 Waste Generation present must be such that the crumb is a 14.1 Waste generation should be minimized solid material, generally less that 10 % of where possible. the dry rubber weight.

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4.0 Interferences 6.3 HP Chemstation consisting of computer, printer and Chemstation software, or 4.1 Contamination is not normally a prob- an equivalent chromatographic data system. lem since samples are sealed into vials im- 6.4 20 ml headspace vials with caps and mediately on sampling. septa. 4.2 Cross contamination in the headspace 6.5 Headspace vial crimper. sampler should not be a problem if the cor- 6.6 Microliter pipetting syringes. rect sampler settings are used. This should 6.7 Drying oven at 100 deg C vented into be verified by running a blank sample imme- cold trap or other means of trapping hydro- diately following a normal or high sample. carbons released. Settings may be modified if necessary if this 6.8 Laboratory shaker or tumbler suitable proves to be a problem, or a blank sample for the headspace vials. may be inserted between samples. 6.9 Personal protective equipment required 4.3 Interferences may occur if volatile hy- for sampling the process such as rubber drocarbons are present which have retention gloves and face and eye protection. times close to that of the components of interest. Since the solvent makeup of the proc- 7.0 Reagents and Standards esses involved are normally fairly well de- 7.1 Toluene, 99.9 + % purity, HPLC grade. fined this should not be a problem. If it is 7.2 Styrene, 99.9 + % purity, HPLC grade. found to be the case, switching to a different 7.3 Dry rubber of same type as the stripper chromatographic column will probably re- crumb samples. solve the situation. 8.0 Sample Collection, Preservation and Storage 5.0 Safety 8.1 Collect a sample of crumb in a manner 5.1 The chemicals specified in this method appropriate for the process equipment being should all be handled according to standard sampled. laboratory practices as well as any special 8.1.1 If conditions permit, this may be done precautions that may be listed in the MSDS by passing a stream of the crumb slurry for that compound. through a strainer, thus separating the 5.2 Sampling of strippers or other process crumb from the water. Allow the water to streams may involve high pressures and tem- drain freely, do not attempt to squeeze any peratures or may have the potential for ex- water from the crumb. Results will not de- posure to chemical fumes. Only personnel pend on the exact water content of the sam- who have been trained in the specific samples. Immediately place several pieces of pling procedures required for that process crumb directly into a headspace vial. This should perform this operation. An under- should be done with rubber gloves to protect standing of the process involved is necessary. the hands from both the heat and from con- Proper personal protective equipment should tact with residual hydrocarbons. The vial be worn. Any sampling devices should be in- should be between 1⁄4 and 1⁄3 full. Results do spected prior to use. A detailed sampling not depend on sample size as long as there is procedure which specifies exactly how to ob- sufficient sample to reach an equilibrium tain the sample must be written and fol- vapor pressure in the headspace of the vial. lowed. Cap and seal the vial. Prepare each sample at least in duplicate. This is to minimize the ef- 6.0 Equipment and Supplies fect of the variation that naturally occurs in 6.1 Hewlett Packard (HP) 7694 Headspace the composition of non homogeneous crumb. sampler, or equivalent, with the following The free water is not analyzed by this meth- conditions: od and should be disposed of appropriately along with any unused rubber crumb. Times (min.): GC cycle time 6.0 , vial equili- 8.1.2 Alternatively the process can be sam- bration 30.0 , pressurization 0.25 , loop fill pled in a specially constructed sealed bomb 0.25, loop equilibration 0.05 , inject 0.25 which can then be transported to the labora- Temperatures (deg C): oven 70, loop 80, trans- tory. The bomb is then cooled to ambient fer line 90 temperature by applying a stream of running Pressurization gas: He @ 16 psi water. The bomb can then be opened and the 6.2 HP 5890 Series II capillary gas chro- crumb separated from the water and the matograph, or equivalent, with the following vials filled as described in section 8.1.1 of conditions: this method. The bomb may be stored up to 8 hours prior to transferring the crumb into Column: Supelco SPB–1, or equivalent, 15m × × μ vials. .25mm .25 film 8.2 The sealed headspace vials may be run Carrier: He @ 6 psi immediately or may be stored up to 72 hours Run time: 4 minutes prior to running. It is possible that even Oven: 70 deg C isothermal longer storage times may be acceptable, but Injector: 200 deg C split ratio 50:1 this must be verified for the particular type Detector: FID @ 220 deg C of sample being analyzed (see section 9.2.3 of

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this method). The main concern here is that ples for 24, 48 and 72 hours or longer if longer some types of rubber eventually may flow, storage times are desired. thus compacting the crumb so that the sur- 9.3 A spiked rubber standard should be run face area is reduced. This may have some ef- on a regular basis to verify system perform- fect on the headspace equilibration. ance. This would probably be done daily if samples are run daily. This is prepared in the 9.0 Quality Control same manner as the calibration standards 9.1 The laboratory is required to operate a (section 10.1 of this method), except that formal quality control program. This con- only one concentration of toluene and sty- sists of an initial demonstration of the capa- rene is prepared. Choose concentrations of bility of the method as well as ongoing anal- toluene and styrene that fall in the middle of ysis of standards, blanks and spiked samples the range expected in the stripper crumb and to demonstrate continued performance. then do not change these unless there is a 9.1.1 When the method is first set up a cali- major change in the composition of the un- bration is run (described in section 10 of this knowns. If it becomes necessary to change method) and an initial demonstration of the composition of this standard the initial method capability is performed (described in performance demonstration must be re- section 9.2 of this method). Also recovery ef- peated with the new standard (section 9.2 of ficiency for each type of sample must be de- this method). termined (see section 9.4 of this method). 9.3.1 Each day prepare one spiked rubber 9.1.2 It is permissible to modify this meth- standard to be run the following day. The od in order to improve separations or make dry rubber may be prepared in bulk and other improvements, provided that all per- stored for any length of time consistent with formance specifications are met. Each time a the shelf life of the product. The addition of modification to the method is made it is nec- water and hydrocarbons must be performed essary to repeat the calibration (section 10 of daily and all the steps described under sec- this method), the demonstration of method tion 10.1 of this method must be followed. performance (section 9.2 of this method) and 9.3.2 Run the spiked rubber standard pre- the recovery efficiency for each type of sam- pared the previous day. Record the results ple (section 9.4 of this method). and plot on an appropriate control chart or 9.1.3 Ongoing performance should be mon- other means of determining statistical con- itored by running a spiked rubber standard. trol. If this test fails to demonstrate that the 9.3.3 If the results for the standard indicate analysis is in control, then corrective action that the test is out of control then correc- must be taken. This method is described in tive action must be taken. This may include section 9.3 of this method. a check on procedures, instrument settings, 9.1.4 If new types of samples are being ana- maintenance or recalibration. Samples may lyzed then recovery efficiency for each new be stored (see section 8.2 of this method) type of sample must be determined. New until compliance is demonstrated. type includes any change, such as polymer 9.4 Recovery efficiency must be determined type, physical form or a significant change once for each sample type and whenever in the composition of the matrix. modifications are made to the method. 9.2 Initial demonstration of method capa- 9.4.1 For each sample type collect 12 sam- bility to establish the accuracy and precision ples from the process (section 8.1 of this of the method. This is to be run following method). This should be done when the proc- the calibration described in section 10 of this ess is operating in a normal manner and re- method. sidual hydrocarbon levels are in the normal 9.2.1 Prepare a series of identical spiked range. Half the vials and caps should be rubber standards as described in section 9.3 tared, labeled ‘‘spiked’’ and numbered 1 of this method. A sufficient number to deter- through 6. The other vials are labeled mine statistical information on the test ‘‘unspiked’’ and need not be tared but are should be run. Ten may be a suitable num- also numbered 1 through 6. Immediately on ber, depending on the quality control meth- sampling, the vials should be capped to pre- odology used at the laboratory running the vent loss of volatiles. Allow all the samples tests. These are run in the same manner as to cool completely to ambient temperature. unknown samples (see section 11 of this Reweigh each of the vials labeled ‘‘spiked’’ method). to determine the weight of wet crumb inside. 9.2.2 Determine mean and standard devi- 9.4.2 The dry weight of rubber present in ation for the results. Use these to determine the wet crumb is estimated by multiplying the capability of the method and to calculate the weight of wet crumb by the fraction of suitable control limits for the ongoing per- nonvolatiles typical for the sample. If this is formance check which will utilize the same not known, an additional quantity of crumb standards. may be sampled, weighed, dried in an oven 9.2.3 Prepare several additional spiked rub- and reweighed to determine the fraction of ber standards and run 2 each day to deter- volatiles and nonvolatiles prior to starting mine the suitability of storage of the sam- this procedure.

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9.4.3 To the vials labeled ‘‘spiked’’ add an 9.4.9 A different R value should be obtained amount of a mixture of toluene and styrene for each compound (styrene and toluene) and that is between 40 and 60 % of the amount for each sample type. expected in the crumb. This is done by re- 9.4.10 A value of R between 0.70 and 1.30 is moving the cap, adding the mixture by sy- acceptable. ringe, touching the tip of the needle to the 9.4.11 R is used to correct all reported re- sample in order to remove the drop and then sults for each compound by dividing the immediately recapping the vials. The mix- measured results of each compound by the R ture is not added through the septum, be- for that compound for the same sample type cause a punctured septum may leak and vent (see section 12.2 of this method.) vapors as the vial is heated. The weights of toluene and styrene added may be calculated 10.0 Calibration from the volumes of the mixture added, its 10.1 Calibration standards are prepared by composition and density, or may be deter- dosing known amounts of the hydrocarbons mined by the weight of the vials and caps of interest into vials containing known prior to and after addition. The exact dry amounts of rubber and water. weight of rubber present and the concentra- 10.1.1 Cut a sufficient quantity of dry rub- tion of residual toluene and styrene are not ber of the same type as will be analyzed into known at this time so an exact calculation pieces about the same size as that of the of the concentration of hydrocarbons is not crumb. Place these in a single layer on a possible until the test is completed. piece of aluminum foil or other suitable sur- 9.4.4 Place all the vials onto a shaker or face and place into a forced air oven at 100 °C tumbler for 24 ±2 hours. This is essential in for four hours. This is to remove any resid- order for the hydrocarbons to be evenly dis- ual hydrocarbons that may be present. This tributed and completely absorbed into the step may be performed in advance. rubber. If this is not followed the toluene 10.1.2 Into each of a series of vials add 3.0 and styrene will be mostly at the surface of g of the dry rubber. the rubber and high results will be obtained. 10.1.3 Into each vial add 1.0 ml distilled 9.4.5 Remove the vials from the shaker and water or an amount that is close to the tap them so that all the crumb settles to the amount that will be present in the un- bottom of the vials. Allow them to stand for knowns. The exact amount of water present 1 hour prior to analysis to allow any liquid does not have much effect on the analysis, to drain fully to the bottom. but it is necessary to have a saturated envi- 9.4.6 Run the spiked and unspiked samples ronment. The water will also aid in the uni- in the normal manner. Record the concentra- form distribution of the spiked hydrocarbons tions of toluene and styrene reported for over the surface of the rubber after the vials each pair of spiked and unspiked samples are placed on the shaker (in step 10.1.5 of this with the same vial number. method). 9.4.7 Open each of the vials labeled 10.1.4 Into each vial add varying amounts ‘‘spiked’’, remove all the rubber crumb and of toluene and styrene by microliter syringe place it into a tarred drying pan. Place in a and cap the vials immediately to prevent 100 deg C oven for two hours, cool and re- loss. The tip of the needle should be carefully weigh. Subtract the weight of the tare to touched to the rubber in order to transfer give the dry weight of rubber in each spiked the last drop to the rubber. Toluene and sty- vial. Calculate the concentration of toluene rene may first be mixed together in suitable and styrene spiked into each vial as percent proportions and added together if desired. of dry rubber weight. This will be slightly The weights of toluene and styrene added different for each vial since the weights of may be calculated from the volumes of the dry rubber will be different. mixture added, its composition and density, 9.4.8 For each hydrocarbon calculate the or may be determined by the weight of the average recovery efficiency (R) using the fol- vials and caps prior to and after addition. lowing equations: Concentrations of added hydrocarbons are

R = RlS(Pn)/6 (average of the 6 individual Rn calculated as percent of the dry rubber values) weight. At least 5 standards should be prepared with the amounts of hydrocarbons Where: added being calculated to cover the entire R = (C —C ) / S n ns nu n range possible in the unknowns. Retain two Where: samples with no added hydrocarbons as n = vial number blanks. Cns = concentration of compound measured 10.1.5 Place all the vials onto a shaker or in spiked sample number n. tumbler for 24 ±2 hours. This is essential in Cnu = concentration of compound measured order for the hydrocarbons to be evenly dis- in unspiked sample number n. tributed and completely absorbed into the Sn = theoretical concentration of compound rubber. If this is not followed the toluene spiked into sample n calculated in step and styrene will be mostly at the surface of 9.4.7 the rubber and high results will be obtained.

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10.1.6 Remove the vials from the shaker 12.0 Data Analysis and Calculations and tap them so that all the crumb settles to 12.1 For each set of duplicate samples cal- the bottom of the vials. Allow them to stand culate the average of the measured con- for 1 hour prior to analysis to allow any liq- centration of toluene and styrene. If more uid to drain fully to the bottom. than two replicates of each sample are run 10.2 Run the standards and blanks in the calculate the average over all replicates. same manner as described for unknowns (sec- 12.2 For each sample correct the measured tion 11 of this method), starting with a amounts of toluene and styrene using the blank, then in order of increasing hydro- following equation: carbon content and ending with the other blank. Corrected Result = Cm/R 10.3 Verify that the blanks are sufficiently Where:

free from toluene and styrene or any inter- Cm = Average measured concentration for fering hydrocarbons. that compound. 10.3.1 It is possible that trace levels may be R = Recovery efficiency for that compound present even in dry product. If levels are in the same sample type (see section 9.4 high enough that they will interfere with the of this method) calibration then the drying procedure in sec- 12.3 Report the recovery efficiency (R) and tion 10.1.1 of this method should be reviewed the corrected results of toluene and styrene and modified as needed to ensure that suit- for each sample. able standards can be prepared. 10.3.2 It is possible that the final blank is 13.0 Method Performance contaminated by the previous standard. If 13.1 This method can be very sensitive and this is the case review and modify the sam- reproducible. The actual performance de- pler parameters as needed to eliminate this pends largely on the exact nature of the sam- problem. If necessary it is possible to run ples being analyzed. Actual performance blank samples between regular samples in must be determined by each laboratory for order to reduce this problem, though it each sample type. should not be necessary if the sampler is 13.2 The main source of variation is the ac- properly set up. tual variation in the composition of non ho- 10.4 Enter the amounts of toluene and sty- mogeneous crumb in a stripping system and rene added to each of the samples (as cal- the small sample sizes employed here. It culated in section 10.1.4 of this method) into therefore is the responsibility of each labora- the calibration table and perform a calibra- tory to determine the optimum number of tion utilizing the external standard method replicates of each sample required to obtain of analysis. accurate results. 10.5 At low concentrations the calibration should be close to linear. If a wide range of 14.0 Pollution Prevention levels are to be determined it may be desirable to apply a nonlinear calibration to get 14.1 Samples should be kept sealed when the best fit. possible in order to prevent evaporation of hydrocarbons. 11.0 Procedure 14.2 When drying of samples is required it should be done in an oven which vents into 11.1 Place the vials in the tray of the a suitable device that can trap the hydro- headspace sampler. Enter the starting and carbons released. ending positions through the console of the 14.3 Dispose of samples as described in sec- sampler. For unknown samples each is run in tion 15. duplicate to minimize the effect of variations in crumb composition. If excessive 15.0 Waste Management variation is noted it may be desirable to run more than two of each sample. 15.1 Excess stripper crumb and water as 11.2 Make sure the correct method is load- well as the contents of the used sample vials ed on the Chemstation. Turn on the gas flows should be properly disposed of in accordance and light the FID flame. with local and federal regulations. 11.3 Start the sequence on the 15.2 Preferably this will be accomplished Chemstation. Press the START button on by having a system of returning unused and the headspace unit. The samples will be spent samples to the process. automatically injected after equilibrating 16.0 References for 30 minutes in the oven. As each sample is completed the Chemstation will calculate 16.1 ‘‘HP 7694 Headspace Sampler—Oper- and print out the results as percent toluene ating and Service Manual’’, Hewlett-Packard and styrene in the crumb based on the dry Company, publication number G1290–90310, weight of rubber. June 1993.

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METHOD 313B—THE DETERMINATION OF RESID- Initial time = 6 min UAL HYDROCARBON IN SOLUTION POLYMERS Program rate = 10 deg C/min BY CAPILLARY GAS CHROMATOGRAPHY Upper limit temperature = 175 deg C Upper limit interval = 10 min 1.0 Scope 6.6.4 Detector parameters: 1.1 This method is applicable to solution Detector temperature = 300 deg C polymerized polybutadiene (PBD). Hydrogen flow = 30 ml/min 1.2 This method quantitatively determines Air flow = 350 ml/min n-hexane in wet crumb polymer at levels Nitrogen make up = 26 ml/min from 0.08 to 0.15% by weight. 1.3 This method may be extended to the de- 6.7 Gas chromatographic columns: SE–54 termination of other hydrocarbons in solu- (5%-phenyl) (1%-vinyl)-methylpolysiloxane, × tion produced polymers with proper experi- 15 M 0.53 mm ID with a 1.2 micron film mentation and documentation. thickness, and a Carbowax 20M (polyethylene glycol), 15 M × 0.53 mm ID with a 1.2 micron 2.0 Principle of Method film thickness. 6.7.1 Column assembly: using a 0.53 mm ID 2.1 A weighed sample of polymer is dis- butt connector union, join the 15 M × 0.53 solved in chloroform and the cement is co- mm SE–54 column to the 15 M × 0.53 mm agulated with an isopropyl alcohol solution Carbowax 20M. The SE–54 column will be in- containing a specific amount of alpha-meth- serted into the injector and the Carbowax yl styrene (AMS) as the internal standard. 20M inserted into the detector after they The extract of this coagulation is then in- have been joined. jected into a gas chromatograph and sepa- 6.7.2 Column parameters: rated into individual components. Quan- tification is achieved by the method of inter- Helium flow = 2.8 ml/min nal standardization. Helium headpressure = 2 psig 6.8 Centrifuge 3.0 Definitions 6.9 Data collection system, Hewlett-Pack- 3.1 The definitions are included in the text ard Model 3396, or equivalent as needed. 6.10 Pipet, 25–ml capacity, automatic dispensing, and 2 liter reservoir 4.0 Interferences [Reserved] 6.11 Pipet, 2–ml capacity, volumetric delivery, class A 5.0 Safety 6.12 Flasks, 100 and 1000-ml capacity, volu- 5.1 This method may involve hazardous metric, class A materials, operations, and equipment. This 6.13 Vial, serum, 50-ml capacity, red rubber method does not purport to address all of the septa and crimp ring seals safety problems associated with its use. It is 6.14 Sample collection basket fabricated the responsibility of the user of this method out of wire mesh to allow for drainage to establish appropriate safety and health practices and determine the applicability of 7.0 Chemicals and Reagents regulatory limitations prior to use. CHEMICALS: 6.0 Equipment and Supplies 7.1 alpha-Methyl Styrene, C9H10, 99 + % purity, CAS 98–83–9 6.1 Analytical balance, 160 g capacity, 0.1 7.2 n-Hexane, C6H14, 99 + % purity, CAS mg resolution 110–54–3 6.2 Bottles, 2-oz capacity with poly-cap 7.3 Isopropyl alcohol, C3H8O 99.5 + % pu- screw lids rity, reagent grade, CAS 67–63–0 6.3 Mechanical shaker 7.4 Chloroform, CHCl3, 99% min., CAS 67– 6.4 Syringe, 10–ul capacity 66–3 6.5 Syringe, 2.5–ml capacity, with 22 gauge REAGENTS: 1.25 inch needle, PP/PE material, disposable 7.5 Internal Standard Stock Solution: 10 6.6 Gas chromatograph, Hewlett-Packard mg/25 ml AMS in isopropyl alcohol. model 5890, or equivalent, configured with 7.5.1 Into a 25-ml beaker, weigh 0.4 g of FID, split injector packed with silanized AMS to the nearest 0.1 mg. glass wool. 7.5.2 Quantitatively transfer this AMS into 6.6.1 Establish the following gas a 1-L volumetric flask. Dilute to the mark chromatographic conditions, and allow the with isopropyl alcohol. system to thoroughly equilibrate before use. 7.5.3 Transfer this solution to the auto- 6.6.2 Injector parameters: matic dispensing pipet reservoir. This will be Injection technique = Split labeled the AMS STOCK SOLUTION. Injector split flow = 86 ml/min 7.6 n-Hexane Stock Solution: 13mg/2ml Injector temperature = 225 deg C hexane in isopropyl alcohol. 6.6.3 Oven temperature program: 7.6.1 Into a 100-ml volumetric flask, weigh Initial temperature = 40 deg C 0.65 g of n-hexane to the nearest 0.1 mg.

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7.6.2 Dilute to the mark with isopropyl al- S = Amount of compound added to the spiked cohol. This solution will be labeled the n- sample HEXANE STOCK SOLUTION. R = Fraction of spiked compound recovered 9.6 Normally a value of R between 0.70 and 8.0 Sample Collection, Preservation and Storage 1.30 is acceptable. 8.1 A sampling device similar to Figure 1 is 9.7 R is used to correct all reported results used to collect a non-vented crumb rubber for each compound by dividing the measured sample at a location that is after the strip- results of each compound by the R for that ping operation but before the sample is ex- compound for the same sample type. posed to the atmosphere. 8.2 The crumb rubber is allowed to cool be- 10.0 Calibration fore opening the sampling device and remov- 10.1 Using the AMS STOCK SOLUTION ing the sample. equipped with the automatic dispensing 8.3 The sampling device is opened and the pipet (7.5.3 of this method), transfer 25.0 ml crumb rubber sample is collected in the sam- of the internal standard solution into an un- pling basket. capped 50-ml serum vial. 8.4 One pound of crumb rubber sample is 10.2 Using a 2.0 ml volumetric pipet, quan- placed into a polyethylene bag. The bag is la- titatively transfer 2.0 ml of the n-HEXANE beled with the time, date and sample loca- STOCK SOLUTION (7.6.2 of this method) into tion. the 50-ml serum vial and cap. This solution 8.5 The sample should be delivered to the will be labeled the CALIBRATION SOLU- laboratory for testing within one hour of TION. sampling. 10.3 Using the conditions prescribed (6.6 of 8.6 Laboratory testing will be done within this method), inject 1 μl of the supernate. 3 hours of the sampling time. 10.4 Obtain the peak areas and calculate 8.7 No special storage conditions are re- the response factor as described in the cal- quired unless the storage time exceeds 3 culations section (12.1 of this method). hours in which case refrigeration of the samples is recommended. 11.0 Procedure 9.0 Quality Control 11.1 Determination of Dry Polymer Weight 11.1.1 Remove wet crumb from the poly- 9.1 For each sample type, 12 samples shall ethylene bag and place on paper towels to be obtained from the process for the recovery absorb excess surface moisture. study. Half of the vials and caps shall be 11.1.2 Cut small slices or cubes from the tared, labeled ‘‘spiked’’, and numbered 1 center of the crumb sample to improve sam- through 6. The other vials shall be labeled ple uniformity and further eliminate surface ‘‘unspiked’’ and need not be tared, but are moisture. also numbered 1 through 6. 11.1.3 A suitable gravimetric measurement 9.2 Determine the % moisture content of should be made on a sample of this wet the crumb sample. After determining the % crumb to determine the correction factor moisture content, the correction factor for needed to calculate the dry polymer weight. calculating the dry crumb weight can be de- 11.2 Determination of n-Hexane in Wet termined by using the equation in section Crumb 12.2 of this method. 11.2.1 Remove wet crumb from the poly- 9.3 Run the spiked and unspiked samples in ethylene bag and place on paper towels to the normal manner. Record the concentra- absorb excess surface moisture. tions of the n-hexane content of the mixed 11.2.2 Cut small slices or cubes from the hexane reported for each pair of spiked and center of the crumb sample to improve sam- unspiked samples. ple uniformity and further eliminate surface 9.4 For the recovery study, each sample of moisture. crumb shall be dissolved in chloroform con- 11.2.3 Into a tared 2 oz bottle, weigh 1.5 g of taining a known amount of mixed hexane wet polymer to the nearest 0.1 mg. solvent. 11.2.4 Add 25 ml of chloroform to the 2 oz 9.5 For each hydrocarbon, calculate the re- bottle and cap. covery efficiency (R) using the following 11.2.5 Using a mechanical shaker, shake equations: the bottle until the polymer dissolves. ¥ Mr = Ms Mu 11.2.6 Using the autodispensing pipet, add R = Mr/S 25.0 ml of the AMS STOCK SOLUTION (7.5.3 Where: of this method) to the dissolved polymer so- Mu = Measured amount of compound in the lution and cap. unspiked sample 11.2.7 Using a mechanical shaker, shake Ms = Measured amount of compound in the the bottle for 10 minutes to coagulate the spiked sample dissolved polymer. Mr = Measured amount of the spiked com- 11.2.8 Centrifuge the sample for 3 minutes pound at 2000 rpm.

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11.2.9 Using the conditions prescribed (6.6 14.0 Waste Generation of this method), chromatograph 1 μl of the supernate. 14.1 Waste generation should be minimized 11.2.10 Obtain the peak areas and calculate where possible. the concentration of the component of inter- 15.0 Waste Management est as described in the calculations (12.2 of this method). 15.1 Discard liquid chemical waste into the chemical waste drum. 12.0 Calculations 15.2 Discard polymer waste into the poly- 12.1 Calibration: mer waste container. × × RFx = (Wx Ais) / (Wis Ax) 16.0 References Where: 16.1 This method is based on Goodyear RFx = the relative response factor for n- hexane Chemical Division Test Method E–964. W = the weight (g) of n-hexane in the CALI- x METHOD 315—DETERMINATION OF PARTICULATE BRATION AND METHYLENE CHLORIDE EXTRACTABLE SOLUTION MATTER (MCEM) FROM SELECTED SOURCES A = the area of AMS is AT PRIMARY ALUMINUM PRODUCTION FACILI- W = the weight (g) of AMS in the CALIBRA- is TIES TION SOLUTION

Ax = the area of n-hexane NOTE: This method does not include all of 12.2 Procedure: the specifications (e.g., equipment and sup- 12.2.1 Correction Factor for calculating dry plies) and procedures (e.g., sampling and an- crumb weight. alytical) essential to its performance. Some material is incorporated by reference from F = 1—(% moisture / 100) other methods in this part. Therefore, to ob- Where: tain reliable results, persons using this F = Correction factor for calculating dry method should have a thorough knowledge of crumb weight at least the following additional test meth- % moisture determined by appropriate methods: Method 1, Method 2, Method 3, and od Method 5 of 40 CFR part 60, appendix A. 12.2.2 Moisture adjustment for chromatographic determination. 1.0 Scope and Application

Ws = F × Wc 1.1 Analytes. Particulate matter (PM). No Where: CAS number assigned. Methylene chloride extractable matter (MCEM). No CAS number Ws = the weight (g) of the dry polymer corrected for moisture assigned. F = Correction factor for calculating dry 1.2 Applicability. This method is applicable crumb weight for the simultaneous determination of PM

Wc = the weight (g) of the wet crumb in sec- and MCEM when specified in an applicable tion 9.6 regulation. This method was developed by 12.2.3 Concentration (ppm) of hexane in the consensus with the Aluminum Association wet crumb. and the U.S. Environmental Protection Agency (EPA) and has limited precision esti- ppmx = (Ax * RFx * Wis * 10000) / (Ais * Ws) mates for MCEM; it should have similar pre- Where: cision to Method 5 for PM in 40 CFR part 60, ppmx = parts per million of n-hexane in the appendix A since the procedures are similar polymer for PM. Ax = the area of n-hexane 1.3 Data quality objectives. Adherence to RFx = the relative response factor for n- the requirements of this method will en- hexane hance the quality of the data obtained from Wis = the weight (g) of AMS in the sample so- air pollutant sampling methods. lution

Ais = the area of AMS 2.0 Summary of Method W = the weight (g) of the dry polymer cor- s Particulate matter and MCEM are with- rected for moisture drawn isokinetically from the source. PM is 13.0 Method Performance collected on a glass fiber filter maintained at a temperature in the range of 120 ±14 °C (248 13.1 Precision for the method was deter- ±25 °F) or such other temperature as speci- mined at the 0.08% level. fied by an applicable subpart of the stand- The standard deviation was 0.01 and the ards or approved by the Administrator for a percent relative standard deviation (RSD) particular application. The PM mass, which was 16.3 % with five degrees of freedom. includes any material that condenses on the

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probe and is subsequently removed in an ace- of taper shall be ≤30 °, and the taper shall be tone rinse or on the filter at or above the fil- on the outside to preserve a constant inter- tration temperature, is determined gravi- nal diameter. The probe nozzle shall be of metrically after removal of uncombined the button-hook or elbow design, unless oth- water. MCEM is then determined by adding a erwise specified by the Administrator. Other methylene chloride rinse of the probe and fil- materials of construction may be used, sub- ter holder, extracting the condensable hydro- ject to the approval of the Administrator. A carbons collected in the impinger water, add- range of nozzle sizes suitable for isokinetic ing an acetone rinse followed by a methylene sampling should be available. Typical nozzle chloride rinse of the sampling train compo- sizes range from 0.32 to 1.27 cm (1⁄8 to 1⁄2 in.) nents after the filter and before the silica gel inside diameter (ID) in increments of 0.16 cm impinger, and determining residue gravi- (1⁄16 in.). Larger nozzle sizes are also avail- metrically after evaporating the solvents. able if higher volume sampling trains are used. Each nozzle shall be calibrated accord- 3.0 Definitions [Reserved] ing to the procedures outlined in section 10.0 of this method. 4.0 Interferences [Reserved] 6.1.1.2 Probe liner. Borosilicate or quartz 5.0 Safety glass tubing with a heating system capable of maintaining a probe gas temperature at This method may involve hazardous mate- the exit end during sampling of 120 ±14 °C (248 rials, operations, and equipment. This meth- ±25 °F), or such other temperature as speci- od does not purport to address all of the safe- fied by an applicable subpart of the stand- ty problems associated with its use. It is the ards or approved by the Administrator for a responsibility of the user of this method to particular application. Because the actual establish appropriate safety and health prac- temperature at the outlet of the probe is not tices and determine the applicability of reg- usually monitored during sampling, probes ulatory limitations prior to performing this constructed according to APTD–0581 and test method. using the calibration curves of APTD–0576 (or calibrated according to the procedure 6.0 Equipment and Supplies outlined in APTD–0576) will be considered ac- NOTE: Mention of trade names or specific ceptable. Either borosilicate or quartz glass products does not constitute endorsement by probe liners may be used for stack tempera- ° ° the EPA. tures up to about 480 C (900 F); quartz liners shall be used for temperatures between 480 6.1 Sample collection. The following items and 900 °C (900 and 1,650 °F). Both types of are required for sample collection: liners may be used at higher temperatures 6.1.1 Sampling train. A schematic of the than specified for short periods of time, sub- sampling train used in this method is shown ject to the approval of the Administrator. in Figure 5–1, Method 5, 40 CFR part 60, ap- The softening temperature for borosilicate pendix A–3. Complete construction details glass is 820 °C (1,500 °F) and for quartz glass are given in APTD–0581 (Reference 2 in sec- it is 1,500 °C (2,700 °F). tion 17.0 of this method); commercial models 6.1.1.3 Pitot tube. Type S, as described in of this train are also available. For changes section 6.1 of Method 2, 40 CFR part 60, ap- from APTD–0581 and for allowable modifica- pendix A, or other device approved by the tions of the train shown in Figure 5–1, Meth- Administrator. The pitot tube shall be at- od 5, 40 CFR part 60, appendix A–3, see the tached to the probe (as shown in Figure 5–1 following subsections. of Method 5, 40 CFR part 60, appendix A) to NOTE: The operating and maintenance pro- allow constant monitoring of the stack gas cedures for the sampling train are described velocity. The impact (high pressure) opening in APTD–0576 (Reference 3 in section 17.0 of plane of the pitot tube shall be even with or this method). Since correct usage is impor- above the nozzle entry plane (see Method 2, tant in obtaining valid results, all users Figure 2–6b, 40 CFR part 60, appendix A) dur- should read APTD–0576 and adopt the oper- ing sampling. The Type S pitot tube assem- ating and maintenance procedures outlined bly shall have a known coefficient, deter- in it, unless otherwise specified herein. Al- mined as outlined in section 10.0 of Method 2, ternative mercury-free thermometers may 40 CFR part 60, appendix A. be used if the thermometers are, at a min- 6.1.1.4 Differential pressure gauge. Inclined imum, equivalent in terms of performance or manometer or equivalent device (two), as de- suitably effective for the specific tempera- scribed in section 6.2 of Method 2, 40 CFR ture measurement application. The use of part 60, appendix A. One manometer shall be grease for sealing sampling train compo- used for velocity head (Dp) readings, and the nents is not recommended because many other, for orifice differential pressure read- greases are soluble in methylene chloride. ings. The sampling train consists of the following 6.1.1.5 Filter holder. Borosilicate glass, components: with a glass frit filter support and a silicone 6.1.1.1 Probe nozzle. Glass or glass lined rubber gasket. The holder design shall pro- with sharp, tapered leading edge. The angle vide a positive seal against leakage from the

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outside or around the filter. The holder shall 6.1.2 Barometer. Mercury, aneroid, or other be attached immediately at the outlet of the barometer capable of measuring atmospheric probe (or cyclone, if used). pressure to within 2.5 mm (0.1 in.) Hg. 6.1.1.6 Filter heating system. Any heating NOTE: The barometric reading may be ob- system capable of maintaining a tempera- tained from a nearby National Weather Serv- ± ° ture around the filter holder of 120 14 C (248 ice station. In this case, the station value ± ° 25 F) during sampling, or such other tem- (which is the absolute barometric pressure) perature as specified by an applicable sub- shall be requested and an adjustment for ele- part of the standards or approved by the Ad- vation differences between the weather sta- ministrator for a particular application. Al- tion and sampling point shall be made at a ternatively, the tester may opt to operate rate of minus 2.5 mm (0.1 in) Hg per 30 m (100 the equipment at a temperature lower than ft) elevation increase or plus 2.5 mm (0.1 in) that specified. A temperature gauge capable Hg per 30 m (100 ft) elevation decrease. of measuring temperature to within 3 °C (5.4 °F) shall be installed so that the temperature 6.1.3 Gas density determination equipment. around the filter holder can be regulated and Temperature sensor and pressure gauge, as monitored during sampling. Heating systems described in sections 6.3 and 6.4 of Method 2, other than the one shown in APTD–0581 may 40 CFR part 60, appendix A, and gas analyzer, be used. if necessary, as described in Method 3, 40 6.1.1.7 Temperature sensor. A temperature CFR part 60, appendix A. The temperature sensor capable of measuring temperature to sensor shall, preferably, be permanently at- within ±3 °C (5.4 °F) shall be installed so that tached to the pitot tube or sampling probe in the sensing tip of the temperature sensor is a fixed configuration, such that the tip of in direct contact with the sample gas, and the sensor extends beyond the leading edge the temperature around the filter holder can of the probe sheath and does not touch any be regulated and monitored during sampling. metal. Alternatively, the sensor may be at- 6.1.1.8 Condenser. The following system tached just prior to use in the field. Note, shall be used to determine the stack gas however, that if the temperature sensor is moisture content: four glass impingers con- attached in the field, the sensor must be nected in series with leak-free ground glass placed in an interference-free arrangement fittings. The first, third, and fourth with respect to the Type S pitot tube open- impingers shall be of the Greenburg-Smith ings (see Method 2, Figure 2–4, 40 CFR part design, modified by replacing the tip with a 60, appendix A). As a second alternative, if a 1.3 cm (1/2 in.) ID glass tube extending to difference of not more than 1 percent in the about 1.3 cm (1/2 in.) from the bottom of the average velocity measurement is to be intro- flask. The second impinger shall be of the duced, the temperature sensor need not be Greenburg-Smith design with the standard attached to the probe or pitot tube. (This al- tip. The first and second impingers shall con- ternative is subject to the approval of the tain known quantities of water (section 8.3.1 Administrator.) of this method), the third shall be empty, 6.2 Sample recovery. The following items and the fourth shall contain a known weight are required for sample recovery: of silica gel or equivalent desiccant. A tem- 6.2.1 Probe-liner and probe-nozzle brushes. perature sensor capable of measuring tem- Nylon or Teflon ® bristle brushes with stain- perature to within 1 °C (2 °F) shall be placed less steel wire handles. The probe brush shall at the outlet of the fourth impinger for mon- have extensions (at least as long as the itoring. probe) constructed of stainless steel, nylon, 6.1.1.9 Metering system. Vacuum gauge, Teflon ®, or similarly inert material. The leak-free pump, temperature sensors capable brushes shall be properly sized and shaped to of measuring temperature to within 3 °C (5.4 brush out the probe liner and nozzle. °F), dry gas meter (DGM) capable of meas- 6.2.2 Wash bottles. Glass wash bottles are uring volume to within 2 percent, and re- recommended. Polyethylene or tetrafluoro- lated equipment, as shown in Figure 5–1 of ethylene (TFE) wash bottles may be used, Method 5, 40 CFR part 60, appendix A. Other but they may introduce a positive bias due metering systems capable of maintaining to contamination from the bottle. It is rec- sampling rates within 10 percent of ommended that acetone not be stored in pol- isokinetic and of determining sample vol- yethylene or TFE bottles for longer than a umes to within 2 percent may be used, sub- month. ject to the approval of the Administrator. 6.2.3 Glass sample storage containers. When the metering system is used in con- Chemically resistant, borosilicate glass bot- junction with a pitot tube, the system shall tles, for acetone and methylene chloride allow periodic checks of isokinetic rates. washes and impinger water, 500 ml or 1,000 6.1.1.10 Sampling trains using metering ml. Screw-cap liners shall either be rubber- systems designed for higher flow rates than backed Teflon ® or shall be constructed so as that described in APTD–0581 or APTD–0576 to be leak-free and resistant to chemical at- may be used provided that the specifications tack by acetone or methylene chloride. (Nar- of this method are met. row-mouth glass bottles have been found to

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be less prone to leakage.) Alternatively, pol- used, subject to the approval of the Adminis- yethylene bottles may be used. trator. 6.2.4 Petri dishes. For filter samples, glass, 7.1.3 Water. When analysis of the material unless otherwise specified by the Adminis- caught in the impingers is required, deion- trator. ized distilled water shall be used. Run blanks 6.2.5 Graduated cylinder and/or balance. To prior to field use to eliminate a high blank measure condensed water, acetone wash and on test samples. methylene chloride wash used during field 7.1.4 Crushed ice. recovery of the samples, to within 1 ml or 1 7.1.5 Stopcock grease. Acetone-insoluble, g. Graduated cylinders shall have subdivi- heat-stable silicone grease. This is not nec- sions no greater than 2 ml. Most laboratory essary if screw-on connectors with Teflon’’ balances are capable of weighing to the near- sleeves, or similar, are used. Alternatively, est 0.5 g or less. Any such balance is suitable other types of stopcock grease may be used, for use here and in section 6.3.4 of this meth- subject to the approval of the Administrator. od. [Caution: Many stopcock greases are meth- 6.2.6 Plastic storage containers. Air-tight ylene chloride-soluble. Use sparingly and containers to store silica gel. carefully remove prior to recovery to pre- 6.2.7 Funnel and rubber policeman. To aid vent contamination of the MCEM analysis.] in transfer of silica gel to container; not nec- 7.2 Sample recovery. The following re- essary if silica gel is weighed in the field. agents are required for sample recovery: 6.2.8 Funnel. Glass or polyethylene, to aid 7.2.1 Acetone. Acetone with blank values in sample recovery. <1 ppm, by weight residue, is required. Ace- 6.3 Sample analysis. The following equip- tone blanks may be run prior to field use, ment is required for sample analysis: and only acetone with low blank values may 6.3.1 Glass or Teflon ® weighing dishes. be used. In no case shall a blank value of 6.3.2 Desiccator. It is recommended that greater than 1E–06 of the weight of acetone fresh desiccant be used to minimize the used be subtracted from the sample weight. chance for positive bias due to absorption of NOTE: This is more restrictive than Method organic material during drying. 5, 40 CFR part 60, appendix A. At least one 6.3.3 Analytical balance. To measure to vendor (Supelco Incorporated located in within 0.l mg. Bellefonte, Pennsylvania) lists <1 mg/l as 6.3.4 Balance. To measure to within 0.5 g. residue for its Environmental Analysis Sol- 6.3.5 Beakers. 250 ml. vents. 6.3.6 Hygrometer. To measure the relative humidity of the laboratory environment. 7.2.2 Methylene chloride. Methylene chlo- 6.3.7 Temperature sensor. To measure the ride with a blank value <1.5 ppm, by weight, temperature of the laboratory environment. residue. Methylene chloride blanks may be 6.3.8 Buchner fritted funnel. 30 ml size, fine run prior to field use, and only methylene (<50 micron)-porosity fritted glass. chloride with low blank values may be used. 6.3.9 Pressure filtration apparatus. In no case shall a blank value of greater than 6.3.10 Aluminum dish. Flat bottom, smooth 1.6E–06 of the weight of methylene chloride sides, and flanged top, 18 mm deep and with used be subtracted from the sample weight. an inside diameter of approximately 60 mm. NOTE: A least one vendor quotes <1 mg/l for Environmental Analysis Solvents-grade 7.0 Reagents and Standards methylene chloride. 7.l Sample collection. The following re- 7.3 Sample analysis. The following reagents are required for sample collection: agents are required for sample analysis: 7.1.1 Filters. Glass fiber filters, without or- 7.3.l Acetone. Same as in section 7.2.1 of ganic binder, exhibiting at least 99.95 percent this method. efficiency (<0.05 percent penetration) on 0.3 7.3.2 Desiccant. Anhydrous calcium sulfate, micron dioctyl phthalate smoke particles. indicating type. Alternatively, other types of The filter efficiency test shall be conducted desiccants may be used, subject to the ap- in accordance with ASTM Method D 2986–95A proval of the Administrator. (incorporated by reference in § 63.841 of this 7.3.3 Methylene chloride. Same as in sec- part). Test data from the supplier’s quality tion 7.2.2 of this method. control program are sufficient for this purpose. In sources containing S02 or S03, the fil- 8.0 Sample Collection, Preservation, Storage, ter material must be of a type that is and Transport unreactive to S02 or S03. Reference 10 in section 17.0 of this method may be used to se- NOTE: The complexity of this method is lect the appropriate filter. such that, in order to obtain reliable results, 7.1.2 Silica gel. Indicating type, 6 to l6 testers should be trained and experienced mesh. If previously used, dry at l75 °C (350 °F) with the test procedures. for 2 hours. New silica gel may be used as re- 8.1 Pretest preparation. It is suggested ceived. Alternatively, other types of that sampling equipment be maintained ac- desiccants (equivalent or better) may be cording to the procedures described in

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APTD–0576. Alternative mercury-free ther- the run, do not change the nozzle size. En- mometers may be used if the thermometers sure that the proper differential pressure are at a minimum equivalent in terms of per- gauge is chosen for the range of velocity formance or suitably effective for the spe- heads encountered (see section 8.2 of Method cific temperature measurement application. 2, 40 CFR part 60, appendix A). 8.1.1 Weigh several 200 g to 300 g portions of 8.2.3 Select a suitable probe liner and probe silica gel in airtight containers to the near- length such that all traverse points can be est 0.5 g. Record on each container the total sampled. For large stacks, consider sampling weight of the silica gel plus container. As an from opposite sides of the stack to reduce alternative, the silica gel need not be the required probe length. preweighed but may be weighed directly in 8.2.4 Select a total sampling time greater its impinger or sampling holder just prior to than or equal to the minimum total sam- train assembly. pling time specified in the test procedures 8.1.2 A batch of glass fiber filters, no more for the specific industry such that: (1) The than 50 at a time, should placed in a soxhlet sampling time per point is not less than 2 extraction apparatus and extracted using minutes (or some greater time interval as methylene chloride for at least 16 hours. specified by the Administrator); and (2) the After extraction, check filters visually sample volume taken (corrected to standard against light for irregularities, flaws, or pin- conditions) will exceed the required min- hole leaks. Label the shipping containers imum total gas sample volume. The latter is (glass or plastic petri dishes), and keep the based on an approximate average sampling filters in these containers at all times except rate. during sampling and weighing. 8.2.5 The sampling time at each point shall 8.1.3 Desiccate the filters at 20 ±5.6 °C (68 be the same. It is recommended that the ±10 °F) and ambient pressure for at least 24 number of minutes sampled at each point be hours and weigh at intervals of at least 6 an integer or an integer plus one-half hours to a constant weight, i.e., <0.5 mg minute, in order to eliminate timekeeping change from previous weighing; record re- errors. sults to the nearest 0.1 mg. During each weighing the filter must not be exposed to 8.2.6 In some circumstances (e.g., batch cy- the laboratory atmosphere for longer than 2 cles), it may be necessary to sample for minutes and a relative humidity above 50 shorter times at the traverse points and to percent. Alternatively (unless otherwise obtain smaller gas sample volumes. In these specified by the Administrator), the filters cases, the Administrator’s approval must may be oven-dried at 104 °C (220 °F) for 2 to first be obtained. 3 hours, desiccated for 2 hours, and weighed. 8.3 Preparation of sampling train. Procedures other than those described, 8.3.1 During preparation and assembly of which account for relative humidity effects, the sampling train, keep all openings where may be used, subject to the approval of the contamination can occur covered until just Administrator. prior to assembly or until sampling is about 8.2 Preliminary determinations. to begin. Place l00 ml of water in each of the 8.2.1 Select the sampling site and the min- first two impingers, leave the third impinger imum number of sampling points according empty, and transfer approximately 200 to 300 to Method 1, 40 CFR part 60, appendix A or as g of preweighed silica gel from its container specified by the Administrator. Determine to the fourth impinger. More silica gel may the stack pressure, temperature, and the be used, but care should be taken to ensure range of velocity heads using Method 2, 40 that it is not entrained and carried out from CFR part 60, appendix A; it is recommended the impinger during sampling. Place the con- that a leak check of the pitot lines (see sec- tainer in a clean place for later use in the tion 8.1 of Method 2, 40 CFR part 60, appendix sample recovery. Alternatively, the weight A) be performed. Determine the moisture of the silica gel plus impinger may be deter- content using Approximation Method 4 (sec- mined to the nearest 0.5 g and recorded. tion 1.2 of Method 4, 40 CFR part 60, appendix 8.3.2 Using a tweezer or clean disposable A) or its alternatives to make isokinetic surgical gloves, place a labeled (identified) sampling rate settings. Determine the stack and weighed filter in the filter holder. Be gas dry molecular weight, as described in sure that the filter is properly centered and section 8.6 of Method 2, 40 CFR part 60, ap- the gasket properly placed so as to prevent pendix A; if integrated Method 3 sampling is the sample gas stream from circumventing used for molecular weight determination, the filter. Check the filter for tears after as- the integrated bag sample shall be taken si- sembly is completed. multaneously with, and for the same total 8.3.3 When glass liners are used, install the length of time as, the particulate sample selected nozzle using a Viton A 0-ring when run. stack temperatures are less than 260 °C (500 8.2.2 Select a nozzle size based on the range °F) and an asbestos string gasket when tem- of velocity heads such that it is not nec- peratures are higher. See APTD–0576 for de- essary to change the nozzle size in order to tails. Mark the probe with heat-resistant maintain isokinetic sampling rates. During tape or by some other method to denote the

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proper distance into the stack or duct for Leakage rates in excess of 4 percent of the each sampling point. average sampling rate or 0.00057 m3/min (0.02 8.3.4 Set up the train as in Figure 5-1 of cfm), whichever is less, are unacceptable. Method 5, 40 CFR part 60, appendix A, using 8.4.2.3 The following leak check instruc- (if necessary) a very light coat of silicone tions for the sampling train described in grease on all ground glass joints, greasing APTD–0576 and APTD–058l may be helpful. only the outer portion (see APTD–0576) to Start the pump with the bypass valve fully avoid possibility of contamination by the sil- open and the coarse adjust valve completely icone grease. Subject to the approval of the closed. Partially open the coarse adjust Administrator, a glass cyclone may be used valve and slowly close the bypass valve until between the probe and filter holder when the the desired vacuum is reached. Do not re- total particulate catch is expected to exceed verse the direction of the bypass valve, as 100 mg or when water droplets are present in this will cause water to back up into the fil- the stack gas. ter holder. If the desired vacuum is exceeded, 8.3.5 Place crushed ice around the either leak-check at this higher vacuum or impingers. end the leak check as shown below and start 8.4 Leak-check procedures. over. 8.4.1 Leak check of metering system shown 8.4.2.4 When the leak check is completed, in Figure 5-1 of Method 5, 40 CFR part 60, ap- first slowly remove the plug from the inlet pendix A. That portion of the sampling train to the probe, filter holder, or cyclone (if ap- from the pump to the orifice meter should be plicable) and immediately turn off the vacu- leak-checked prior to initial use and after um pump. This prevents the water in the each shipment. Leakage after the pump will impingers from being forced backward into result in less volume being recorded than is the filter holder and the silica gel from being actually sampled. The following procedure is entrained backward into the third impinger. suggested (see Figure 5–2 of Method 5, 40 CFR part 60, appendix A): Close the main valve on 8.4.3 Leak checks during sample run. If, the meter box. Insert a one-hole rubber stop- during the sampling run, a component (e.g., per with rubber tubing attached into the ori- filter assembly or impinger) change becomes fice exhaust pipe. Disconnect and vent the necessary, a leak check shall be conducted low side of the orifice manometer. Close off immediately before the change is made. The the low side orifice tap. Pressurize the sys- leak check shall be done according to the tem to 13 to 18 cm (5 to 7 in.) water column procedure outlined in section 8.4.2 of this by blowing into the rubber tubing. Pinch off method, except that it shall be done at a vac- the tubing, and observe the manometer for 1 uum equal to or greater than the maximum minute. A loss of pressure on the manometer value recorded up to that point in the test. If indicates a leak in the meter box; leaks, if the leakage rate is found to be no greater present, must be corrected. than 0.00057 m3/min (0.02 cfm) or 4 percent of 8.4.2 Pretest leak check. A pretest leak- the average sampling rate (whichever is check is recommended but not required. If less), the results are acceptable, and no cor- the pretest leak-check is conducted, the fol- rection will need to be applied to the total lowing procedure should be used. volume of dry gas metered; if, however, a 8.4.2.1 After the sampling train has been higher leakage rate is obtained, either assembled, turn on and set the filter and record the leakage rate and plan to correct probe heating systems to the desired oper- the sample volume as shown in section 12.3 ating temperatures. Allow time for the tem- of this method or void the sample run. peratures to stabilize. If a Viton A 0-ring or NOTE: Immediately after component other leak-free connection is used in assem- changes, leak checks are optional; if such bling the probe nozzle to the probe liner, leak checks are done, the procedure outlined leak-check the train at the sampling site by in section 8.4.2 of this method should be plugging the nozzle and pulling a 380 mm (15 used. in.) Hg vacuum. 8.4.4 Post-test leak check. A leak check is NOTE: A lower vacuum may be used, pro- mandatory at the conclusion of each sam- vided that it is not exceeded during the test. pling run. The leak check shall be performed 8.4.2.2 If an asbestos string is used, do not in accordance with the procedures outlined connect the probe to the train during the in section 8.4.2 of this method, except that it leak check. Instead, leak-check the train by shall be conducted at a vacuum equal to or first plugging the inlet to the filter holder greater than the maximum value reached (cyclone, if applicable) and pulling a 380 mm during the sampling run. If the leakage rate (15 in.) Hg vacuum. (See NOTE in section is found to be no greater than 0.00057 m3/min 8.4.2.1 of this method). Then connect the (0.02 cfm) or 4 percent of the average sam- probe to the train and perform the leak pling rate (whichever is less), the results are check at approximately 25 mm (1 in.) Hg vac- acceptable, and no correction need be applied uum; alternatively, the probe may be leak- to the total volume of dry gas metered. If, checked with the rest of the sampling train, however, a higher leakage rate is obtained, in one step, at 380 mm (15 in.) Hg vacuum. either record the leakage rate and correct

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the sample volume, as shown in section 12.4 being careful not to bump the probe nozzle of this method, or void the sampling run. into the stack walls when sampling near the 8.5 Sampling train operation. During the walls or when removing or inserting the sampling run, maintain an isokinetic sam- probe through the portholes; this minimizes pling rate (within l0 percent of true the chance of extracting deposited material. isokinetic unless otherwise specified by the 8.5.6 During the test run, make periodic ad- Administrator) and a temperature around justments to keep the temperature around the filter of 120 14 °C (248 25 °F), or such other the filter holder at the proper level; add temperature as specified by an applicable more ice and, if necessary, salt to maintain subpart of the standards or approved by the a temperature of less than 20 °C (68 °F) at the Administrator. condenser/silica gel outlet. Also, periodically 8.5.1 For each run, record the data required check the level and zero of the manometer. on a data sheet such as the one shown in Fig- 8.5.7 If the pressure drop across the filter ure 5–2 of Method 5, 40 CFR part 60, appendix becomes too high, making isokinetic sam- A. Be sure to record the initial reading. pling difficult to maintain, the filter may be Record the DGM readings at the beginning replaced in the midst of the sample run. It is and end of each sampling time increment, recommended that another complete filter when changes in flow rates are made, before assembly be used rather than attempting to and after each leak-check, and when sam- change the filter itself. Before a new filter pling is halted. Take other readings indi- assembly is installed, conduct a leak check cated by Figure 5–2 of Method 5, 40 CFR part 60, appendix A at least once at each sample (see section 8.4.3 of this method). The total point during each time increment and addi- PM weight shall include the summation of tional readings when significant changes (20 the filter assembly catches. percent variation in velocity head readings) 8.5.8 A single train shall be used for the en- necessitate additional adjustments in flow tire sample run, except in cases where simul- rate. Level and zero the manometer. Because taneous sampling is required in two or more the manometer level and zero may drift due separate ducts or at two or more different lo- to vibrations and temperature changes, cations within the same duct, or in cases make periodic checks during the traverse. where equipment failure necessitates a 8.5.2 Clean the portholes prior to the test change of trains. In all other situations, the run to minimize the chance of sampling de- use of two or more trains will be subject to posited material. To begin sampling, remove the approval of the Administrator. the nozzle cap and verify that the filter and NOTE: When two or more trains are used, probe heating systems are up to temperature separate analyses of the front-half and (if ap- and that the pitot tube and probe are prop- plicable) impinger catches from each train erly positioned. Position the nozzle at the shall be performed, unless identical nozzle first traverse point with the tip pointing di- sizes were used in all trains, in which case rectly into the gas stream. Immediately the front-half catches from the individual start the pump and adjust the flow to trains may be combined (as may the im- isokinetic conditions. Nomographs are avail- pinger catches) and one analysis of the front- able, which aid in the rapid adjustment of half catch and one analysis of the impinger the isokinetic sampling rate without exces- catch may be performed. sive computations. These nomographs are designed for use when the Type S pitot tube 8.5.9 At the end of the sample run, turn off the coarse adjust valve, remove the probe coefficient (Cp) is 0.85 # 0.02 and the stack gas equivalent density (dry molecular weight) is and nozzle from the stack, turn off the pump, 29 ±4. APTD–0576 details the procedure for record the final DGM reading, and then conduct a post-test leak check, as outlined in using the nomographs. If Cp and Md are outside the above-stated ranges, do not use the section 8.4.4 of this method. Also leak-check nomographs unless appropriate steps (see the pitot lines as described in section 8.1 of Reference 7 in section 17.0 of this method) Method 2, 40 CFR part 60, appendix A. The are taken to compensate for the deviations. lines must pass this leak check in order to 8.5.3 When the stack is under significant validate the velocity head data. negative pressure (height of impinger stem), 8.6 Calculation of percent isokinetic. Cal- close the coarse adjust valve before inserting culate percent isokinetic (see Calculations, the probe into the stack to prevent water section 12.12 of this method) to determine from backing into the filter holder. If nec- whether a run was valid or another test run essary, the pump may be turned on with the should be made. If there was difficulty in coarse adjust valve closed. maintaining isokinetic rates because of 8.5.4 When the probe is in position, block source conditions, consult the Administrator off the openings around the probe and port- for possible variance on the isokinetic rates. hole to prevent unrepresentative dilution of 8.7 Sample recovery. the gas stream. 8.7.1 Proper cleanup procedure begins as 8.5.5 Traverse the stack cross-section, as soon as the probe is removed from the stack required by Method 1, 40 CFR part 60, appen- at the end of the sampling period. Allow the dix A or as specified by the Administrator, probe to cool.

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8.7.2 When the probe can be safely handled, after which make a final rinse of the inside wipe off all external PM near the tip of the surface with acetone. probe nozzle and place a cap over it to pre- 8.7.6.2.2 Brush and rinse the inside parts of vent losing or gaining PM. Do not cap off the the Swagelok fitting with acetone in a simi- probe tip tightly while the sampling train is lar way until no visible particles remain. cooling down. This would create a vacuum in 8.7.6.2.3 Rinse the probe liner with acetone the filter holder, thus drawing water from by tilting and rotating the probe while the impingers into the filter holder. squirting acetone into its upper end so that 8.7.3 Before moving the sample train to the all inside surfaces are wetted with acetone. cleanup site, remove the probe from the sam- Let the acetone drain from the lower end ple train, wipe off the silicone grease, and into the sample container. A funnel (glass or cap the open outlet of the probe. Be careful polyethylene) may be used to aid in transfer- not to lose any condensate that might be ring liquid washes to the container. Follow present. Wipe off the silicone grease from the the acetone rinse with a probe brush. Hold filter inlet where the probe was fastened and the probe in an inclined position, squirt ace- cap it. Remove the umbilical cord from the tone into the upper end as the probe brush is last impinger and cap the impinger. If a being pushed with a twisting action through flexible line is used between the first im- the probe, hold a sample container under the pinger or condenser and the filter holder, dis- lower end of the probe, and catch any ace- connect the line at the filter holder and let tone and PM that is brushed from the probe. any condensed water or liquid drain into the Run the brush through the probe three times impingers or condenser. After wiping off the or more until no visible PM is carried out silicone grease, cap off the filter holder out- with the acetone or until none remains in let and impinger inlet. Ground-glass stop- the probe liner on visual inspection. With pers, plastic caps, or serum caps may be used stainless steel or other metal probes, run the to close these openings. brush through in the above-described manner at least six times, since metal probes have 8.7.4 Transfer the probe and filter-impinger small crevices in which PM can be en- assembly to the cleanup area. This area trapped. Rinse the brush with acetone and should be clean and protected from the wind quantitatively collect these washings in the so that the chances of contaminating or los- sample container. After the brushing, make ing the sample will be minimized. a final acetone rinse of the probe as de- 8.7.5 Save a portion of the acetone and scribed above. methylene chloride used for cleanup as 8.7.6.2.4 It is recommended that two people blanks. Take 200 ml of each solvent directly clean the probe to minimize sample losses. from the wash bottle being used and place it Between sampling runs, keep brushes clean in glass sample containers labeled ‘‘acetone and protected from contamination. blank’’ and ‘‘methylene chloride blank,’’ re- 8.7.6.2.5 After ensuring that all joints have spectively. been wiped clean of silicone grease, clean the 8.7.6 Inspect the train prior to and during inside of the front half of the filter holder by disassembly and note any abnormal condi- rubbing the surfaces with a nylon bristle tions. Treat the samples as follows: brush and rinsing with acetone. Rinse each 8.7.6.1 Container No. 1. Carefully remove surface three times or more if needed to re- the filter from the filter holder, and place it move visible particulate. Make a final rinse in its identified petri dish container. Use a of the brush and filter holder. Carefully rinse pair of tweezers and/or clean disposable sur- out the glass cyclone also (if applicable). gical gloves to handle the filter. If it is nec- 8.7.6.2.6 After rinsing the nozzle, probe, and essary to fold the filter, do so such that the front half of the filter holder with acetone, PM cake is inside the fold. Using a dry nylon repeat the entire procedure with methylene bristle brush and/or a sharp-edged blade, chloride and save in a separate No. 2M con- carefully transfer to the petri dish any PM tainer. and/or filter fibers that adhere to the filter 8.7.6.2.7 After acetone and methylene chlo- holder gasket. Seal the container. ride washings and PM have been collected in 8.7.6.2 Container No. 2. Taking care to see the proper sample containers, tighten the lid that dust on the outside of the probe or other on the sample containers so that acetone and exterior surfaces does not get into the sam- methylene chloride will not leak out when it ple, quantitatively recover PM or any con- is shipped to the laboratory. Mark the height densate from the probe nozzle, probe fitting, of the fluid level to determine whether leak- probe liner, and front half of the filter holder age occurs during transport. Label each con- by washing these components with acetone tainer to identify clearly its contents. and placing the wash in a glass container. 8.7.6.3 Container No. 3. Note the color of Perform the acetone rinse as follows: the indicating silica gel to determine wheth- 8.7.6.2.1 Carefully remove the probe nozzle er it has been completely spent, and make a and clean the inside surface by rinsing with notation of its condition. Transfer the silica acetone from a wash bottle and brushing gel from the fourth impinger to its original with a nylon bristle brush. Brush until the container and seal the container. A funnel acetone rinse shows no visible particles, may make it easier to pour the silica gel

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without spilling. A rubber policeman may be tone and methylene chloride used to the used as an aid in removing the silica gel nearest 1 ml or 0.5g. from the impinger. It is not necessary to re- NOTE: Because the subsequent analytical move the small amount of dust particles finish is gravimetric, it is okay to recover that may adhere to the impinger wall and both solvents to the same container. This are difficult to remove. Since the gain in would not be recommended if other analyt- weight is to be used for moisture calcula- ical finishes were required. tions, do not use any water or other liquids to transfer the silica gel. If a balance is 8.8 Sample transport. Whenever possible, available in the field, follow the procedure containers should be shipped in such a way for Container No. 3 in section 11.2.3 of this that they remain upright at all times. method. 8.7.6.4 Impinger water. Treat the impingers 9.0 Quality Control as follows: 9.1 Miscellaneous quality control meas- 8.7.6.4.1 Make a notation of any color or ures. film in the liquid catch. Measure the liquid that is in the first three impingers to within Quality control meas- 1 ml by using a graduated cylinder or by Section ure Effect weighing it to within 0.5 g by using a balance (if one is available). Record the volume or 8.4, 10.1– Sampling and equip- Ensure accurate weight of liquid present. This information is 10.6. ment leak check measurement of required to calculate the moisture content of and calibration. stack gas flow rate, the effluent gas. sample volume. 8.7.6.4.2 Following the determination of the volume of liquid present, rinse the back half 9.2 Volume metering system checks. The of the train with water, add it to the im- following quality control procedures are sug- pinger catch, and store it in a container la- gested to check the volume metering system beled 3W (water). calibration values at the field test site prior 8.7.6.4.3 Following the water rinse, rinse to sample collection. These procedures are the back half of the train with acetone to re- optional. move the excess water to enhance subse- 9.2.1 Meter orifice check. Using the calibra- quent organic recovery with methylene chlo- tion data obtained during the calibration ride and quantitatively recover to a con- procedure described in section 10.3 of this tainer labeled 3S (solvent) followed by at method, determine the DHa for the metering least three sequential rinsings with aliquots system orifice. The DHa is the orifice pres- of methylene chloride. Quantitatively re- sure differential in units of in. H20 that cor- cover to the same container labeled 3S. relates to 0.75 cfm of air at 528 °R and 29.92 Record separately the amount of both ace- in. Hg. The DHa is calculated as follows:

T Θ2 ΔΔHH= 0.. 0319 m a 22 PYVbar m

Where 1 0.0319 = (0.0567 in. Hg/ °R)(0.75 cfm)2; ⎡0. 0319 T ⎤ 2 DH = Average pressure differential across the = 10 m Yc ⎢ ⎥ orifice meter, in. H20; Vm ⎣ Pbar ⎦ Tm = Absolute average DGM temperature, °R; Q = Total sampling time, min; Where

Pbar = Barometric pressure, in. Hg; Yc = DGM calibration check value, Y = DGM calibration factor, dimensionless; dimensionless; Vm = Volume of gas sample as measured by 10 = Run time, min. DGM, dcf. 9.2.1.2 Compare the Yc value with the dry 9.2.1.1 Before beginning the field test (a set gas meter calibration factor Y to determine of three runs usually constitutes a field that: 0.97 Y

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be inserted at the inlet of the sampling CFR part 60, appendix A. Allowable toler- meter box, may be used as a quality control ances for individual Y and DHa values are check by following the procedure of section given in Figure 5–6 of Method 5, 40 CFR part 16.2 of this method. 60, appendix A. Use the average of the Y values in the calculations in section 12 of this 10.0 Calibration and Standardization method. 10.3.1.1 Before calibrating the metering NOTE: Maintain a laboratory log of all cali- system, it is suggested that a leak check be brations. conducted. For metering systems having dia- 10.1 Probe nozzle. Probe nozzles shall be phragm pumps, the normal leak check proce- calibrated before their initial use in the dure will not detect leakages within the field. Using a micrometer, measure the ID of pump. For these cases the following leak the nozzle to the nearest 0.025 mm (0.001 in.). check procedure is suggested: make a 10- Make three separate measurements using minute calibration run at 0.00057 m3/min (0.02 different diameters each time, and obtain cfm); at the end of the run, take the dif- the average of the measurements. The difference of the measured wet test meter and ference between the high and low numbers DGM volumes; divide the difference by 10 to shall not exceed 0.1 mm (0.004 in.). When noz- get the leak rate. The leak rate should not zles become nicked, dented, or corroded, exceed 0.00057 m3/min (0.02 cfm). they shall be reshaped, sharpened, and re- 10.3.2 Calibration after use. After each field calibrated before use. Each nozzle shall be use, the calibration of the metering system permanently and uniquely identified. shall be checked by performing three cali- 10.2 Pitot tube assembly. The Type S pitot bration runs at a single, intermediate orifice tube assembly shall be calibrated according setting (based on the previous field test) to the procedure outlined in section 10.1 of with the vacuum set at the maximum value Method 2, 40 CFR part 60, appendix A. reached during the test series. To adjust the 10.3 Metering system. vacuum, insert a valve between the wet test 10.3.1 Calibration prior to use. Before its meter and the inlet of the metering system. initial use in the field, the metering system Calculate the average value of the DGM cali- shall be calibrated as follows: Connect the bration factor. If the value has changed by metering system inlet to the outlet of a wet more than 5 percent, recalibrate the meter test meter that is accurate to within 1 per- over the full range of orifice settings, as pre- cent. Refer to Figure 5–5 of Method 5, 40 CFR viously detailed. part 60, appendix A. The wet test meter NOTE: Alternative procedures, e.g., re- should have a capacity of 30 liters/revolution checking the orifice meter coefficient, may 3 3 (1 ft /rev). A spirometer of 400 liters (14 ft ) or be used, subject to the approval of the Ad- more capacity, or equivalent, may be used ministrator. for this calibration, although a wet test meter is usually more practical. The wet test 10.3.3 Acceptable variation in calibration. meter should be periodically calibrated with If the DGM coefficient values obtained be- a spirometer or a liquid displacement meter fore and after a test series differ by more to ensure the accuracy of the wet test meter. than 5 percent, either the test series shall be Spirometers or wet test meters of other sizes voided or calculations for the test series may be used, provided that the specified ac- shall be performed using whichever meter curacies of the procedure are maintained. coefficient value (i.e., before or after) gives Run the metering system pump for about 15 the lower value of total sample volume. 10.4 Probe heater calibration. Use a heat minutes with the orifice manometer indi- source to generate air heated to selected cating a median reading, as expected in field temperatures that approximate those ex- use, to allow the pump to warm up and to pected to occur in the sources to be sampled. permit the interior surface of the wet test Pass this air through the probe at a typical meter to be thoroughly wetted. Then, at sample flow rate while measuring the probe each of a minimum of three orifice manom- inlet and outlet temperatures at various eter settings, pass an exact quantity of gas probe heater settings. For each air tempera- through the wet test meter and note the gas ture generated, construct a graph of probe volume indicated by the DGM. Also note the heating system setting versus probe outlet barometric pressure and the temperatures of temperature. The procedure outlined in the wet test meter, the inlet of the DGM, and APTD–0576 can also be used. Probes con- the outlet of the DGM. Select the highest structed according to APTD–0581 need not be and lowest orifice settings to bracket the ex- calibrated if the calibration curves in APTD– pected field operating range of the orifice. 0576 are used. Also, probes with outlet tem- Use a minimum volume of 0.15 m3 (5 cf) at all perature monitoring capabilities do not re- orifice settings. Record all the data on a quire calibration. form similar to Figure 5–6 of Method 5, 40 CFR part 60, appendix A, and calculate Y NOTE: The probe heating system shall be calibrated before its initial use in the field. (the DGM calibration factor) and DHa (the orifice calibration factor) at each orifice set- 10.5 Temperature sensors. Use the proce- ting, as shown on Figure 5–6 of Method 5, 40 dure in Section 10.3 of Method 2, 40 CFR part

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60, appendix A–1 to calibrate in-stack tem- 11.2.2 Container No. 2. perature sensors. Dial thermometers, such as 11.2.2.1 PM analysis. Note the level of liq- are used for the DGM and condenser outlet, uid in the container, and confirm on the shall be calibrated against mercury-in-glass analysis sheet whether leakage occurred dur- thermometers. An alternative mercury-free ing transport. If a noticeable amount of thermometer may be used if the thermom- leakage has occurred, either void the sample eter is, at a minimum, equivalent in terms of or use methods, subject to the approval of performance or suitably effective for the spe- the Administrator, to correct the final re- cific temperature measurement application. sults. Measure the liquid in this container ei- 10.6 Barometer. Calibrate against a mer- ther volumetrically to ±1 ml or gravimetri- cury barometer. cally to 1 ±0.5 g. Transfer the contents to a tared 250 ml beaker and evaporate to dryness 11.0 Analytical Procedure at ambient temperature and pressure. Des- 11.1 Record the data required on a sheet iccate for 24 hours, and weigh to a constant such as the one shown in Figure 315–1 of this weight. Report the results to the nearest 0.1 method. mg. 11.2 Handle each sample container as fol- 11.2.2.2 MCEM analysis. Add 25 ml meth- lows: ylene chloride to the beaker and cover with 11.2.1 Container No. 1. aluminum foil. Sonicate for 3 minutes then 11.2.1.1 PM analysis. Leave the contents in allow to stand for 20 minutes; combine with the shipping container or transfer the filter contents of Container No. 2M and pressure and any loose PM from the sample container filter and evaporate as described for Con- to a tared glass weighing dish. Desiccate for tainer 1 in section 11.2.1.2 of this method. 24 hours in a desiccator containing anhydrous calcium sulfate. Weigh to a constant Notes for MCEM Analysis weight and report the results to the nearest 0.1 mg. For purposes of this section, the term 1. Light finger pressure only is necessary ‘‘constant weight’’ means a difference of no on 24/40 adaptor. A Chemplast adapter more than 0.5 mg or 1 percent of total weight #15055–240 has been found satisfactory. less tare weight, whichever is greater, be- 2. Avoid aluminum dishes made with fluted tween two consecutive weighings, with no sides, as these may promote solvent ‘‘creep,’’ less than 6 hours of desiccation time between resulting in possible sample loss. weighings (overnight desiccation is a com- 3. If multiple samples are being run, rinse mon practice). If a third weighing is required the Buchner fritted funnel twice between and it agrees within ±0.5 mg, then the results samples with 5 ml solvent using pressure fil- of the second weighing should be used. For tration. After the second rinse, continue the quality assurance purposes, record and re- flow of air until the glass frit is completely port each individual weighing; if more than dry. Clean the Buchner fritted funnels thor- three weighings are required, note this in the oughly after filtering five or six samples. results for the subsequent MCEM results. 11.2.3 Container No. 3. Weigh the spent sili- 11.2.1.2 MCEM analysis. Transfer the filter ca gel (or silica gel plus impinger) to the and contents quantitatively into a beaker. nearest 0.5 g using a balance. This step may Add 100 ml of methylene chloride and cover be conducted in the field. with aluminum foil. Sonicate for 3 minutes 11.2.4 Container 3W (impinger water). then allow to stand for 20 minutes. Set up 11.2.4.1 MCEM analysis. Transfer the solu- the filtration apparatus. Decant the solution tion into a 1,000 ml separatory funnel quan- into a clean Buchner fritted funnel. Imme- titatively with methylene chloride washes. diately pressure filter the solution through Add enough solvent to total approximately the tube into another clean, dry beaker. Con- 50 ml, if necessary. Shake the funnel for 1 tinue decanting and pressure filtration until minute, allow the phases to separate, and all the solvent is transferred. Rinse the drain the solvent layer into a 250 ml beaker. beaker and filter with 10 to 20 ml methylene Repeat the extraction twice. Evaporate with chloride, decant into the Buchner fritted low heat (less than 40 °C) until near dryness. funnel and pressure filter. Place the beaker Transfer the remaining few milliliters of sol- on a low-temperature hot plate (maximum 40 vent quantitatively with small solvent wash- °C) and slowly evaporate almost to dryness. es into a clean, dry, tared aluminum dish Transfer the remaining last few milliliters of solution quantitatively from the beaker and evaporate to dryness. Remove from heat (using at least three aliquots of methylene once solvent is evaporated. Reweigh the dish chloride rinse) to a tared clean dry alu- after a 30-minute equilibration in the bal- minum dish and evaporate to complete dry- ance room and determine the weight to the ness. Remove from heat once solvent is evap- nearest 0.1 mg. orated. Reweigh the dish after a 30-minute 11.2.5 Container 3S (solvent). equilibrium in the balance room and deter- 11.2.5.1 MCEM analysis. Transfer the mixed mine the weight to the nearest 0.1 mg. Con- solvent to 250 ml beaker(s). Evaporate and duct a methylene chloride blank run in an weigh following the procedures detailed for identical fashion. container 3W in section 11.2.4 of this method.

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11.2.6 Blank containers. Measure the dis- Pstd = Standard absolute pressure, 760 mm Hg tilled water, acetone, or methylene chloride (29.92 in. Hg). in each container either volumetrically or R = Ideal gas constant, 0.06236 [(mm Hg)(m3)]/ gravimetrically. Transfer the ‘‘solvent’’ to a [(°K) (g-mole)] ’61’ 21.85 [(in. Hg)(ft3)]/ tared 250 ml beaker, and evaporate to dry- [(°R)(lb-mole)’61’ ]. ness at ambient temperature and pressure. Tm = Absolute average dry gas meter (DGM) (Conduct a solvent blank on the distilled de- temperature (see Figure 5–2 of Method 5, ionized water blank in an identical fashion 40 CFR part 60, appendix A), °K (°R). to that described in section 11.2.4.1 of this Ts = Absolute average stack gas temperature method.) Desiccate for 24 hours, and weigh to (see Figure 5–2 of Method 5, 40 CFR part a constant weight. Report the results to the 60, appendix A), °K(°R). nearest 0.l mg. Tstd = Standard absolute temperature, 293 °K NOTE: The contents of Containers No. 2, (528 °R). 3W, and 3M as well as the blank containers Va = Volume of acetone blank, ml. may be evaporated at temperatures higher Vaw = Volume of acetone used in wash, ml. than ambient. If evaporation is done at an Vt = Volume of methylene chloride blank, elevated temperature, the temperature must ml. be below the boiling point of the solvent; Vtw = Volume of methylene chloride used in also, to prevent ‘‘bumping,’’ the evaporation wash, ml. process must be closely supervised, and the Vlc = Total volume liquid collected in contents of the beaker must be swirled occa- impingers and silica gel (see Figure 5–3 of sionally to maintain an even temperature. Method 5, 40 CFR part 60, appendix A), Use extreme care, as acetone and methylene ml. chloride are highly flammable and have a Vm = Volume of gas sample as measured by low flash point. dry gas meter, dcm (dcf). Vm(std) = Volume of gas sample measured by 12.0 Data Analysis and Calculations the dry gas meter, corrected to standard conditions, dscm (dscf). 12.1 Carry out calculations, retaining at V ( ) = Volume of water vapor in the gas least one extra decimal figure beyond that of w std sample, corrected to standard conditions, the acquired data. Round off figures after the scm (scf). final calculation. Other forms of the equa- V = Stack gas velocity, calculated by Equa- tions may be used as long as they give equiv- s tion 2–9 in Method 2, 40 CFR part 60, ap- alent results. pendix A, using data obtained from 12.2 Nomenclature. Method 5, 40 CFR part 60, appendix A, m/ 3 3 An = Cross-sectional area of nozzle, m (ft ). sec (ft/sec). Bws = Water vapor in the gas stream, propor- Wa = Weight of residue in acetone wash, mg. tion by volume. Y = Dry gas meter calibration factor. Ca = Acetone blank residue concentration, DH = Average pressure differential across the mg/g. orifice meter (see Figure 5–2 of Method 5, Cs = Concentration of particulate matter in 40 CFR part 60, appendix A), mm H2O (in stack gas, dry basis, corrected to stand- H2O). ard conditions, g/dscm (g/dscf). ra = Density of acetone, 785.1 mg/ml (or see I = Percent of isokinetic sampling. label on bottle). La = Maximum acceptable leakage rate for rw = Density of water, 0.9982 g/ml (0.00220l lb/ either a pretest leak check or for a leak ml). check following a component change; rt = Density of methylene chloride, 1316.8 mg/ equal to 0.00057 m3/min (0.02 cfm) or 4 per- ml (or see label on bottle). cent of the average sampling rate, which- Q = Total sampling time, min. ever is less. Q1 = Sampling time interval, from the begin- Li = Individual leakage rate observed during ning of a run until the first component the leak check conducted prior to the change, min. th ‘‘i ’’ component change (I = l, 2, 3...n), Q1 = Sampling time interval, between two m3/min (cfm). successive component changes, beginning Lp = Leakage rate observed during the post- with the interval between the first and test leak check, m3/min (cfm). second changes, min. ma = Mass of residue of acetone after evapo- Qp = Sampling time interval, from the final ration, mg. (nth) component change until the end of mn = Total amount of particulate matter col- the sampling run, min. lected, mg. 13.6 = Specific gravity of mercury. Mw = Molecular weight of water, 18.0 g/g- 60 = Sec/min. mole (18.0 lb/lb-mole). 100 = Conversion to percent. Pbar = Barometric pressure at the sampling 12.3 Average dry gas meter temperature site, mm Hg (in Hg). and average orifice pressure drop. See data Ps = Absolute stack gas pressure, mm Hg (in. sheet (Figure 5–2 of Method 5, 40 CFR part 60, Hg). appendix A).

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12.4 Dry gas volume. Correct the sample standard conditions (20 °C, 760 mm Hg or 68 volume measured by the dry gas meter to °F, 29.92 in Hg) by using Equation 315–1.

ΔΔ ⎛ + H ⎞ + ⎛ H ⎞ TPstd⎝ bar ⎠ Pbar ⎝ ⎠ = 13.. 6== 13 6 VVYm VKVY1 m Eq.-1315 TPm std Tm

Where (a) Case I. No component changes made

Kl = 0.3858 °K/mm Hg for metric units, during sampling run. In this case, replace Vm = 17.64 °R/in Hg for English units. in Equation 315–1 with the expression:

NOTE: Equation 315–1 can be used as writ- [Vm—(Lp—La) Q] ten unless the leakage rate observed during (b) Case II. One or more component any of the mandatory leak checks (i.e., the changes made during the sampling run. In post-test leak check or leak checks con- this case, replace V in Equation 315–1 by the ducted prior to component changes) exceeds m expression: La. If Lp or Li exceeds La, Equation 315–1 must be modified as follows:

⎡ n ⎤ −−ΘΘΘ−− −− ⎢VLLma()11∑() LL iaipap() LL ⎥ ⎣ i=2 ⎦

and substitute only for those leakage rates 12.5 Volume of water vapor condensed. (Li or Lp) which exceed La.

ρ ==wRT std VVw() std121 c KVc Eq. 315-2 MPw std

Where the in-stack temperature sensor is ±1 °C (2 3 °F). K2 = 0.001333 m /ml for metric units; = 0.04706 ft3/ml for English units. 12.7 Acetone blank concentration. 12.6 Moisture content. M C = a Eq. 315-4 Vw() std a ρ B = Eq. 315-3 Vaa ws + VVm() std w () std 12.8 Acetone wash blank. NOTE: In saturated or water droplet-laden Wa = Ca Vaw ra Eq. 315–5 gas streams, two calculations of the mois- 12.9 Total particulate weight. Determine ture content of the stack gas shall be made, the total PM catch from the sum of the one from the impinger analysis (Equation weights obtained from Containers l and 2 less 315-3), and a second from the assumption of the acetone blank associated with these two saturated conditions. The lower of the two containers (see Figure 315–1). values of Bws shall be considered correct. The NOTE: Refer to section 8.5.8 of this method procedure for determining the moisture con- to assist in calculation of results involving tent based upon assumption of saturated two or more filter assemblies or two or more conditions is given in section 4.0 of Method 4, sampling trains. 40 CFR part 60, appendix A. For the purposes 12.10 Particulate concentration. of this method, the average stack gas tem- c = K m /V ( ) Eq. 315–6 perature from Figure 5–2 of Method 5, 40 CFR s 3 n m std part 60, appendix A may be used to make this where determination, provided that the accuracy of K = 0.001 g/mg for metric units;

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= 0.0154 gr/mg for English units. From To Multiply by 12.11 Conversion factors. mg ...... g ...... 0.001 ¥ From To Multiply by gr ...... lb ...... 1.429 × 10 4

ft 3 ...... m 3 ...... 0.02832 12.12 Isokinetic variation. gr ...... mg ...... 64.80004 12.12.1 Calculation from raw data. gr/ft3 ...... mg/m3 ...... 2288.4

⎛ ⎞⎛ Δ ⎞ + VYm + H 100 TKVsc41 ⎜ ⎟⎝Pbar ⎠ ⎝ Tm ⎠ 13. 6 I = Eq.-315 7 Θ 60 VPAss n

where = 0.002669 [(in Hg)(ft3)]/[(m1)(°R)] for English 3 units. K4 = 0.003454 [(mm Hg)(m )]/[(m1)(°K)] for metric units; 12.12.2 Calculation from intermediate values.

TV P 100 TV I = s m() std std = K s m () std Eq. 315-8 ΘΘ− 5 − TVstd s AP n s60() 1 B ws PVAss n() 1 B ws

where standard for volume measurements in place of the wet test meter specified in section 16.1 K5 = 4.320 for metric units; = 0.09450 for English units. of this method, provided that it is calibrated 12.12.3 Acceptable results. If 90 percent ≤I initially and recalibrated periodically as fol- ≤110 percent, the results are acceptable. If lows: the PM or MCEM results are low in compari- 16.1.1 Standard dry gas meter calibration. 16.1.1.1. The DGM to be calibrated and used son to the standard, and ‘‘I’’ is over 110 per- as a secondary reference meter should be of cent or less than 90 percent, the Adminis- high quality and have an appropriately sized trator may opt to accept the results. Ref- capacity, e.g., 3 liters/rev (0.1 ft 3/rev). A spi- erence 4 in the Bibliography may be used to rometer (400 liters or more capacity), or make acceptability judgments. If ‘‘I’’ is equivalent, may be used for this calibration, judged to be unacceptable, reject the results, although a wet test meter is usually more and repeat the test. 12.13 Stack gas velocity and volumetric practical. The wet test meter should have a 3 flow rate. Calculate the average stack gas capacity of 30 liters/rev (1 ft /rev) and be ca- velocity and volumetric flow rate, if needed, pable of measuring volume to within 1.0 per- using data obtained in this method and the cent; wet test meters should be checked equations in sections 5.2 and 5.3 of Method 2, against a spirometer or a liquid displace- 40 CFR part 60, appendix A. ment meter to ensure the accuracy of the 12.14 MCEM results. Determine the MCEM wet test meter. Spirometers or wet test me- concentration from the results from Con- ters of other sizes may be used, provided that tainers 1, 2, 2M, 3W, and 3S less the acetone, the specified accuracies of the procedure are methylene chloride, and filter blanks value maintained. as determined in the following equation: 16.1.1.2 Set up the components as shown in Figure 5–7 of Method 5, 40 CFR part 60, ap- ¥ ¥ ¥ mmcem = Smtotal wa wt fb pendix A. A spirometer, or equivalent, may 13.0 Method Performance [Reserved] be used in place of the wet test meter in the system. Run the pump for at least 5 minutes 14.0 Pollution Prevention [Reserved] at a flow rate of about 10 liters/min (0.35 cfm) to condition the interior surface of the wet 15.0 Waste Management [Reserved] test meter. The pressure drop indicated by the manometer at the inlet side of the DGM 16.0 Alternative Procedures should be minimized (no greater than 100 mm 16.1 Dry gas meter as a calibration stand- H2O [4 in. H2O] at a flow rate of 30 liters/min ard. A DGM may be used as a calibration [1 cfm]). This can be accomplished by using

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large-diameter tubing connections and min (0.35 and 1.2 cfm) or over the expected straight pipe fittings. operating range. 16.1.1.3 Collect the data as shown in the ex- 16.1.1.4 Calculate flow rate, Q, for each run ample data sheet (see Figure 5–8 of Method 5, using the wet test meter volume, Vw, and the 40 CFR part 60, appendix A). Make triplicate run time, q. Calculate the DGM coefficient, runs at each of the flow rates and at no less Yds, for each run. These calculations are as than five different flow rates. The range of follows: flow rates should be between 10 and 34 liters/

PV QK= bar w Eq. 315-9 1 + Θ ()ttw std VT()+ T P Y = w ds std bar Eq. 315-10 ds ⎛ Δp ⎞ VT()+ T P + ds w std⎝ bar 13. 6⎠

Where a laboratory and, if transported, cared for as any other laboratory instrument. Abuse to K1 = 0.3858 for international system of units (SI); 17.64 for English units; the standard meter may cause a change in the calibration and will require more fre- Pbar = Barometric pressure, mm Hg (in Hg); 3 quent recalibrations. Vw = Wet test meter volume, liter (ft ); 16.1.2.2 As an alternative to full recalibra- tw = Average wet test meter temperature, °C (°F); tion, a two-point calibration check may be made. Follow the same procedure and equip- tstd = 273 °C for SI units; 460 °F for English units; ment arrangement as for a full recalibration, Q = Run time, min; but run the meter at only two flow rates tds = Average dry gas meter temperature, °C (suggested rates are 14 and 28 liters/min [0.5 (°F); and 1.0 cfm]). Calculate the meter coeffi- 3 Vds = Dry gas meter volume, liter (ft ); cients for these two points, and compare the Dp = Dry gas meter inlet differential pres- values with the meter calibration curve. If sure, mm H2O (in H2O). the two coefficients are within 1.5 percent of the calibration curve values at the same flow 16.1.1.5 Compare the three Yds values at each of the flow rates and determine the rates, the meter need not be recalibrated maximum and minimum values. The dif- until the next date for a recalibration check. ference between the maximum and minimum 6.2 Critical orifices as calibration stand- values at each flow rate should be no greater ards. Critical orifices may be used as calibra- than 0.030. Extra sets of triplicate runs may tion standards in place of the wet test meter be made in order to complete this require- specified in section 10.3 of this method, pro- ment. In addition, the meter coefficients vided that they are selected, calibrated, and should be between 0.95 and 1.05. If these spec- used as follows: ifications cannot be met in three sets of suc- 16.2.1 Selection of critical orifices. cessive triplicate runs, the meter is not suit- 16.2.1.1 The procedure that follows de- able as a calibration standard and should not scribes the use of hypodermic needles or be used as such. If these specifications are stainless steel needle tubing that has been found suitable for use as critical orifices. met, average the three Yds values at each flow rate resulting in five average meter co- Other materials and critical orifice designs efficients, Yds. may be used provided the orifices act as true 16.1.1.6 Prepare a curve of meter coeffi- critical orifices; i.e., a critical vacuum can cient, Yds, versus flow rate, Q, for the DGM. be obtained, as described in section 7.2.2.2.3 This curve shall be used as a reference when of Method 5, 40 CFR part 60, appendix A. Se- the meter is used to calibrate other DGMs lect five critical orifices that are appro- and to determine whether recalibration is re- priately sized to cover the range of flow quired. rates between 10 and 34 liters/min or the ex- 16.1.2 Standard dry gas meter recalibra- pected operating range. Two of the critical tion. orifices should bracket the expected oper- 16.1.2.1 Recalibrate the standard DGM ating range. A minimum of three critical against a wet test meter or spirometer annu- orifices will be needed to calibrate a Method ally or after every 200 hours of operation, 5 DGM; the other two critical orifices can whichever comes first. This requirement is serve as spares and provide better selection valid provided the standard DGM is kept in for bracketing the range of operating flow

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rates. The needle sizes and tubing lengths Method 5, 40 CFR part 60, appendix A. Check shown in Table 315–1 give the approximate the water level in the wet test meter. Record flow rates indicated in the table. the DGM calibration factor, Y. 16.2.1.2 These needles can be adapted to a 16.2.2.2 Calibration of critical orifices. Set Method 5 type sampling train as follows: In- up the apparatus as shown in Figure 5–10 of sert a serum bottle stopper, 13 × 20 mm Method 5, 40 CFR part 60, appendix A. sleeve type, into a 0.5 in Swagelok quick con- 16.2.2.2.1 Allow a warm-up time of 15 min- nect. Insert the needle into the stopper as utes. This step is important to equilibrate shown in Figure 5–9 of Method 5, 40 CFR part the temperature conditions through the 60, appendix A. DGM. 16.2.2 Critical orifice calibration. The pro- 16.2.2.2.2 Leak-check the system as in sec- cedure described in this section uses the tion 7.2.2.1.1 of Method 5, 40 CFR part 60, ap- Method 5 meter box configuration with a pendix A. The leakage rate shall be zero. DGM as described in section 6.1.1.9 of this 16.2.2.2.3 Before calibrating the critical ori- method to calibrate the critical orifices. fice, determine its suitability and the appro- Other schemes may be used, subject to the priate operating vacuum as follows: turn on approval of the Administrator. the pump, fully open the coarse adjust valve, 16.2.2.1 Calibration of meter box. The crit- and adjust the bypass valve to give a vacuum ical orifices must be calibrated in the same reading corresponding to about half of at- configuration as they will be used; i.e., there mospheric pressure. Observe the meter box should be no connections to the inlet of the orifice manometer reading, DH. Slowly in- orifice. crease the vacuum reading until a stable 16.2.2.1.1 Before calibrating the meter box, reading is obtained on the meter box orifice leak-check the system as follows: Fully open manometer. Record the critical vacuum for the coarse adjust valve and completely close each orifice. Orifices that do not reach a the bypass valve. Plug the inlet. Then turn critical value shall not be used. on the pump and determine whether there is 16.2.2.2.4 Obtain the barometric pressure any leakage. The leakage rate shall be zero; using a barometer as described in section i.e., no detectable movement of the DGM 6.1.2 of this method. Record the barometric dial shall be seen for 1 minute. pressure, Pbar, in mm Hg (in. Hg). 16.2.2.1.2 Check also for leakages in that 16.2.2.2.5 Conduct duplicate runs at a vacu- portion of the sampling train between the um of 25 to 50 mm Hg (1 to 2 in. Hg) above pump and the orifice meter. See section 5.6 the critical vacuum. The runs shall be at of Method 5, 40 CFR part 60, appendix A for least 5 minutes each. The DGM volume read- the procedure; make any corrections, if nec- ings shall be in increments of complete revo- essary. If leakage is detected, check for lutions of the DGM. As a guideline, the times cracked gaskets, loose fittings, worn 0-rings, should not differ by more than 3.0 seconds etc. and make the necessary repairs. (this includes allowance for changes in the 16.2.2.1.3 After determining that the meter DGM temperatures) to achieve ±0.5 percent box is leakless, calibrate the meter box ac- in K′. Record the information listed in Fig- cording to the procedure given in section 5.3 ure 5–11 of Method 5, 40 CFR part 60, appen- of Method 5, 40 CFR part 60, appendix A. dix A. Make sure that the wet test meter meets the 16.2.2.2.6 Calculate K′ using Equation 315– requirements stated in section 7.1.1.1 of 11.

1 ⎛ ΔH ⎞ KV Y P + T 2 1 m⎝ bar 13. 6⎠ amb K' = Eq. 315-11 Θ PTbar m

where 16.2.3.1 Record the barometric pressure.

K′ = Critical orifice coefficient, [m3)(°K)1⁄2]/ 16.2.3.2 Calibrate the metering system ac- [(mm Hg)(min)] [(ft3)(°R)1⁄2)]/[(in. cording to the procedure outlined in sections Hg)(min)] 7.2.2.2.1 to 7.2.2.2.5 of Method 5, 40 CFR part

Tamb = Absolute ambient temperature, °K 60, appendix A. Record the information listed (°R). in Figure 5–12 of Method 5, 40 CFR part 60, 16.2.2.2.7 Average the K′ values. The indi- appendix A. vidual K′ values should not differ by more 16.2.3.3 Calculate the standard volumes of than ±0.5 percent from the average. air passed through the DGM and the critical 16.2.3 Using the critical orifices as calibra- orifices, and calculate the DGM calibration tion standards. factor, Y, using the equations below:

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Vm(std) = K1 Vm [Pbar + (DH/13.6)]/Tm Eq. 315–12 nual Meeting of the Air Pollution Control 1 Vcr(std) = K′ (Pbar Q)/Tamb ⁄2 Eq. 315–13 Association, St. Louis, MO. June 14–19, 1970. Y = Vcr(std)/Vm(std) Eq. 315–14 5. Smith, W.S., et al. Stack Gas Sampling where Improved and Simplified With New Equip- Vcr(std) = Volume of gas sample passed through ment. APCA Paper No. 67–119. 1967. the critical orifice, corrected to standard 6. Specifications for Incinerator Testing at conditions, dscm (dscf). Federal Facilities. PHS, NCAPC. 1967. K′ = 0.3858 °K/mm Hg for metric units 7. Shigehara, R.T. Adjustment in the EPA = 17.64 °R/in Hg for English units. Nomograph for Different Pitot Tube Coeffi- 16.2.3.4 Average the DGM calibration val- cients and Dry Molecular Weights. Stack ues for each of the flow rates. The calibra- Sampling News 2:4–11. October 1974. tion factor, Y, at each of the flow rates 8. Vollaro, R.F. A Survey of Commercially should not differ by more than ±2 percent Available Instrumentation for the Measure- from the average. ment of Low-Range Gas Velocities. U.S. En- 16.2.3.5 To determine the need for recali- vironmental Protection Agency, Emission brating the critical orifices, compare the Measurement Branch. Research Triangle DGM Y factors obtained from two adjacent Park, NC. November 1976 (unpublished orifices each time a DGM is calibrated; for paper). example, when checking orifice 13/2.5, use 9. Annual Book of ASTM Standards. Part orifices 12/10.2 and 13/5.1. If any critical ori- 26. Gaseous Fuels; Coal and Coke; Atmos- fice yields a DGM Y factor differing by more pheric Analysis. American Society for Test- than 2 percent from the others, recalibrate the critical orifice according to section ing and Materials. Philadelphia, PA. 1974. pp. 7.2.2.2 of Method 5, 40 CFR part 60, appendix 617–622. A. 10. Felix, L.G., G.I. Clinard, G.E. Lacy, and J.D. McCain. Inertial Cascade Impactor Sub- 17.0 References strate Media for Flue Gas Sampling. U.S. En- vironmental Protection Agency. Research 1. Addendum to Specifications for Inciner- Triangle Park, NC 27711. Publication No. ator Testing at Federal Facilities. PHS, EPA–600/7–77–060. June 1977. 83 p. NCAPC. December 6, 1967. 2. Martin, Robert M. Construction Details 11. Westlin, P.R., and R.T. Shigehara. Pro- of Isokinetic Source-Sampling Equipment. cedure for Calibrating and Using Dry Gas Environmental Protection Agency. Research Volume Meters as Calibration Standards. Triangle Park, NC. APTD–0581. April 1971. Source Evaluation Society Newsletter. 3 3. Rom, Jerome J. Maintenance, Calibra- (1):17–30. February 1978. tion, and Operation of Isokinetic Source 12. Lodge, J.P., Jr., J.B. Pate, B.E. Sampling Equipment. Environmental Pro- Ammons, and G.A. Swanson. The Use of tection Agency. Research Triangle Park, NC. Hypodermic Needles as Critical Orifices in APTD–0576. March 1972. Air Sampling. J. Air Pollution Control Asso- 4. Smith, W.S., R.T. Shigehara, and W.F. ciation. 16:197–200. 1966. Todd. A Method of Interpreting Stack Sam- 18.0 Tables, Diagrams, Flowcharts, and pling Data. Paper Presented at the 63rd An- Validation Data

TABLE 315–1. FLOW RATES FOR VARIOUS NEEDLE SIZES AND TUBE LENGTHS.

Gauge/length Flow rate Gauge/length Flow rate (cm) (liters/min) (cm) (liters/min)

12/7.6 ...... 32.56 14/2.5 ...... 19.54 12/10.2 ...... 30.02 14/5.1 ...... 17.27 13/2.5 ...... 25.77 14/7.6 ...... 16.14 13/5.1 ...... 23.50 15/3.2 ...... 14.16 13/7.6 ...... 22.37 15/7.6 ...... 11.61 13/10.2 ...... 20.67 115/10.2 ...... 10.48

FIGURE 315–1. PARTICULATE AND MCEM ANALYSES

Particulate Analysis

Plant ...... Date ...... Run No...... Filter No...... Amount liquid lost during transport ...... Acetone blank volume (ml) ...... Acetone blank concentration (Eq. 315–4) (mg/mg) ......

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FIGURE 315–1. PARTICULATE AND MCEM ANALYSES—Continued Acetone wash blank (Eq. 315–5) (mg) ......

Final weight Tare weight Weight gain % (mg) (mg) (mg)

Container No. 1 ...... Container No. 2 ......

Total ...... Less Acetone blank ...... Weight of particulate matter ......

Final volume Initial Liquid (mg) volume (mg) collected (mg) Moisture Analysis

Impingers ...... Note 1 Note 1 Silica gel ......

Total ...... NOTE 1: Convert volume of water to weight by multiplying by the density of water (1 g/ml).

Methylene Final weight Tare of alu- Acetone chloride Container No. (mg) minum dish Weight gain wash vol- wash vol- (mg) ume (ml) ume (ml)

MCEM Analysis

1. 2 + 2M. 3W. 3S.

Total ...... 7mtotal 7Vaw 7Vtw

Less acetone wash blank (mg) (not to exceed 1 mg/l of acetone wa = capa 7Vaw used).

Less methylene chloride wash blank (mg) (not to exceed 1.5 mg/l wt = ctpt 7Vtw of methylene chloride used).

Less filter blank (mg) (not to exceed . . . (mg/filter) ...... Fb

MCEM weight (mg) ...... mMCEOM = 7mtotal ¥ wa ¥ wt¥ fb

METHOD 316—SAMPLING AND ANALYSIS FOR 1010 lbs/cu ft (11.3 ppbv) or as high as 1.8 × 103 FORMALDEHYDE EMISSIONS FROM STA- lbs/cu ft (23,000,000 ppbv), at standard condi- TIONARY SOURCES IN THE MINERAL WOOL tions over a 1 hour sampling period, sam- AND WOOL FIBERGLASS INDUSTRIES pling approximately 30 cu ft. 1.0 Introduction 2.0 Summary of Method This method is applicable to the deter- Gaseous and particulate pollutants are mination of formaldehyde, CAS Registry withdrawn isokinetically from an emission number 50–00–0, from stationary sources in source and are collected in high purity the mineral wool and wool fiber glass indus- water. Formaldehyde present in the emis- tries. High purity water is used to collect the sions is highly soluble in high purity water. formaldehyde. The formaldehyde concentra- The high purity water containing formalde- tions in the stack samples are determined hyde is then analyzed using the modified using the modified pararosaniline method. pararosaniline method. Formaldehyde in the Formaldehyde can be detected as low as 8.8 × sample reacts with acidic pararosaniline,

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and the sodium sulfite, forming a purple to overcome the interference by each com- chromophore. The intensity of the purple pound has been described by Miksch, et al. color, measured spectrophotometrically, provides an accurate and precise measure of the 5.0 Safety [Reserved] formaldehyde concentration in the sample. 6.0 Apparatus and Materials 3.0 Definitions 6.1 A schematic of the sampling train is See the definitions in the General Provi- shown in Figure 1. This sampling train con- sions of this Subpart. figuration is adapted from EPA Method 5, 40 CFR part 60, appendix A, procedures. 4.0 Interferences Sulfite and cyanide in solution interfere with the pararosaniline method. A procedure

The sampling train consists of the fol- isokinetic sampling should be available in lowing components: probe nozzle, probe increments of 0.15 cm (1⁄16 in), e.g., 0.32 to 1.27 liner, pitot tube, differential pressure gauge, cm (1⁄8 to 1⁄2 in), or larger if higher volume impingers, metering system, barometer, and sampling trains are used. Each nozzle shall gas density determination equipment. be calibrated according to the procedure out- 6.1.1 Probe Nozzle: Quartz, glass, or stain- lined in Section 10.1. less steel with sharp, tapered (30 ° angle) 6.1.2 Probe Liner: Borosilicate glass or leading edge. The taper shall be on the out- quartz shall be used for the probe liner. The side to preserve a constant inner diameter. probe shall be maintained at a temperature The nozzle shall be buttonhook or elbow de- of 120 °C ±14 °C (248 °F ±25 °F). sign. A range of nozzle sizes suitable for

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6.1.3 Pitot Tube: The pitot tube shall be gauge (as described in Sections 2.3 and 2.3 of Type S, as described in Section 2.1 of EPA EPA Method 2, 40 CFR part 60, appendix A), Method 2, 40 CFR part 60, appendix A, or any and gas analyzer, if necessary (as described other appropriate device. The pitot tube in EPA Method 3, 40 CFR part 60, appendix shall be attached to the probe to allow con- A). The temperature sensor ideally should be stant monitoring of the stack gas velocity. permanently attached to the pitot tube or The impact (high pressure) opening plane of sampling probe in a fixed configuration such the pitot tube shall be even with or above that the top of the sensor extends beyond the the nozzle entry plane (see Figure 2–6b, EPA leading edge of the probe sheath and does not Method 2, 40 CFR part 60, appendix A) during touch any metal. Alternatively, the sensor sampling. The Type S pitot tube assembly may be attached just prior to use in the shall have a known coefficient, determined field. Note, however, that if the temperature as outlined in Section 4 of EPA Method 2, 40 sensor is attached in the field, the sensor CFR part 60, appendix A. must be placed in an interference-free ar- 6.1.4 Differential Pressure Gauge: The dif- rangement with respect to the Type S pitot ferential pressure gauge shall be an inclined openings (see Figure 2–7, EPA Method 2, 40 manometer or equivalent device as described CFR part 60, appendix A). As a second alter- in Section 2.2 of EPA Method 2, 40 CFR part native, if a difference of no more than 1 per- 60, appendix A. One manometer shall be used cent in the average velocity measurement is for velocity-head reading and the other for to be introduced, the temperature gauge orifice differential pressure readings. need not be attached to the probe or pitot 6.1.5 Impingers: The sampling train re- tube. quires a minimum of four impingers, con- 6.2 Sample Recovery nected as shown in Figure 1, with ground 6.2.1 Probe Liner: Probe nozzle and brushes; glass (or equivalent) vacuum-tight fittings. bristle brushes with stainless steel wire han- For the first, third, and fourth impingers, dles are required. The probe brush shall have use the Greenburg-Smith design, modified by extensions of stainless steel, Teflon TM, or replacing the tip with a 1.3 cm inside diame- inert material at least as long as the probe. 1 1 ters ( ⁄2 in) glass tube extending to 1.3 cm ( ⁄2 The brushes shall be properly sized and in) from the bottom of the flask. For the sec- shaped to brush out the probe liner, the ond impinger, use a Greenburg-Smith im- probe nozzle, and the impingers. pinger with the standard tip. Place a ther- 6.2.2 Wash Bottles: One wash bottle is re- mometer capable of measuring temperature quired. Polyethylene, Teflon TM, or glass to within 1 °C (2 °F) at the outlet of the wash bottles may be used for sample recov- fourth impinger for monitoring purposes. ery. 6.1.6 Metering System: The necessary com- 6.2.3 Graduated Cylinder and/or Balance: A ponents are a vacuum gauge, leak-free pump, graduated cylinder or balance is required to thermometers capable of measuring tem- measure condensed water to the nearest 1 ml peratures within 3 °C (5.4 °F), dry-gas meter capable of measuring volume to within 1 per- or 1 g. Graduated cylinders shall have divi- cent, and related equipment as shown in Fig- sion not >2 ml. Laboratory balances capable ± ure 1. At a minimum, the pump should be ca- of weighing to 0.5 g are required. pable of 4 cfm free flow, and the dry gas 6.2.4 Polyethylene Storage Containers: 500 meter should have a recording capacity of 0– ml wide-mouth polyethylene bottles are re- 999.9 cu ft with a resolution of 0.005 cu ft. quired to store impinger water samples. Other metering systems may be used which 6.2.5 Rubber Policeman and Funnel: A rub- are capable of maintaining sample volumes ber policeman and funnel are required to aid to within 2 percent. The metering system the transfer of material into and out of con- may be used in conjunction with a pitot tube tainers in the field. to enable checks of isokinetic sampling 6.3 Sample Analysis rates. 6.3.1 Spectrophotometer—B&L 70, 710, 2000, 6.1.7 Barometer: The barometer may be etc., or equivalent; 1 cm pathlength cuvette mercury, aneroid, or other barometer capa- holder. ble of measuring atmospheric pressure to 6.3.2 Disposable polystyrene cuvettes, within 2.5 mm Hg (0.1 in Hg). In many cases, pathlengh 1 cm, volume of about 4.5 ml. the barometric reading may be obtained 6.3.3 Pipettors—Fixed-volume Oxford pipet from a nearby National Weather Service Sta- (250 μl; 500 μl; 1000 μl); adjustable volume Ox- tion, in which case the station value (which ford or equivalent pipettor 1–5 ml model, set is the absolute barometric pressure) is re- to 2.50 ml. quested and an adjustment for elevation dif- 6.3.4 Pipet tips for pipettors above. ferences between the weather station and 6.3.5 Parafilm, 2 ° wide; cut into about 1’’ sampling point is applied at a rate of minus squares. 2.5 mm Hg (0.1 in Hg) per 30 m (100 ft) ele- 7.0 Reagents vation increase (rate is plus 2.5 mm Hg per 30 m (100 ft) of elevation decrease). 7.1 High purity water: All references to 6.1.8 Gas Density Determination Equip- water in this method refer to high purity ment: Temperature sensor and pressure water (ASTM Type I water or equivalent).

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The water purity will dictate the lower lim- flask which is about half full of high-purity its of formaldehyde quantification. water. Dilute to the mark with high-purity 7.2 Silica Gel: Silica gel shall be indicting water, and invert 15–20 times to mix thor- type, 6–16 mesh. If the silica gel has been oughly. This solution contains nominally 100 used previously, dry at 175 °C (350 °F) for 2 μg/ml formaldehyde. Prepare the working hours before using. New silica gel may be standards from this 100 μg/ml standard solu- used as received. Alternatively, other types tion and using the Oxford pipets: of desiccants (equivalent or better) may be used. Volumetric 7.3 Crushed Ice: Quantities ranging from μL or 100 flask volume Working standard, μ/mL μg/mL solu- (dilute to 10–50 lbs may be necessary during a sampling tion mark with run, depending upon ambient temperature. water) Samples which have been taken must be stored and shipped cold; sufficient ice for 0.250 ...... 250 100 0.500 ...... 500 100 this purpose must be allowed. 1.00 ...... 1000 100 7.4 Quaternary ammonium compound stock 2.00 ...... 2000 100 solution: Prepare a stock solution of 3.00 ...... 1500 50 dodecyltrimethylammonium chloride (98 percent minimum assay, reagent grade) by dis- The 100 μg/ml stock solution is stable for 4 solving 1.0 gram in 1000 ml water. This solu- weeks if kept refrigerated between analyses. tion contains nominally 1000 μg/ml quater- The working standards (0.25–3.00 μg/ml) nary ammonium compound, and is used as a should be prepared fresh every day, con- biocide for some sources which are prone to sistent with good laboratory practice for microbial contamination. trace analysis. If the laboratory water is not 7.5 Pararosaniline: Weigh 0.16 grams of sufficient purity, it may be necessary to pararosaniline (free base; assay of 95 percent prepare the working standards every day. or greater, C.I. 42500; Sigma P7632 has been The laboratory must establish that the found to be acceptable) into a 100 ml flask. working standards are stable—DO NOT as- Exercise care, since pararosaniline is a dye sume that your working standards are stable and will stain. Using a wash bottle with for more than a day unless you have verified high-purity water, rinse the walls of the this by actual testing for several series of flask. Add no more than 25 ml water. Then, working standards. carefully add 20 ml of concentrated hydrochloric acid to the flask. The flask will be- 8.0 Sample Collection come warm after the addition of acid. Add a magnetic stir bar to the flask, cap, and place 8.1 Because of the complexity of this meth- on a magnetic stirrer for approximately 4 od, field personnel should be trained in and hours. Then, add additional water so the experienced with the test procedures in order total volume is 100 ml. This solution is sta- to obtain reliable results. ble for several months when stored tightly 8.2 Laboratory Preparation capped at room temperature. 7.6 Sodium sulfite: Weigh 0.10 grams anhy- 8.2.1 All the components shall be main- drous sodium sulfite into a 100 ml flask. Di- tained and calibrated according to the proce- lute to the mark with high purity water. In- dure described in APTD–0576, unless other- vert 15–20 times to mix and dissolve the so- wise specified. dium sulfite. This solution must be prepared 8.2.2 Weigh several 200 to 300 g portions of fresh every day. silica gel in airtight containers to the near- 7.7 Formaldehyde standard solution: Pipet est 0.5 g. Record on each container the total exactly 2.70 ml of 37 percent formaldehyde weight of the silica gel plus containers. As solution into a 1000 ml volumetric flask an alternative to preweighing the silica gel, which contains about 500 ml of high-purity it may instead be weighed directly in the im- water. Dilute to the mark with high-purity pinger or sampling holder just prior to train water. This solution contains nominally 1000 assembly. μg/ml of formaldehyde, and is used to prepare 8.3 Preliminary Field Determinations the working formaldehyde standards. The 8.3.1 Select the sampling site and the min- exact formaldehyde concentration may be imum number of sampling points according determined if needed by suitable modifica- to EPA Method 1, 40 CFR part 60, appendix tion of the sodium sulfite method (Ref- A, or other relevant criteria. Determine the erence: J.F. Walker, Formaldehyde (Third stack pressure, temperature, and range of ve- Edition), 1964.). The 1000 μg/ml formaldehyde locity heads using EPA Method 2, 40 CFR stock solution is stable for at least a year if part 60, appendix A. A leak-check of the kept tightly closed, with the neck of the pitot lines according to Section 3.1 of EPA flask sealed with Parafilm. Store at room Method 2, 40 CFR part 60, appendix A, must temperature. be performed. Determine the stack gas mois- 7.8 Working formaldehyde standards: Pipet ture content using EPA Approximation exactly 10.0 ml of the 1000 μg/ml formalde- Method 4,40 CFR part 60, appendix A, or its hyde stock solution into a 100 ml volumetric alternatives to establish estimates of

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isokinetic sampling rate settings. Determine fourth impinger. Care should be taken to en- the stack gas dry molecular weight, as de- sure that the silica gel is not entrained and scribed in EPA Method 2, 40 CFR part 60, ap- carried out from the impinger during sam- pendix A, Section 3.6. If integrated EPA pling. Place the silica gel container in a Method 3, 40 CFR part 60, appendix A, sam- clean place for later use in the sample recov- pling is used for molecular weight deter- ery. Alternatively, the weight of the silica mination, the integrated bag sample shall be gel plus impinger may be determined to the taken simultaneously with, and for the same nearest 0.5 g and recorded. total length of time as, the sample run. 8.4.3 With a glass or quartz liner, install 8.3.2 Select a nozzle size based on the range the selected nozzle using a Viton-A O-ring of velocity heads so that it is not necessary when stack temperatures are <260 °C (500 °F) to change the nozzle size in order to main- and a woven glass-fiber gasket when tem- tain isokinetic sampling rates below 28 l/min peratures are higher. See APTD–0576 for de- (1.0 cfm). During the run do not change the tails. Other connection systems utilizing ei- nozzle. Ensure that the proper differential ther 316 stainless steel or Teflon TM ferrules pressure gauge is chosen for the range of ve- may be used. Mark the probe with heat-re- locity heads encountered (see Section 2.2 of sistant tape or by some other method to de- EPA Method 2, 40 CFR part 60, appendix A). note the proper distance into the stack or 8.3.3 Select a suitable probe liner and probe duct for each sampling point. length so that all traverse points can be 8.4.4 Assemble the train as shown in Figure sampled. For large stacks, to reduce the 1. During assembly, a very light coating of length of the probe, consider sampling from silicone grease may be used on ground-glass opposite sides of the stack. joints of the impingers, but the silicone 8.3.4 A minimum of 30 cu ft of sample vol- grease should be limited to the outer portion ume is suggested for emission sources with (see APTD–0576) of the ground-glass joints to stack concentrations not greater than minimize silicone grease contamination. If 23,000,000 ppbv. Additional sample volume TM shall be collected as necessitated by the ca- necessary, Teflon tape may be used to pacity of the water reagent and analytical seal leaks. Connect all temperature sensors detection limit constraint. Reduced sample to an appropriate potentiometer/display volume may be collected as long as the final unit. Check all temperature sensors at ambi- concentration of formaldehyde in the stack ent temperatures. sample is greater than 10 (ten) times the de- 8.4.5 Place crushed ice all around the tection limit. impingers. 8.3.5 Determine the total length of sam- 8.4.6 Turn on and set the probe heating sys- pling time needed to obtain the identified tem at the desired operating temperature. minimum volume by comparing the antici- Allow time for the temperature to stabilize. pated average sampling rate with the volume 8.5 Leak-Check Procedures requirement. Allocate the same time to all 8.5.1 Pre-test Leak-check: Recommended, traverse points defined by EPA Method 1, 40 but not required. If the tester elects to con- CFR part 60, appendix A. To avoid duct the pre-test leak-check, the following timekeeping errors, the length of time sam- procedure shall be used. pled at each traverse point should be an inte- 8.5.1.1 After the sampling train has been ger or an integer plus 0.5 min. assembled, turn on and set probe heating 8.3.6 In some circumstances (e.g., batch cy- system at the desired operating temperature. cles) it may be necessary to sample for Allow time for the temperature to stabilize. shorter times at the traverse points and to If a Viton-a O-ring or other leak-free connec- obtain smaller gas-volume samples. In these tion is used in assembling the probe nozzle to cases, careful documentation must be main- the probe liner, leak-check the train at the tained in order to allow accurate calcula- sampling site by plugging the nozzle and tions of concentrations. pulling a 381 mm Hg (15 in Hg) vacuum. 8.4 Preparation of Collection Train 8.4.1 During preparation and assembly of NOTE: A lower vacuum may be used, pro- the sampling train, keep all openings where vided that the lower vacuum is not exceeded contamination can occur covered with Tef- during the test. lon TM film or aluminum foil until just prior If a woven glass fiber gasket is used, do not to assembly or until sampling is about to connect the probe to the train during the begin. leak-check. Instead, leak-check the train by 8.4.2 Place 100 ml of water in each of the first attaching a carbon-filled leak-check im- first two impingers, and leave the third impinger to the inlet and then plugging the pinger empty. If additional capacity is re- inlet and pulling a 381 mm Hg (15 in Hg) vac- quired for high expected concentrations of uum. (A lower vacuum may be used if this formaldehyde in the stack gas, 200 ml of lower vacuum is not exceeded during the water per impinger may be used or addi- test.) Next connect the probe to the train tional impingers may be used for sampling. and leak-check at about 25 mm Hg (1 in Hg) Transfer approximately 200 to 300 g of pre- vacuum. Alternatively, leak-check the probe weighed silica gel from its container to the with the rest of the sampling train in one

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step at 381 mm Hg (15 in Hg) vacuum. Leak- NOTE: Any correction of the sample volume age rates in excess of (a) 4 percent of the av- by calculation reduces the integrity of the erage sampling rate or (b) 0.00057 m3/min (0.02 pollutant concentration data generated and cfm), whichever is less, are unacceptable. must be avoided. 8.5.1.2 The following leak-check instruc- 8.5.2.2 Immediately after component tions for the sampling train described in changes, leak-checks are optional. If per- APTD–0576 and APTD–0581 may be helpful. formed, the procedure described in section Start the pump with the fine-adjust valve 8.5.1.1 shall be used. fully open and coarse-valve completely 8.5.3 Post-test Leak-check: closed. Partially open the coarse-adjust 8.5.3.1 A leak-check is mandatory at the valve and slowly close the fine-adjust valve conclusion of each sampling run. The leak- until the desired vacuum is reached. Do not check shall be done with the same proce- reverse direction of the fine-adjust valve, as dures as the pre-test leak-check, except that liquid will back up into the train. If the de- the post-test leak-check shall be conducted sired vacuum is exceeded, either perform the at a vacuum greater than or equal to the leak-check at this higher vacuum or end the maximum value reached during the sampling leak-check, as described below, and start run. If the leakage rate is found to be no over. greater than 0.00057 m3/min (0.02 cfm) or 4 8.5.1.3 When the leak-check is completed, percent of the average sampling rate (which- first slowly remove the plug from the inlet ever is less), the results are acceptable. If, to the probe. When the vacuum drops to 127 however, a higher leakage rate is obtained, mm (5 in) Hg or less, immediately close the the tester shall record the leakage rate and coarse-adjust valve. Switch off the pumping void the sampling run. system and reopen the fine-adjust valve. Do 8.6 Sampling Train Operation not reopen the fine-adjust valve until the 8.6.1 During the sampling run, maintain an coarse-adjust valve has been closed to pre- isokinetic sampling rate to within 10 percent vent the liquid in the impingers from being of true isokinetic, below 28 l/min (1.0 cfm). forced backward in the sampling line and Maintain a temperature around the probe of silica gel from being entrained backward 120 °C ±14 °C (248 ° ±25 °F). into the third impinger. 8.6.2 For each run, record the data on a 8.5.2 Leak-checks During Sampling Run: data sheet such as the one shown in Figure 8.5.2.1 If, during the sampling run, a com- 2. Be sure to record the initial dry-gas meter ponent change (e.g., impinger) becomes nec- reading. Record the dry-gas meter readings essary, a leak-check shall be conducted im- at the beginning and end of each sampling mediately after the interruption of sampling time increment, when changes in flow rates and before the change is made. The leak- are made, before and after each leak-check, check shall be done according to the proce- and when sampling is halted. Take other dure described in Section 10.3.3, except that readings required by Figure 2 at least once it shall be done at a vacuum greater than or at each sample point during each time incre- equal to the maximum value recorded up to ment and additional readings when signifi- that point in the test. If the leakage rate is cant adjustments (20 percent variation in ve- found to be no greater than 0.0057 m3/min locity head readings) necessitate additional (0.02 cfm) or 4 percent of the average sam- adjustments in flow rate. Level and zero the pling rate (whichever is less), the results are manometer. Because the manometer level acceptable. If a higher leakage rate is ob- and zero may drift due to vibrations and tained, the tester must void the sampling temperature changes, make periodic checks run. during the traverse.

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Pres- Gas sample tem- Tem- sure dif- perature at dry gas perature Sam- Stack Velocity ferential Gas meter Filter of gas Traverse point pling Vacuum tem- head across sample holder leaving number time mm Hg perature ( P) mm orifice volume tem- con- (in. Hg) (T) D m3 perature denser (e) min. (in) H2O meter Inlet Outlet °C (°F) (ft3) ° ° ° ° °C (°F) or last mm H2O C ( F) C ( F) impinger (in. H2O) °C (°F)

...... Total ...... Avg. Avg......

Average ...... Avg......

8.6.3 Clean the stack access ports prior to perature of <20 °C (68 °F) at the silica gel the test run to eliminate the chance of sam- outlet. pling deposited material. To begin sampling, 8.6.8 A single train shall be used for the en- remove the nozzle cap, verify that the probe tire sampling run, except in cases where si- heating system are at the specified tempera- multaneous sampling is required in two or ture, and verify that the pitot tube and probe more separate ducts or at two or more dif- are properly positioned. Position the nozzle ferent locations within the same duct, or in at the first traverse point, with the tip cases where equipment failure necessitates a pointing directly into the gas stream. Imme- change of trains. An additional train or diately start the pump and adjust the flow to trains may also be used for sampling when isokinetic conditions. Nomographs, which the capacity of a single train is exceeded. aid in the rapid adjustment of the isokinetic 8.6.9 When two or more trains are used, sampling rate without excessive computa- separate analyses of components from each tions, are available. These nomographs are train shall be performed. If multiple trains designed for use when the Type S pitot tube have been used because the capacity of a sin- coefficient is 0.84 ±0.02 and the stack gas gle train would be exceeded, first impingers equivalent density (dry molecular weight) is from each train may be combined, and sec- equal to 29 ±4. APTD–0576 details the proce- ond impingers from each train may be com- dure for using the nomographs. If the stack bined. gas molecular weight and the pitot tube co- 8.6.10 At the end of the sampling run, turn efficient are outside the above ranges, do not off the coarse-adjust valve, remove the probe use the nomographs unless appropriate steps and nozzle from the stack, turn off the pump, are taken to compensate for the deviations. record the final dry gas meter reading, and 8.6.4 When the stack is under significant conduct a post-test leak-check. Also, check negative pressure (equivalent to the height the pitot lines as described in EPA Method 2, of the impinger stem), take care to close the 40 CFR part 60, appendix A. The lines must coarse-adjust valve before inserting the pass this leak-check in order to validate the probe into the stack in order to prevent liq- velocity-head data. uid from backing up through the train. If 8.6.11 Calculate percent isokineticity (see necessary, a low vacuum on the train may Method 2) to determine whether the run was have to be started prior to entering the valid or another test should be made. stack. 8.7 Sample Preservation and Handling 8.6.5 When the probe is in position, block 8.7.1 Samples from most sources applicable off the openings around the probe and stack to this method have acceptable holding access port to prevent unrepresentative dilu- times using normal handling practices (ship- tion of the gas stream. ping samples iced, storing in refrigerator at 8.6.6 Traverse the stack cross section, as 2 °C until analysis). However, forming sec- required by EPA Method 1, 40 CFR part 60, tion stacks and other sources using waste appendix A, being careful not to bump the water sprays may be subject to microbial probe nozzle into the stack walls when sam- contamination. For these sources, a biocide pling near the walls or when removing or in- (quaternary ammonium compound solution) serting the probe through the access port, in may be added to collected samples to im- order to minimize the chance of extracting prove sample stability and method rugged- deposited material. ness. 8.6.7 During the test run, make periodic ad- 8.7.2 Sample holding time: Samples should justments to keep the temperature around be analyzed within 14 days of collection. the probe at the proper levels. Add more ice Samples must be refrigerated/kept cold for and, if necessary, salt, to maintain a tem- the entire period preceding analysis. After

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the samples have been brought to room tem- 8.8.2.1.1 Carefully remove the probe nozzle perature for analysis, any analyses needed and rinse the inside surface with water from should be performed on the same day. Re- a wash bottle. Brush with a bristle brush and peated cycles of warming the samples to rinse until the rinse shows no visible par- room temperature/refrigerating/rewarming, ticles, after which make a final rinse of the then analyzing again, etc., have not been in- inside surface. Brush and rinse the inside vestigated in depth to evaluate if analyte parts of the Swagelok (or equivalent) fitting levels remain stable for all sources. with water in a similar way. 8.7.3 Additional studies will be performed 8.8.2.1.2 Rinse the probe liner with water. to evaluate whether longer sample holding While squirting the water into the upper end times are feasible for this method. of the probe, tilt and rotate the probe so that 8.8 Sample Recovery all inside surfaces will be wetted with water. 8.8.1 Preparation: Let the water drain from the lower end into 8.8.1.1 Proper cleanup procedure begins as the sample container. The tester may use a soon as the probe is removed from the stack funnel (glass or polyethylene) to aid in at the end of the sampling period. Allow the transferring the liquid washes to the con- probe to cool. When the probe can be handled tainer. Follow the rinse with a bristle brush. safely, wipe off all external particulate mat- Hold the probe in an inclined position, and ter near the tip of the probe nozzle and place squirt water into the upper end as the probe a cap over the tip to prevent losing or gain- brush is being pushed with a twisting action ing particulate matter. Do not cap the probe through the probe. Hold the sample con- tightly while the sampling train is cooling tainer underneath the lower end of the because a vacuum will be created, drawing probe, and catch any water and particulate liquid from the impingers back through the matter that is brushed from the probe. Run sampling train. the brush through the probe three times or 8.8.1.2 Before moving the sampling train to more. Rinse the brush with water and quan- the cleanup site, remove the probe from the titatively collect these washings in the sam- sampling train and cap the open outlet, ple container. After the brushing, make a being careful not to lose any condensate that final rinse of the probe as describe above. might be present. Remove the umbilical cord from the last impinger and cap the impinger. NOTE: Two people should clean the probe in If a flexible line is used, let any condensed order to minimize sample losses. Between water or liquid drain into the impingers. Cap sampling runs, brushes must be kept clean off any open impinger inlets and outlets. and free from contamination. Ground glass stoppers, Teflon TM caps, or 8.8.2.1.3 Rinse the inside surface of each of caps of other inert materials may be used to the first three impingers (and connecting seal all openings. tubing) three separate times. Use a small 8.8.1.3 Transfer the probe and impinger as- portion of water for each rinse, and brush sembly to an area that is clean and protected each surface to which the sample is exposed from wind so that the chances of contami- with a bristle brush to ensure recovery of nating or losing the sample are minimized. fine particulate matter. Make a final rinse of 8.8.1.4 Inspect the train before and during each surface and of the brush, using water. disassembly, and note any abnormal condi- 8.8.2.1.4 After all water washing and partic- tions. ulate matter have been collected in the sam- 8.8.1.5 Save a portion of the washing solu- ple container, tighten the lid so the sample tion (high purity water) used for cleanup as will not leak out when the container is a blank. shipped to the laboratory. Mark the height 8.8.2 Sample Containers: of the fluid level to determine whether leak- 8.8.2.1 Container 1: Probe and Impinger age occurs during transport. Label the con- Catches. Using a graduated cylinder, meas- tainer clearly to identify its contents. ure to the nearest ml, and record the volume 8.8.2.1.5 If the first two impingers are to be of the solution in the first three impingers. analyzed separately to check for break- Alternatively, the solution may be weighed through, separate the contents and rinses of to the nearest 0.5 g. Include any condensate the two impingers into individual con- in the probe in this determination. Transfer tainers. Care must be taken to avoid phys- the combined impinger solution from the ical carryover from the first impinger to the graduated cylinder into the polyethylene second. Any physical carryover of collected bottle. Taking care that dust on the outside moisture into the second impinger will in- of the probe or other exterior surfaces does validate a breakthrough assessment. not get into the sample, clean all surfaces to 8.8.2.2 Container 2: Sample Blank. Prepare which the sample is exposed (including the a blank by using a polyethylene container probe nozzle, probe fitting, probe liner, first and adding a volume of water equal to the three impingers, and impinger connectors) total volume in Container 1. Process the with water. Use less than 400 ml for the en- blank in the same manner as Container 1. tire waste (250 ml would be better, if pos- 8.8.2.3 Container 3: Silica Gel. Note the sible). Add the rinse water to the sample color of the indicating silica gel to deter- container. mine whether it has been completely spent

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and make a notation of its condition. The fication and quantitation of formaldehyde impinger containing the silica gel may be are dependent on the integrity of the sam- used as a sample transport container with ples received and the precision and accuracy both ends sealed with tightly fitting caps or of the analytical methodology. Quality as- plugs. Ground-glass stoppers or Teflon TM surance procedures for this method are de- caps maybe used. The silica gel impinger signed to monitor the performance of the an- should then be labeled, covered with alu- alytical methodology and to provide the re- minum foil, and packaged on ice for trans- quired information to take corrective action port to the laboratory. If the silica gel is re- if problems are observed in laboratory oper- moved from the impinger, the tester may use ations or in field sampling activities. a funnel to pour the silica gel and a rubber 9.2.1 Field Blanks: Field blanks must be policeman to remove the silica gel from the submitted with the samples collected at each impinger. It is not necessary to remove the sampling site. The field blanks include the small amount of dust particles that may ad- sample bottles containing aliquots of sample here to the impinger wall and are difficult to recover water, and water reagent. At a min- remove. Since the gain in weight is to be imum, one complete sampling train will be used for moisture calculations, do not use assembled in the field staging area, taken to water or other liquids to transfer the silica the sampling area, and leak-checked at the gel. If a balance is available in the field, the beginning and end of the testing (or for the spent silica gel (or silica gel plus impinger) same total number of times as the actual may be weighed to the nearest 0.5 g. sampling train). The probe of the blank train 8.8.2.4 Sample containers should be placed must be heated during the sample test. The in a cooler, cooled by (although not in con- train will be recovered as if it were an actual tact with) ice. Putting sample bottles in Zip- test sample. No gaseous sample will be Lock TM bags can aid in maintaining the in- passed through the blank sampling train. tegrity of the sample labels. Sample con- 9.2.2 Blank Correction: The field blank tainers should be placed vertically to avoid formaldehyde concentrations will be sub- leakage during shipment. Samples should be tracted from the appropriate sample form- cooled during shipment so they will be re- aldehyde concentrations. Blank formalde- ceived cold at the laboratory. It is critical hyde concentrations above 0.25 μg/ml should that samples be chilled immediately after re- be considered suspect, and subtraction from covery. If the source is susceptible to micro- the sample formaldehyde concentrations bial contamination from wash water (e.g. should be performed in a manner acceptable forming section stack), add biocide as di- to the Administrator. rected in section 8.2.5. 9.2.3 Method Blanks: A method blank must 8.8.2.5 A quaternary ammonium compound be prepared for each set of analytical oper- can be used as a biocide to stabilize samples ations, to evaluate contamination and arti- against microbial degradation following col- facts that can be derived from glassware, re- lection. Using the stock quaternary ammo- agents, and sample handling in the labora- nium compound (QAC) solution; add 2.5 ml tory. QAC solution for every 100 ml of recovered sample volume (estimate of volume is satis- 10 Calibration factory) immediately after collection. The 10.1 Probe Nozzle: Probe nozzles shall be total volume of QAC solution must be accu- calibrated before their initial use in the rately known and recorded, to correct for field. Using a micrometer, measure the in- any dilution caused by the QAC solution ad- side diameter of the nozzle to the nearest dition. 0.025 mm (0.001 in). Make measurements at 8.8.3 Sample Preparation for Analysis three separate places across the diameter 8.8.3.1 The sample should be refrigerated if and obtain the average of the measurements. the analysis will not be performed on the day The difference between the high and low of sampling. Allow the sample to warm at numbers shall not exceed 0.1 mm (0.004 in). room temperature for about two hours (if it When the nozzle becomes nicked or corroded, has been refrigerated) prior to analyzing. it shall be repaired and calibrated, or re- 8.8.3.2 Analyze the sample by the placed with a calibrated nozzle before use. pararosaniline method, as described in Sec- Each nozzle must be permanently and tion 11. If the color-developed sample has an uniquely identified. absorbance above the highest standard, a 10.2 Pitot Tube: The Type S pitot tube as- suitable dilution in high purity water should sembly shall be calibrated according to the be prepared and analyzed. procedure outlined in Section 4 of EPA Method 2, or assigned a nominal coefficient 9.0 Quality Control of 0.84 if it is not visibly nicked or corroded 9.1 Sampling: See EPA Manual 600/4–77–02b and if it meets design and intercomponent for Method 5 quality control. spacing specifications. 9.2 Analysis: The quality assurance pro- 10.3 Metering System gram required for this method includes the 10.3.1 Before its initial use in the field, the analysis of the field and method blanks, and metering system shall be calibrated accord- procedure validations. The positive identi- ing to the procedure outlined in APTD–0576.

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Instead of physically adjusting the dry-gas thermometers, such as are used for the dry meter dial readings to correspond to the wet- gas meter and condenser outlet, shall be cali- test meter readings, calibration factors may brated against mercury-in-glass thermom- be used to correct the gas meter dial read- eters. An alternative mercury-free thermom- ings mathematically to the proper values. eter may be used if the thermometer is, at a Before calibrating the metering system, it is minimum, equivalent in terms of perform- suggested that a leak-check be conducted. ance or suitably effective for the specific For metering systems having diaphragm temperature measurement application. pumps, the normal leak-check procedure will 10.6 Barometer: Adjust the barometer ini- not delete leakages with the pump. For these tially and before each test series to agree to cases, the following leak-check procedure within ±2.5 mm Hg (0.1 in Hg) of the mercury will apply: Make a ten-minute calibration barometer. Alternately, if a National Weath- run at 0.00057 m3/min (0.02 cfm). At the end of er Service Station (NWSS) is located at the the run, take the difference of the measured same altitude above sea level as the test site, wet-test and dry-gas meter volumes and di- the barometric pressure reported by the vide the difference by 10 to get the leak rate. NWSS may be used. The leak rate should not exceed 0.00057 m3/ 10.7 Balance: Calibrate the balance before min (0.02 cfm). each test series, using Class S standard 10.3.2 After each field use, check the cali- weights. The weights must be within ±0.5 bration of the metering system by per- percent of the standards, or the balance forming three calibration runs at a single in- must be adjusted to meet these limits. termediate orifice setting (based on the previous field test). Set the vacuum at the max- 11.0 Procedure for Analysis imum value reached during the test series. The working formaldehyde standards (0.25, To adjust the vacuum, insert a valve be- 0.50, 1.0, 2.0, and 3.0 μg/ml) are analyzed and tween the wet-test meter and the inlet of the a calibration curve is calculated for each metering system. Calculate the average day’s analysis. The standards should be ana- value of the calibration factor. If the calibra- lyzed first to ensure that the method is tion has changed by more than 5 percent, re- working properly prior to analyzing the sam- calibrate the meter over the full range of ples. In addition, a sample of the high-purity orifice settings, as outlined in APTD–0576. water should also be analyzed and used as a 10.3.3 Leak-check of metering system: The ‘‘0’’ formaldehyde standard. portion of the sampling train from the pump The procedure for analysis of samples and to the orifice meter (see Figure 1) should be standards is identical: Using the pipet set to leak-checked prior to initial use and after 2.50 ml, pipet 2.50 ml of the solution to be each shipment. Leakage after the pump will analyzed into a polystyrene cuvette. Using result in less volume being recorded than is the 250 μl pipet, pipet 250 μl of the actually sampled. Use the following proce- pararosaniline reagent solution into the dure: Close the main valve on the meter box. cuvette. Seal the top of the cuvette with a Insert a one-hole rubber stopper with rubber Parafilm square and shake at least 30 sec- tubing attached into the orifice exhaust onds to ensure the solution in the cuvette is pipe. Disconnect and vent the low side of the well-mixed. Peel back a corner of the orifice manometer. Close off the low side ori- Parafilm so the next reagent can be added. fice tap. Pressurize the system to 13–18 cm Using the 250 μl pipet, pipet 250 μl of the so- (5–7 in) water column by blowing into the dium sulfite reagent solution into the rubber tubing. Pinch off the tubing and ob- cuvette. Reseal the cuvette with the serve the manometer for 1 min. A loss of Parafilm, and again shake for about 30 sec- pressure on the manometer indicates a leak onds to mix the solution in the cuvette. in the meter box. Leaks must be corrected. Record the time of addition of the sodium NOTE: If the dry-gas meter coefficient val- sulfite and let the color develop at room ues obtained before and after a test series temperature for 60 minutes. Set the spectro- differ by >5 percent, either the test series photometer to 570 nm and set to read in Ab- must be voided or calculations for test series sorbance Units. The spectrophotometer must be performed using whichever meter should be equipped with a holder for the 1-cm coefficient value (i.e., before or after) gives pathlength cuvettes. Place cuvette(s) con- the lower value of total sample volume. taining high-purity water in the spectro- 10.4 Probe Heater: The probe heating sys- photometer and adjust to read 0.000 AU. tem must be calibrated before its initial use After the 60 minutes color development pe- in the field according to the procedure out- riod, read the standard and samples in the lined in APTD–0576. Probes constructed ac- spectrophotometer. Record the absorbance cording to APTD–0581 need not be calibrated reading for each cuvette. The calibration if the calibration curves in APTD–0576 are curve is calculated by linear regression, with used. the formaldehyde concentration as the ‘‘x’’ 10.5 Temperature gauges: Use the proce- coordinate of the pair, and the absorbance dure in Section 4.3 of EPA Method 2 to cali- reading as the ‘‘y’’ coordinate. The procedure brate in-stack temperature gauges. Dial is very reproducible, and typically will yield

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values similar to these for the calibration Total mg formaldehyde= curve: ×× × μ Correlation Coefficient: 0.9999 Cd V DF0./ 001 mg g Slope: 0.50 Where: Y-Intercept: 0.090 Cd = measured conc. formaldehyde, μg/ml The formaldehyde concentration of the sam- V = total volume of stack sample, ml ples can be found by using the trend-line fea- DF = dilution factor ture of the calculator or computer program used for the linear regression. For example, 12.1.2 To determine the total formaldehyde the TI–55 calculators use the ‘‘X’’ key (this in mg, use the following equation if biocide gives the predicted formaldehyde concentra- was used: tion for the value of the absorbance you key Total mg formaldehyde= in for the sample). Multiply the formalde- × hyde concentration from the sample by the CVd dilution factor, if any, for the sample to give ()− ×× μ the formaldehyde concentration of the origi- V B DF0./ 001 mg g nal, undiluted, sample (units will be Where: micrograms/ml). C = measured conc. formaldehyde, μg/ml 11.1 Notes on the Pararosaniline Procedure d V = total volume of stack sample, ml 11.1.1 The pararosaniline method is tem- B = total volume of biocide added to sample, perature-sensitive. However, the small fluc- ml tuations typical of a laboratory will not significantly affect the results. DF = dilution factor 11.1.2 The calibration curve is linear to be- 12.2 Formaldehyde concentration (mg/m3) yond 4 ‘‘μg/ml’’ formaldehyde, however, a re- in stack gas. Determine the formaldehyde search-grade spectrophotometer is required concentration (mg/m3) in the stack gas using to reproducibly read the high absorbance the following equation: Formaldehyde con- values. Consult your instrument manual to centration (mg/m3) = evaluate the capability of the spectrophotometer. K× [,] total formaldehyde mg 11.1.3 The quality of the laboratory water used to prepare standards and make dilu- Vm () std tions is critical. It is important that the cau- Where: tions given in the Reagents section be ob- 3 served. This procedure allows quantitation of K = 35.31 cu ft/m for Vm (std) in English formaldehyde at very low levels, and thus it units, or 3 3 is imperative to avoid contamination from K = 1.00 m /m for Vm (std) in metric units other sources of formaldehyde and to exer- Vm (std) = volume of gas sample measured by cise the degree of care required for trace a dry gas meter, corrected to standard analyses. conditions, dscm (dscf) 11.1.4 The analyst should become familiar 12.3 Average dry gas meter temperature with the operation of the Oxford or equiva- and average orifice pressure drop are ob- lent pipettors before using them for an anal- tained from the data sheet. ysis. Follow the instructions of the manufac- 12.4 Dry Gas Volume: Calculate Vm (std) turer; one can pipet water into a tared con- and adjust for leakage, if necessary, using tainer on any analytical balance to check the equation in Section 6.3 of EPA Method 5, pipet accuracy and precision. This will also 40 CFR part 60, appendix A. establish if the proper technique is being 12.5 Volume of Water Vapor and Moisture used. Always use a new tip for each pipetting Content: Calculated the volume of water operation. vapor and moisture content from equations 11.1.5 This procedure follows the rec- 5–2 and 5–3 of EPA Method 5. ommendations of ASTM Standard Guide D 3614, reading all solutions versus water in the 13.0 Method Performance reference cell. This allows the absorbance of The precision of this method is estimated the blank to be tracked on a daily basis. to be better than ±5 percent, expressed as Refer to ASTM D 3614 for more information. ±the percent relative standard deviation.

12.0 Calculations 14.0 Pollution Prevention [Reserved] Carry out calculations, retaining at least one extra decimal figure beyond that of the 15.0 Waste Management [Reserved] acquired data. Round off figures after final 16.0 References calculations. 12.1 Calculations of Total Formaldehyde R.R. Miksch, et al., Analytical Chemistry, 12.1.1 To determine the total formaldehyde November 1981, 53 pp. 2118–2123. in mg, use the following equation if biocide J.F. Walker, Formaldehyde, Third Edition, was not used: 1964.

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US EPA 40 CFR, part 60, Appendix A, Test Carbon Monoxide 630–08–0 Methods 1–5 Carbonyl Sulfide 463–58–1 Formaldehyde 50–00–0 METHOD 318—EXTRACTIVE FTIR METHOD FOR Methanol 1455–13–6 THE MEASUREMENT OF EMISSIONS FROM THE MINERAL WOOL AND WOOL FIBERGLASS IN- Phenol 108–95–2 DUSTRIES 1.2 Applicability 1.2.1 This method is applicable for the de- 1.0 Scope and Application termination of formaldehyde, phenol, meth- This method has been validated and ap- anol, carbonyl sulfide (COS) and carbon mon- proved for mineral wool and wool fiberglass oxide (CO) concentrations in controlled and sources. This method may not be applied to uncontrolled emissions from manufacturing other source categories without validation processes using phenolic resins. The com- and approval by the Administrator according pounds are analyzed in the mid-infrared to the procedures in Test Method 301, 40 CFR spectral region (about 400 to 4000 cm¥1 or 25 part 63, appendix A. For sources seeking to to 2.5 μm). Suggested analytical regions are apply FTIR to other source categories, Test given below (Table 1). Slight deviations from Method 320 (40 CFR part 63, appendix A) may these recommended regions may be nec- be utilized. essary due to variations in moisture content 1.1 Scope. The analytes measured by this and ammonia concentration from source to method and their CAS numbers are: source.

TABLE 1—EXAMPLE ANALYTICAL REGIONS

¥ Compound Analytical region (cm 1) Potential interferants FLm ¥ FUm

Formaldehyde ...... 2840.93¥2679.83 ...... Water, Methane. Phenol ...... 1231.32¥1131.47 ...... Water, Ammonia, Methane. Methanol ...... 1041.56¥1019.95 ...... Water, Ammonia. a COS ...... 2028.4¥2091.9 ...... Water, CO2 CO. a CO ...... 2092.1¥2191.8 ...... Water, CO2, COS.

a Suggested analytical regions assume about 15 percent moisture and CO2, and that COS and CO have about the same absorbance (in the range of 10 to 50 ppm). If CO and COS are hundreds of ppm or higher, then CO2 and moisture interference is reduced. If CO or COS is present at high concentration and the other at low concentration, then a shorter cell pathlength may be necessary to measure the high concentration component.

1.2.2 This method does not apply when: (a) cell due to high concentration levels. For Polymerization of formaldehyde occurs, (b) these two compounds, make sure absorbance moisture condenses in either the sampling of highest concentration component is <1.0. system or the instrumentation, and (c) when 1.4 Data Quality Objectives moisture content of the gas stream is so high 1.4.1 In designing or configuring the system, relative to the analyte concentrations that the analyst first sets the data quality objec- it causes severe spectral interference. tives, i.e., the desired lower detection limit 1.3 Method Range and Sensitivity (DLi) and the desired analytical uncertainty 1.3.1 The analytical range is a function of (AUi) for each compound. The instrumental instrumental design and composition of the parameters (factors b, c, d, and e in Section gas stream. Theoretical detection limits de- 1.3.1) are then chosen to meet these require- pend, in part, on (a) the absorption coeffi- ments, using Appendix D of the FTIR Pro- cient of the compound in the analytical fre- tocol. quency region, (b) the spectral resolution, (c) 1.4.2 Data quality for each application is de- interferometer sampling time, (d) detector termined, in part, by measuring the RMS sensitivity and response, and (e) absorption (Root Mean Square) noise level in each ana- pathlength. lytical spectral region (Appendix C of the 1.3.2 Practically, there is no upper limit to FTIR Protocol). The RMS noise is defined as the range. The practical lower detection the RMSD (Root Mean Square Deviation) of limit is usually higher than the theoretical the absorbance values in an analytical re- value, and depends on (a) moisture content gion from the mean absorbance value of the of the flue gas, (b) presence of interferants, region. Appendix D of the FTIR Protocol de- and (c) losses in the sampling system. In gen- fines the MAUim (minimum analyte uncer- eral, a 22 meter pathlength cell in a suitable tainty of the ith analyte in the mth analyt- sampling system can achieve practical detec- ical region). The MAU is the minimum tion limits of 1.5 ppm for three compounds analyte concentration for which the analyt- (formaldehyde, phenol, and methanol) at ical uncertainty limit (AUi) can be main- moisture levels up to 15 percent by volume. tained: if the measured analyte concentra- Sources with uncontrolled emissions of CO tion is less than MAUi, then data quality is and COS may require a 4 meter pathlength unacceptable. Table 2 gives some example

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DL and AU values along with calculated areas and MAU values using the protocol procedures.

TABLE 2—EXAMPLE PRE-TEST PROTOCOL CALCULATIONS

Protocol Protocol value Form Phenol Methanol appendix

Reference concentration a (ppm-meters)/K ...... 3.016 3.017 5.064 Reference Band Area ...... 8.2544 16.6417 4.9416 B DL (ppm-meters)/K...... 0.1117 0.1117 0.1117 B AU ...... 0.2 0.2 0.2 B CL ...... 0.02234 0.02234 0.02234 B FL ...... 2679.83 1131.47 1019.95 B FU ...... 2840.93 1231.32 1041.56 B FC ...... 2760.38 1181.395 1030.755 B AAI (ppm-meters)/K...... 0.18440 0.01201 0.00132 B RMSD ...... 2.28E–03 1.21E–03 1.07E–03 C MAU (ppm-meters)/K...... 4.45E–02 7.26E–03 4.68E–03 D MAU (ppm at 22) ...... 0.0797 0.0130 0.0084 D a Concentration units are: ppm concentration of the reference sample (ASC), times the path length of the FTIR cell used when the reference spectrum was measured (meters), divided by the absolute temperature of the reference sample in Kelvin (K), or (ppm-meters)/K.

2.0 Summary of Method 2.2.1 Flue gas is continuously extracted from the source, and the gas or a portion of 2.1 Principle the gas is conveyed to the FTIR gas cell, 2.1.1 Molecules are composed of chemically where a spectrum of the flue gas is recorded. bonded atoms, which are in constant motion. The atomic motions result in bond deforma- Absorbance band intensities are related to tions (bond stretching and bond-angle bend- sample concentrations by Beer’s Law. ing). The number of fundamental (or inde- = pendent) vibrational motions depends on the Aabcv∑ i i ()6 number of atoms (N) in the molecule. At typical testing temperatures, most molecules Where: th are in the ground-state vibrational state for An = absorbance of the i component at the most of their fundamental vibrational mo- given frequency, n. tions. A molecule can undergo a transition a = absorption coefficient of the ith compo- from its ground state (for a particular vibra- nent at the frequency, n. tion) to the first excited state by absorbing b = path length of the cell. a quantum of light at a frequency char- c = concentration of the ith compound in the acteristic of the molecule and the molecular sample at frequency n. motion. Molecules also undergo rotational transitions by absorbing energies in the far- 2.2.2 After identifying a compound from infrared or microwave spectral regions. Ro- the infrared spectrum, its concentration is tational transition absorbencies are super- determined by comparing band intensities in imposed on the vibrational absorbencies to the sample spectrum to band intensities in give a characteristic shape to each rota- ‘‘reference spectra’’ of the formaldehyde, tional-vibrational absorbance ‘‘band.’’ phenol, methanol, COS and CO. These ref- 2.1.2 Most molecules exhibit more than one erence spectra are available in a permanent absorbance band in several frequency regions soft copy from the EPA spectral library on to produce an infrared spectrum (a char- the EMTIC bulletin board. The source may acteristic pattern of bands or a ‘‘finger- also prepare reference spectra according to print’’) that is unique to each molecule. The Section 4.5 of the FTIR Protocol. infrared spectrum of a molecule depends on NOTE: Reference spectra not prepared ac- its structure (bond lengths, bond angles, bond strengths, and atomic masses). Even cording to the FTIR Protocol are not accept- small differences in structure can produce able for use in this test method. Documenta- significantly different spectra. tion detailing the FTIR Protocol steps used 2.1.3 Spectral band intensities vary with in preparing any non-EPA reference spectra the concentration of the absorbing com- shall be included in each test report sub- pound. Within constraints, the relationship mitted by the source. between absorbance and sample concentra- 2.3 Operator Requirements. The analyst tion is linear. Sample spectra are compared must have some knowledge of source sam- to reference spectra to determine the species pling and of infrared spectral patterns to op- and their concentrations. erate the sampling system and to choose a 2.2 Sampling and Analysis

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suitable instrument configuration. The ana- tester(s) to ensure proper safety and health lyst should also understand FTIR instru- practices, and to determine the applicability ment operation well enough to choose an in- of regulatory limitations before performing strument configuration consistent with the this test method. data quality objectives. 6.0 Equipment and Supplies 3.0 Definitions The equipment and supplies are based on See Appendix A of the FTIR Protocol. the schematic of a sampling train shown in 4.0 Interferences Figure 1. Either the evacuated or purged sampling technique may be used with this 4.1 Analytical (or Spectral) Interferences. sampling train. Alternatives may be used, Water vapor. High concentrations of ammo- provided that the data quality objectives of nia (hundreds of ppm) may interfere with the this method are met. analysis of low concentrations of methanol 6.1 Sampling Probe. Glass, stainless steel, (1 to 5 ppm). For CO, carbon dioxide and or other appropriate material of sufficient water may be interferants. In cases where length and physical integrity to sustain COS levels are low relative to CO levels, CO heating, prevent adsorption of analytes, and and water may be interferants. to reach gas sampling point. 4.2 Sampling System Interferences. Water, if it condenses, and ammonia, which reacts 6.2 Particulate Filters. A glass wool plug with formaldehyde. (optional) inserted at the probe tip (for large particulate removal) and a filter rated at 1- 5.0 Safety micron (e.g., Balston TM) for fine particulate removal, placed immediately after the heat- 5.1 Formaldehyde is a suspected cared probe. cinogen; therefore, exposure to this compound must be limited. Proper monitoring 6.3 Sampling Line/Heating System. Heated ± and safety precautions must be practiced in (maintained at 250 25 degrees F) stainless TM any atmosphere with potentially high con- steel, Teflon , or other inert material that centrations of CO. does not adsorb the analytes, to transport 5.2 This method may involve sampling at the sample to analytical system. locations having high positive or negative 6.4 Stainless Steel Tubing. Type 316, e.g., 3⁄8 pressures, high temperatures, elevated in. diameter, and appropriate length for heights, high concentrations of hazardous or heated connections. toxic pollutants, or other diverse sampling 6.5 Gas Regulators. Appropriate for indi- conditions. It is the responsibility of the vidual gas cylinders.

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6.6 Teflon TM Tubing. Diameter (e.g., 3⁄8 in.) 6.10 FTIR Analytical System. Spectrom- and length suitable to connect cylinder regu- eter and detector, capable of measuring lators. formaldehyde, phenol, methanol, COS and 6.7 Sample Pump. A leak-free pump (e.g., CO to the predetermined minimum detect- KNF TM), with by-pass valve, capable of pull- able level. The system shall include a per- ing sample through entire sampling system sonal computer with compatible software at a rate of about 10 to 20 L/min. If placed be- that provides real-time updates of the spec- fore the analytical system, heat the pump tral profile during sample collection and and use a pump fabricated from materials spectral collection. 6.11 FTIR Cell Pump. Required for the non-reactive to the target pollutants. If the evacuated sampling technique, capable of pump is located after the instrument, sys- evacuating the FTIR cell volume within 2 tematically record the sample pressure in minutes. The FTIR cell pump should allow the gas cell. the operator to obtain at least 8 sample spec- 6.8 Gas Sample Manifold. A heated mani- tra in 1 hour. fold that diverts part of the sample stream 6.12 Absolute Pressure Gauge. Heatable and to the analyzer, and the rest to the by-pass capable of measuring pressure from 0 to 1000 discharge vent or other analytical instru- mmHg to within ±2.5 mmHg (e.g., mentation. Baratron TM). 6.9 Rotameter. A calibrated 0 to 20 L/min 6.13 Temperature Gauge. Capable of meas- range rotameter. uring the cell temperature to within ±2 °C.

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7.0 Reagents and Standards pump, and determine the change in pressure P after 2 minutes. 7.1 Ethylene (Calibration Transfer Stand- D v ard). Obtain NIST traceable (or Protocol) 8.3.2 For both the evacuated sample and cylinder gas. purging techniques, pressurize the system to 7.2 Nitrogen. Ultra high purity (UHP) about 100 mmHg above atmospheric pressure. grade. Isolate the pump and determine the change 7.3 Reference Spectra. Obtain reference in pressure DPp after 2 minutes. spectra for the target pollutants at con- 8.3.3 Measure the barometric pressure, Pb centrations that bracket (in ppm-meter/K) in mmHg. the emission source levels. Also, obtain ref- 8.3.4 Determine the percent leak volume %V for the signal integration time t and erence spectra for SF6 and ethylene. Suitable L SS concentrations are 0.0112 to 0.112 (ppm- for DPmax, i.e., the larger of DPv or DPp, as follows: meter)/K for SF6 and 5.61 (ppm-meter)/K or less for ethylene. The reference spectra shall Δ meet the criteria for acceptance outlined in = Pmax Section 2.2.2. The optical density (ppm-me- %VtLSS50 (2) ters/K) of the reference spectrum must PSS match the optical density of the sample Where: spectrum within (less than) 25 percent. 50 = 100% divided by the leak-check time of 8.0 Sample Collection, Preservation, and Storage 2 minutes. 8.3.5 Leak volumes in excess of 4 percent of Sampling should be performed in the fol- the sample system volume V are unaccept- lowing sequence: Collect background, collect SS able. CTS spectrum, collect samples, collect post- test CTS spectrum, verify that two copies of 8.4 Background Spectrum. Evacuate the ≤ all data were stored on separate computer gas cell to 5 mmHg, and fill with dry nitro- media. gen gas to ambient pressure. Verify that no 8.1 Pretest Preparations and Evaluations. significant amounts of absorbing species (for Using the procedure in Section 4.0 of the example water vapor and CO2) are present. FTIR Protocol, determine the optimum sam- Collect a background spectrum, using a sig- pling system configuration for sampling the nal averaging period equal to or greater than target pollutants. Table 2 gives some exam- the averaging period for the sample spectra. ple values for AU, DL, and MAU. Based on a Assign a unique file name to the background study (Reference 1), an FTIR system using 1 spectrum. Store the spectra of the back- cm¥1 resolution, 22 meter path length, and a ground interferogram and processed single- broad band MCT detector was suitable for beam background spectrum on two separate meeting the requirements in Table 2. Other computer media (one is used as the back-up). factors that must be determined are: If continuous sampling will be used during a. Test requirements: AU , CMAX , DL , sample collection, collect the background i i i spectrum with nitrogen gas flowing through OFUi, and tAN for each. b. Interferants: See Table 1. the cell at the same pressure and temperature as will be used during sampling. c. Sampling system: LS′, Pmin, PS′, TS′, tSS, 8.5 Pre-Test Calibration Transfer Standard. VSS; fractional error, MIL. Evacuate the gas cell to ≤5 mmHg absolute d. Analytical regions: 1 through Nm, FLm, pressure, and fill the FTIR cell to atmos- FCm, and FUm, plus interferants, FFUm, pheric pressure with the CTS gas. Or, purge FFLm, wavenumber range FNU to FNL. See Tables 1 and 2. the cell with 10 cell volumes of CTS gas. 8.1.1 If necessary, sample and acquire an Record the spectrum. If continuous sampling initial spectrum. Then determine the proper will be used during sample collection, collect operational pathlength of the instrument to the CTS spectrum with CTS gas flowing obtain non-saturated absorbances of the tar- through the cell at the same pressure and get analytes. temperature as will be used during sampling. 8.1.2 Set up the sampling train as shown in 8.6 Samples Figure 1. 8.6.1 Evacuated Samples. Evacuate the ab- 8.2 Sampling System Leak-check. Leak- sorbance cell to ≤5 mmHg absolute pressure. check from the probe tip to pump outlet as Fill the cell with flue gas to ambient pres- follows: Connect a 0- to 250-mL/min rate sure and record the spectrum. Before taking meter (rotameter or bubble meter) to the the next sample, evacuate the cell until no outlet of the pump. Close off the inlet to the further evidence of absorption exists. Repeat probe, and note the leakage rate. The leak- this procedure to collect at least 8 separate age rate shall be ≤200 mL/min. spectra (samples) in 1 hour. 8.3 Analytical System Leak-check. 8.6.2 Purge Sampling. Purge the FTIR cell 8.3.1 For the evacuated sample technique, with 10 cell volumes of flue gas and at least close the valve to the FTIR cell, and evac- for about 10 minutes. Discontinue the gas uate the absorption cell to the minimum ab- cell purge, isolate the cell, and record the solute pressure Pmin. Close the valve to the sample spectrum and the pressure. Before 803

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taking the next sample, purge the cell with tions 8.5 and 8.9) and the post-test quality as- 10 cell volumes of flue gas. surance procedures in Section 8.10. 8.6.3 Continuous Sampling. Spectra can be collected continuously while the FTIR cell is 10.0 Calibration and Standardization being purged. The sample integration time, 10.1 Signal-to-Noise Ratio (S/N). The S/N tss, the sample flow rate through the FTIR shall be sufficient to meet the MAU in each gas cell, and the total run time must be cho- analytical region. sen so that the collected data consist of at 10.2 Absorbance Pathlength. Verify the ab- least 10 spectra with each spectrum being of sorbance path length by comparing CTS a separate cell volume of flue gas. More spec- spectra to reference spectra of the calibra- tra can be collected over the run time and tion gas(es). See FTIR Protocol, Appendix E. the total run time (and number of spectra) 10.3 Instrument Resolution. Measure the can be extended as well. line width of appropriate CTS band(s) and 8.7 Sampling QA, Data Storage and Report- compare to reference CTS spectra to verify ing instrumental resolution. 8.7.1 Sample integration times should be 10.4 Apodization Function. Choose appro- sufficient to achieve the required signal-to- priate apodization function. Determine any noise ratios. Obtain an absorbance spectrum appropriate mathematical transformations by filling the cell with nitrogen. Measure the that are required to correct instrumental er- RMSD in each analytical region in this ab- rors by measuring the CTS. Any mathe- sorbance spectrum. Verify that the number matical transformations must be docu- of scans is sufficient to achieve the target mented and reproducible. MAU (Table 2). 10.5 FTIR Cell Volume. Evacuate the cell 8.7.2 Identify all sample spectra with to ≤5 mmHg. Measure the initial absolute unique file names. temperature (Ti) and absolute pressure (Pi). 8.7.3 Store on two separate computer media Connect a wet test meter (or a calibrated dry a copy of sample interferograms and proc- gas meter), and slowly draw room air into essed spectra. The data shall be available to the cell. Measure the meter volume (Vm), the Administrator on request for the length meter absolute temperature (T ), and meter of time specified in the applicable regula- m absolute pressure (Pm), and the cell final ab- tion. solute temperature (T ) and absolute pres- 8.7.4 For each sample spectrum, document f sure (Pf). Calculate the FTIR cell volume Vss, the sampling conditions, the sampling time including that of the connecting tubing, as (while the cell was being filled), the time the follows: spectrum was recorded, the instrumental conditions (path length, temperature, pres- P sure, resolution, integration time), and the V m spectral file name. Keep a hard copy of these m T data sheets. = m VSS (8) 8.8 Signal Transmittance. While sampling, ⎡ P P ⎤ monitor the signal transmittance through ⎢ f − i ⎥ the instrumental system. If signal transmit- ⎣Tf Ti ⎦ tance (relative to the background) drops below 95 percent in any spectral region As an alternative to the wet test meter/cali- where the sample does not absorb infrared brated dry gas meter procedure, measure the energy, obtain a new background spectrum. inside dimensions of the cell cylinder and 8.9 Post-run CTS. After each sampling run, calculate its volume. record another CTS spectrum. 11.0 Procedure 8.10 Post-test QA 8.10.1 Inspect the sample spectra imme- Refer to Sections 4.6–4.11, Sections 5, 6, and diately after the run to verify that the gas 7, and the appendices of the FTIR Protocol. matrix composition was close to the expected (assumed) gas matrix. 12.0 Data Analysis and Calculations 8.10.2 Verify that the sampling and instru- a. Data analysis is performed using appro- mental parameters were appropriate for the priate reference spectra whose concentra- conditions encountered. For example, if the tions can be verified using CTS spectra. Var- moisture is much greater than anticipated, ious analytical programs are available to re- it will be necessary to use a shorter path late sample absorbance to a concentration length or dilute the sample. standard. Calculated concentrations should 8.10.3 Compare the pre and post-run CTS be verified by analyzing spectral baselines spectra. They shall agree to within ¥5 per- after mathematically subtracting scaled ref- cent. See FTIR Protocol, Appendix E. erence spectra from the sample spectra. A full description of the data analysis and cal- 9.0 Quality Control culations may be found in the FTIR Protocol Follow the quality assurance procedures in (Sections 4.0, 5.0, 6.0 and appendices). the method, including the analysis of pre and b. Correct the calculated concentrations in post-run calibration transfer standards (Sec- sample spectra for differences in absorption

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pathlength between the reference and sample media. The method is applicable to effi- spectra by: ciency determinations from 0 to 99 percent. Two test aerosols are used—one liquid phase ⎡L ⎤ ⎡ T ⎤ and one solid phase. Oleic acid, a low-vola- = r s tility liquid (CAS Number 112–80–1), is used Ccorr ⎢ ⎥ ⎢ ⎥Ccalc (9) ⎣ Ls ⎦ ⎣Tr ⎦ to simulate the behavior of wet paint overspray. The solid-phase aerosol is potas- Where: sium chloride salt (KCl, CAS Number 7447– Ccorr = The pathlength corrected concentra- 40–7) and is used to simulate the behavior of tion. a dry overspray. The method is limited to de- Ccalc = The initial calculated concentration termination of the initial, clean filtration ef- (output of the Multicomp program de- ficiency of the arrestor. Changes in effi- signed for the compound). ciency (either increase or decrease) due to L = The pathlength associated with the ref- r the accumulation of paint overspray on and erence spectra. within the arrestor are not evaluated. Ls = The pathlength associated with the sample spectra. 1.2 Efficiency is defined as 1—Penetration (e.g., 70 percent efficiency is equal to 0.30 Ts = The absolute temperature (K) of the sample gas. penetration). Penetration is based on the ratio of the downstream particle concentra- Tr = The absolute gas temperature (K) at which reference spectra were recorded. tion to the upstream concentration. It is often more useful, from a mathematical or 13.0 Reporting and Recordkeeping statistical point of view, to discuss the up- All interferograms used in determining stream and downstream counts in terms of source concentration shall be stored for the penetration rather than the derived effi- period of time required in the applicable reg- ciency value. Thus, this document uses both ulation. The Administrator has the option of penetration and efficiency as appropriate. requesting the interferograms recorded dur- 1.3 For a paint arrestor system or sub- ing the test in electronic form as part of the system which has been tested by this meth- test report. od, adding additional filtration devices to the system or subsystem shall be assumed to 14.0 Method Performance result in an efficiency of at least that of the Refer to the FTIR Protocol. original system without the requirement for additional testing. (For example, if the final 15.0 Pollution Prevention [Reserved] stage of a three-stage paint arrestor system has been tested by itself, then the addition of 16.0 Waste Management the other two stages shall be assumed to Laboratory standards prepared from the maintain, as a minimum, the filtration effi- formaldehyde and phenol are handled accord- ciency provided by the final stage alone. ing to the instructions in the materials safe- Thus, in this example, if the final stage has ty data sheets (MSDS). been shown to meet the filtration requirements of Table 1 of § 63.745 of subpart GG, 17.0 References then the final stage in combination with any (1) ‘‘Field Validation Test Using Fourier additional paint arrestor stages also passes Transform Infrared (FTIR) Spectrometry To the filtration requirements.) Measure Formaldehyde, Phenol and Meth- anol at a Wool Fiberglass Production Facil- 2.0 Summary of Method ity.’’ Draft. U.S. Environmental Protection 2.1 This method applies to the determina- Agency Report, Entropy, Inc., EPA Contract tion of the fractional (i.e., particle-size de- No. 68D20163, Work Assignment I–32, Decem- pendent) aerosol penetration of several types ber 1994 (docket item II-A-13). (2) ‘‘Method 301—Field Validation of Pol- of paint arrestors. Fractional penetration is lutant Measurement Methods from Various computed from aerosol concentrations meas- Waste Media,’’ 40 CFR part 63, appendix A. ured upstream and downstream of an arrestor installed in a laboratory test rig. The METHOD 319—DETERMINATION OF FILTRATION aerosol concentrations upstream and down- EFFICIENCY FOR PAINT OVERSPRAY ARRES- stream of the arrestors are measured with an TORS aerosol analyzer that simultaneously counts and sizes the particles in the aerosol stream. 1.0 Scope and Application The aerosol analyzer covers the particle di- 1.1 This method applies to the determina- ameter size range from 0.3 to 10 μm in a min- tion of the initial, particle size dependent, imum of 12 contiguous sizing channels. Each filtration efficiency for paint arrestors over sizing channel covers a narrow range of par- the particle diameter range from 0.3 to 10 ticle diameters. For example, Channel 1 may μm. The method applies to single and mul- cover from 0.3 to 0.4 μm, Channel 2 from 0.4 tiple stage paint arrestors or paint arrestor to 0.5 μm, * * * By taking the ratio of the

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downstream to upstream counts on a chan- eters based on size, index of refraction, and nel by channel basis, the penetration is com- shape. puted for each of the sizing channels. Penetration—the fraction of the aerosol 2.2 The upstream and downstream aerosol that penetrates the filter at a given particle measurements are made while injecting the diameter. Penetration equals the down- test aerosol into the air stream upstream of stream concentration divided by the up- the arrestor (ambient aerosol is removed stream concentration. with HEPA filters on the inlet of the test rig). This test aerosol spans the particle size 4.0 Interferences range from 0.3 to 10 μm and provides suffi- 4.1 The influence of the known inter- cient upstream concentration in each of the ferences (particle losses) are negated by cor- optical particle counter (OPC) sizing chan- rection of the data using blanks. nels to allow accurate calculation of penetration, down to penetrations of approxi- 5.0 Safety mately 0.01 (i.e., 1 percent penetration; 99 percent efficiency). Results are presented as 5.1 There are no specific safety precautions a graph and a data table showing the aero- for this method above those of good labora- dynamic particle diameter and the cor- tory practice. This standard does not purport responding fractional efficiency. to address all of the safety problems, if any, associated with its use. It is the responsi- 3.0 Definitions bility of the user of this method to establish Aerodynamic Diameter—diameter of a unit appropriate safety and health practices and density sphere having the same aerodynamic determine the applicability of regulatory properties as the particle in question. limitations prior to use. Efficiency is defined as equal to 1—Pene- 6.0 Equipment and Supplies tration. Optical Particle Counter (OPC)—an instru- 6.1 Test Facility. A schematic diagram of a ment that counts particles by size using test duct used in the development of the light scattering. An OPC gives particle diam- method is shown in Figure 319–1.

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6.1.1 The test section, paint spray section, polyvinyl chloride (PVC). The upstream and attached transitions are constructed of transition provides a 7 ° angle of expansion stainless and galvanized steel. The upstream to provide a uniform air flow distribution to and downstream ducting is 20 cm diameter the paint arrestors. Aerosol concentration is

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measured upstream and downstream of the to the surrounding room; the challenge air test section to obtain the challenge and pen- has a temperature between 50 ° and 100 °F etrating aerosol concentrations, respec- and a relative humidity of less than 65 per- tively. Because the downstream ducting runs cent; the angle of the upstream transition (if back under the test section, the challenge used) to the paint arrestor must not exceed and penetrating aerosol taps are located 7 °; the angle of the downstream transition physically near each other, thereby facili- (if used) from the paint arrestor must not ex- tating aerosol sampling and reducing sam- ceed 30 °; the test duct must provide a means ple-line length. The inlet nozzles of the up- for mixing the challenge aerosol with the upstream and downstream aerosol probes are stream flow (in lieu of any mixing device, a designed to yield isokinetic sampling condi- duct length of 15 duct diameters fulfills this tions. requirement); the test duct must provide a 6.1.2 The configuration and dimensions of means for mixing any penetrating aerosol the test duct can deviate from those of Fig- with the downstream flow (in lieu of any ure 319–1 provided that the following key ele- mixing device, a duct length of 15 duct diam- ments are maintained: the test duct must eters fulfills this requirement); the test sec- meet the criteria specified in Table 319–1; the tion must provide a secure and leak-free inlet air is HEPA filtered; the blower is on mounting for single and multiple stage ar- the upstream side of the duct thereby cre- restors; and the test duct may utilize a 180 ° ating a positive pressure in the duct relative bend in the downstream duct.

TABLE 319–1—QC CONTROL LIMITS

h Frequency and description Control limits

OPC zero count ...... Each Test. OPC samples HEPA-filtered <50 counts per minute. air. OPC sizing accuracy check ...... Daily. Sample aerosolized PSL spheres Peak of distribution should be in correct OPC channel. Minimum counts per channel for chal- Each Test ...... Minimum total of 500 particle counts per lenge aerosol. channel. Maximum particle concentration ...... Each Test. Needed to ensure OPC is <10% of manufacturer’s claimed upper not overloaded. limit corresponding to a 10% count error. Standard Deviation of Penetration ...... Computed for each test based on the <0.10 for 0.3 to 3 μm diameter. CV of the upstream and downstream <0.30 for >3 μm diameter. counts. 0% Penetration ...... Monthly ...... <0.01. 100% Penetration—KCl ...... Triplicate tests performed immediately 0.3 to 1 μm: 0.90 to 1.10. before, during, or after triplicate arres- 1 to 3 μm: 0.75 to 1.25. tor tests. 3 to 10 μm: 0.50 to 1.50. 100% Penetration—Oleic Acid...... Triplicate tests performed immediately 0.3 to 1 μm: 0.90 to 1.10. before, during, or after triplicate arres- 1 to 3 μm: 0.75 to 1.25. tor tests. 3 to 10 μm: 0.50 to 1.50.

6.2 Aerosol Generator. The aerosol gener- the 0.3 to 10 μm diameter size range; provide ator is used to produce a stable aerosol cov- a means of ensuring the complete drying of ering the particle size range from 0.3 to 10 the KCl aerosol; and utilize a charge neutral- μm diameter. The generator used in the de- izer to neutralize any electrostatic charge on velopment of this method consists of an air the aerosol. The resultant challenge aerosol atomizing nozzle positioned at the top of a must meet the minimum count per channel 0.30–m (12-in.) diameter, 1.3–m (51-in.) tall, and maximum concentration criteria of acrylic, transparent, spray tower. This tower Table 319–1. allows larger sized particles, which would 6.3 Installation of Paint Arrestor. The otherwise foul the test duct and sample paint arrestor is to be installed in the test lines, to fall out of the aerosol. It also adds duct in a manner that precludes air bypass- drying air to ensure that the KCl droplets ing the arrestor. Since arrestor media are dry to solid salt particles. After generation, often sold unmounted, a mounting frame the aerosol passes through an aerosol neu- may be used to provide back support for the tralizer (Kr85 radioactive source) to neu- media in addition to sealing it into the duct. tralize any electrostatic charge on the aer- The mounting frame for 20 in. × 20 in. arres- osol (electrostatic charge is an unavoidable tors will have minimum open internal di- consequence of most aerosol generation mensions of 18 in. square. Mounting frames methods). To improve the mixing of the aer- for 24 in. × 24 in. arrestors will have min- osol with the air stream, the aerosol is in- imum open internal dimensions of 22 in. jected counter to the airflow. Generators of square. The open internal dimensions of the other designs may be used, but they must mounting frame shall not be less than 75 per- produce a stable aerosol concentration over cent of the approach duct dimensions.

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6.4 Optical Particle Counter. The upstream 6.5.1 The sampling system may be designed and downstream aerosol concentrations are to acquire the upstream and downstream measured with a high-resolution optical par- samples using (a) sequential upstream-down- ticle counter (OPC). To ensure comparability stream sampling with a single OPC, (b) si- of test results, the OPC shall utilize an opti- multaneous upstream and downstream sam- cal design based on wide-angle light scat- pling with two OPC’s, or (c) sequential up- tering and provided a minimum of 12 contig- stream-downstream sampling with two uous particle sizing channels from 0.3 to 10 OPC’s. μm diameter (based on response to PSL) 6.5.2 When two particle counters are used where, for each channel, the ratio of the di- to acquire the upstream and downstream ameter corresponding to the upper channel counts, they must be closely matched in bound to the lower channel bound must not flowrate and optical design. exceed 1.5. 6.6 Airflow Monitor. The volumetric air- 6.5 Aerosol Sampling System. The up- flow through the system shall be measured stream and downstream sample lines must with a calibrated orifice plate, flow nozzle, be made of rigid electrically-grounded metal- or laminar flow element. The measurement lic tubing having a smooth inside surface, device must have an accuracy of 5 percent or and they must be rigidly secured to prevent better. movement during testing. The upstream and 7.0 Reagents and Standards downstream sample lines are to be nominally identical in geometry. The use of a 7.1 The liquid test aerosol is reagent grade, short length (100 mm maximum) of straight 98 percent pure, oleic acid (Table 319–2). The flexible tubing to make the final connection solid test aerosol is KCl aerosolized from a to the OPC is acceptable. The inlet nozzles of solution of KCl in water. In addition to the the upstream and downstream probes must test aerosol, a calibration aerosol of be sharp-edged and of appropriate entrance monodisperse polystyrene latex (PSL) diameter to maintain isokinetic sampling spheres is used to verify the calibration of within 20 percent of the air velocity. the OPC.

TABLE 319–2—PROPERTIES OF THE TEST AND CALIBRATION AEROSOLS

Refractive index Density, Shape g/cm 3

Oleic Acid (liquid-phase challenge 1.46 nonabsorbing ...... 0.89 Spherical. aerosol). KCl (solid-phase challenge aer- 1.49 ...... 1.98 Cubic or agglomerated cubes. osol). PSL (calibration aerosol) ...... 1.59 nonabsorbing ...... 1.05 Spherical.

8.0 Sample Collection, Preservation, and Storage Each arrestor is clearly labeled for tracking purposes. 8.1 In this test, all sampling occurs in real- time, thus no samples are collected that re- 9.0 Quality Control quire preservation or storage during the test. 9.1 Table 319–1 lists the QC control limits. The paint arrestors are shipped and stored to 9.2 The standard deviation (s) of the pene- avoid structural damage or soiling. Each ar- tration (P) for a given test at each of the 15 restor may be shipped in its original box OPC sizing channels is computed from the from the manufacturer or similar cardboard coefficient of variation (CV, the standard de- box. Arrestors are stored at the test site in viation divided by the mean) of the upstream a location that keeps them clean and dry. and downstream measurements as:

σ =+22 PPCV() upstream CV downstream (Eq. 319-1)

For a properly operating system, the stand- 9.3.1 Fractional Penetration. From the ard deviation of the penetration is <0.10 at triplicate tests of each paint arrestor model, particle diameters from 0.3 to 3 μm and less the standard deviation for the penetration than 0.30 at diameters >3 μm. measurements at each particle size (i.e., for 9.3 Data Quality Objectives (DQO). each sizing channel of the OPC) is computed as:

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1 =−⎡ ()2 ()− ⎤ 2 sPPn⎣⎢∑ i /1 ⎦⎥ (Eq. 319-2)

where Pi represents an individual penetra- Brand/Model llllllllllllllll tion measurement, and P the average of the Arrestor Assigned ID # llllllllll 3 (n = 3) individual measurements. Condition of arrestor (i.e., is there any 9.3.2 Bias of the fractional penetration val- damage? Must be new condition to proceed): ues is determined from triplicate no-filter llllllllllllllllllllllll and HEPA filter tests. These tests determine Manometer zero and level confirmed? the measurement bias at 100 percent penetration and 0 percent penetration, respectively. llllllllllllllllllllllll 9.3.3 PSL-Equivalent Light Scattering Di- Part 2. Clean Efficiency Test ameter. The precision and bias of the OPC sizing determination are based on sampling a Date and Time: lllllllllllllll known diameter of PSL and noting whether Optical Particle Counter: the particle counts peak in the correct chan- 20 min. warm up llllllllllllll nel of the OPC. This is a pass/fail measure- Zero count (<50 counts/min) lllllll ment with no calculations involved. 9.3.4 Airflow. The precision of the measure- Daily PSL check lllllllllllll ment must be within 5 percent of the set PSL Diam: lll μm point. File name for OPC data: lllllllll 10.0 Calibration and Standardization Test Conditions: Air Flow: lll 10.1 Optical Particle Counter. The OPC Temp & RH: Temp lll °F RH lll % must have an up-to-date factory calibration. Check the OPC zero at the beginning and end Atm. Pressure: lllin. Hg of each test by sampling HEPA-filtered air. (From mercury barometer) Verify the sizing accuracy on a daily basis Aerosol Generator: (record all operating pa- (for days when tests are performed) with 1- rameters) size PSL spheres. llllllllllllllllllllllll 10.2 Airflow Measurement. Airflow meas- llllllllllllllllllllllll urement devices must have an accuracy of 5 percent or better. Manometers used in con- llllllllllllllllllllllll junction with the orifice plate must be in- llllllllllllllllllllllll spected prior to use for proper level, zero, Test Aerosol: and mechanical integrity. Tubing connec- (Oleic acid or KCl) llllllllllll tions to the manometer must be free from Arrestor: kinks and have secure connections. Pressure drop: at start lll in. H O 10.3 Pressure Drop. Measure pressure drop 2 across the paint arrestor with an inclined at end lll in. H2O manometer readable to within 0.01 in. H2O. Condition of arrestor at end of test (note Prior to use, the level and zero of the ma- any physical deterioration): nometer, and all tubing connections, must be llllllllllllllllllllllll inspected and adjusted as needed. llllllllllllllllllllllll 11.0 Procedure FIGURE 319–2. TEST RUN SHEET 11.1 Filtration Efficiency. For both the Other report formats which contain the oleic acid and KCl challenges, this procedure same information are acceptable. is performed in triplicate using a new arres- 11.1.1.2 Record the date, time, test oper- tor for each test. ator, Test #, paint arrestor brand/model and 11.1.1 General Information and Test Duct its assigned ID number. For tests with no ar- Preparation restor, record none. 11.1.1.1 Use the ‘‘Test Run Sheet’’ form (Figure 319–2) to record the test information. 11.1.1.3 Ensure that the arrestor is undamaged and is in ‘‘new’’ condition. RUN SHEET 11.1.1.4 Mount the arrestor in the appropriate frame. Inspect for any airflow leak Part 1. General Information paths. Date and Time: lllllllllllllll 11.1.1.5 Install frame-mounted arrestor in the test duct. Examine the installed arrestor Test Operator: lllllllllllllll to verify that it is sealed in the duct. For Test #: lllllllllllllllllll tests with no arrestor, install the empty Paint Arrestor: frame.

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11.1.1.6 Visually confirm the manometer 11.1.2.4.3 Obtain one set of upstream-down- zero and level. Adjust as needed. stream background measurements. 11.1.2 Clean Efficiency Test. 11.1.2.4.4 After obtaining the upstream- 11.1.2.1 Record the date and time upon be- downstream measurements, stop data acqui- ginning this section. sition. 11.1.2.2 Optical Particle Counter. 11.1.2.5 Efficiency Measurements: 11.1.2.2.1 General: Operate the OPC per the 11.1.2.5.1 Record the arrestor pressure drop. manufacturer’s instructions allowing a min- 11.1.2.5.2 Turn on the Aerosol Generator. imum of 20 minutes warm up before making Begin aerosol generation and record the op- any measurements. erating parameters. 11.1.2.2.2 Overload: The OPC will yield inac- 11.1.2.5.3 Monitor the particle counts. curate data if the aerosol concentration it is Allow a minimum of 5 minutes for the gener- attempting to measure exceeds its operating ator to stabilize. limit. To ensure reliable measurements, the 11.1.2.5.4 Confirm that the total particle maximum aerosol concentration will not ex- count does not exceed the predetermined ceed 10 percent of the manufacturer’s upper limit. Adjust generator as needed. claimed upper concentration limit cor- 11.1.2.5.5 Confirm that a minimum of 50 particle counts are measured in the up- responding to a 10 percent count error. If stream sample in each of the OPC channels this value is exceeded, reduce the aerosol per sample. (A minimum of 50 counts per concentration until the acceptable condi- channel per sample will yield the required tions are met. minimum 500 counts per channel total for 11.1.2.2.3 Zero Count: Connect a HEPA cap- the 10 upstream samples as specified in Table sule to the inlet of the OPC and obtain print- 319–1.) Adjust generator or sample time as outs for three samples (each a minimum of 1- needed. minute each). Record maximum cumulative 11.1.2.5.6 If you are unable to obtain a sta- zero count. If the count rate exceeds 50 ble concentration within the concentration counts per minute, the OPC requires serv- limit and with the 50 count minimum per icing before continuing. channel, adjust the aerosol generator. 11.1.2.2.4 PSL Check of OPC Calibration: 11.1.2.5.7 When the counts are stable, per- Confirm the calibration of the OPC by sam- form repeated upstream-downstream sampling a known size PSL aerosol. Aerosolize pling until 10 upstream-downstream meas- the PSL using an appropriate nebulizer. urements are obtained. Record whether the peak count is observed 11.1.2.5.8 After collection of the 10 up- in the proper channel. If the peak is not seen stream-downstream samples, stop data ac- in the appropriate channel, have the OPC re- quisition and allow 2 more minutes for final calibrated. purging of generator. 11.1.2.3 Test Conditions: 11.1.2.5.9 Obtain one additional set of up- 11.1.2.3.1 Airflow: The test airflow cor- stream-downstream background samples. responds to a nominal face velocity of 120 11.1.2.5.10 After obtaining the upstream- FPM through the arrestor. For arrestors downstream background samples, stop data having nominal 20 in. × 20 in. face dimen- acquisition. sions, this measurement corresponds to an 11.1.2.5.11 Record the arrestor pressure airflow of 333 cfm. For arrestors having drop. nominal face dimensions of 24 in. × 24 in., 11.1.2.5.12 Turn off blower. this measurement corresponds to an airflow 11.1.2.5.13 Remove the paint arrestor as- of 480 cfm. sembly from the test duct. Note any signs of 11.1.2.3.2 Temperature and Relative Humid- physical deterioration. ity: The temperature and relative humidity 11.1.2.5.14 Remove the arrestor from the of the challenge air stream will be measured frame and place the arrestor in an appro- to within an accuracy of ±2 °F and ±10 per- priate storage bag. cent RH. To protect the probe from fouling, 11.2 Control Test: 100 Percent Penetration it may be removed during periods of aerosol Test. A 100 percent penetration test must be generation. performed immediately before each indi- 11.1.2.3.3 Barometric Pressure: Use a mer- vidual paint arrestor test using the same cury barometer. Record the atmospheric challenge aerosol substance (i.e., oleic acid pressure. or KCl) as to be used in the arrestor test. 11.1.2.4 Upstream and Downstream Back- These tests are performed with no arrestor ground Counts. installed in the test housing. This test is a 11.1.2.4.1 With the arrestor installed in the relatively stringent test of the adequacy of test duct and the airflow set at the proper the overall duct, sampling, measurement, value, turn on the data acquisition computer and aerosol generation system. The test is and bring up the data acquisition program. performed as a normal penetration test ex- 11.1.2.4.2 Set the OPC settings for the ap- cept the paint arrestor is not used. A perfect propriate test sample duration with output system would yield a measured penetration for both printer and computer data collec- of 1 at all particle sizes. Deviations from 1 tion. can occur due to particle losses in the duct,

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differences in the degree of aerosol uniformity (i.e., mixing) at the upstream and ()DD− downstream probes, and differences in par- = b P100 ticle transport efficiency in the upstream ()UU− and downstream sampling lines. b 11.3 Control Test: 0 Percent Penetration. P = Penetration of the arrestor corrected for One 0 percent penetration test must be per- P100 formed at least monthly during testing. The r= sample standard deviation test is performed by using a HEPA filter CV = coefficient of variation = r/mean rather than a paint arrestor. This test as- E = Efficiency. sesses the adequacy of the instrument re- Overbar denotes arithmetic mean of quan- sponse time and sample line lag. tity. Analysis of each test involves the fol- 12.0 Data Analysis and Calculations lowing quantities: • 12.1 Analysis. The analytical procedures P100 value for each sizing channel from the 100 percent penetration control test, for the fractional penetration and flow veloc- • 2 upstream background values, ity measurements are described in Section • 2 downstream background values, 11. Note that the primary measurements, • 10 upstream values with aerosol gener- those of the upstream and downstream aer- ator on, and osol concentrations, are performed with the • 10 downstream values with aerosol gener- OPC which acquires the sample and analyzes ator on. it in real time. Because all the test data are Using the values associated with each collected in real time, there are no analyt- sizing channel, the penetration associated ical procedures performed subsequent to the with each particle-sizing channel is cal- actual test, only data analysis. culated as: 12.2 Calculations. 12.2.1 Penetration. ⎧ ⎫ ⎪()DD− b ⎪ = Nomenclature P ⎨ ⎬ /(P100 Eq. 319-3) ⎪()UU− b ⎪ U = Upstream particle count ⎩ ⎭ D = Downstream particle count =− Ub = Upstream background count EP1 (Eq. 319-4) Db = Downstream background count Most often, the background levels are P100 = 100 percent penetration value deter- small compared to the values when the aer- mined immediately prior to the arrestor osol generator is on. test computed for each channel as: 12.3 The relationship between the physical diameter (DPhysical) as measured by the OPC to the aerodynamic diameter (DAero) is given by:

ρ CCF DD= Particle Physical (Eq. 319-5 ) Aero Physical ρ o CCFAero

Where: • Triplicate 100 percent penetration tests 3 with the solid-phase challenge aerosol, and pO = unit density of 1 g/cm . 3 • pParticle = the density of the particle, 0.89 g/cm One 0 percent filter test (using either the for oleic acid. liquid-phase or solid-phase aerosol and per- CCFPhysical = the Cunningham Correction Fac- formed at least monthly). tor at DPhysical. 12.4.1 Results for the paint arrestor test CCFAero = the Cunningham Correction Factor must be presented in both graphical and tab- at DAero. ular form. The X-axis of the graph will be a 12.4 Presentation of Results. For a given logarithmic scale of aerodynamic diameter arrestor, results will be presented for: from 0.1 to 100 μm. The Y-axis will be effi- • Triplicate arrestor tests with the liquid- ciency (%) on a linear scale from 0 to 100. phase challenge aerosol, Plots for each individual run and a plot of • Triplicate arrestor tests with the solid- the average of triplicate solid-phase and of phase challenge aerosol, the average triplicate liquid-phase tests • Triplicate 100 percent penetration tests must be prepared. All plots are to be based with the liquid-phase challenge aerosol,

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on point-to-point plotting (i.e., no curve fit- method are given in appendix A of the Pro- ting is to be used). The data are to be plotted tocol. References to specific sections in the based on the geometric mean diameter of Protocol are made throughout this Method. each of the OPC’s sizing channels. For additional information refer to ref- 12.4.2 Tabulated data from each test must erences 1 and 2, and other EPA reports, be provided. The data must include the upper which describe the use of FTIR spectrometry and lower diameter bound and geometric in specific field measurement applications mean diameter of each of the OPC sizing and validation tests. The sampling procedure channels, the background particle counts for described here is extractive. Flue gas is ex- each channel for each sample, the upstream tracted through a heated gas transport and particle counts for each channel for each handling system. For some sources, sample sample, the downstream particle counts for conditioning systems may be applicable. each channel for each sample, the 100 percent Some examples are given in this method. penetration values computed for each chan- NOTE: Sample conditioning systems may nel, and the 0 percent penetration values be used providing the method validation re- computed for each channel. quirements in Sections 9.2 and 13.0 of this 13.0 Pollution Prevention method are met. 1.1 Scope and Applicability. 13.1 The quantities of materials to be aero- 1.1.1 Analytes. Analytes include hazardous solized should be prepared in accord with the air pollutants (HAPs) for which EPA ref- amount needed for the current tests so as to erence spectra have been developed. Other prevent wasteful excess. compounds can also be measured with this 14.0 Waste Management method if reference spectra are prepared according to section 4.6 of the protocol. 14.1 Paint arrestors may be returned to 1.1.2 Applicability. This method applies to originator, if requested, or disposed of with the analysis of vapor phase organic or inor- regular laboratory waste. ganic compounds which absorb energy in the mid-infrared spectral region, about 400 to 15.0 References 4000 cm¥1 (25 to 2.5 μm). This method is used 1. Hanley, J.T., D.D. Smith and L. Cox. to determine compound-specific concentra- ‘‘Fractional Penetration of Paint Overspray tions in a multi-component vapor phase sam- Arrestors, Draft Final Report,’’ EPA Cooper- ple, which is contained in a closed-path gas ative Agreement CR–817083–01–0, January cell. Spectra of samples are collected using 1994. double beam infrared absorption spectros- 2. Hanley, J.T., D.D. Smith, and D.S. copy. A computer program is used to analyze Ensor. ‘‘Define a Fractional Efficiency Test spectra and report compound concentrations. Method that is Compatible with Particulate 1.2 Method Range and Sensitivity. Analytical Removal Air Cleaners Used in General Ven- range and sensitivity depend on the fre- tilation,’’ Final Report, 671–RP, American quency-dependent analyte absorptivity, in- Society of Heating, Refrigerating, and Air- strument configuration, data collection pa- Conditioning Engineers, Inc., December 1993. rameters, and gas stream composition. In- 3. ‘‘Project Work and Quality Assurance strument factors include: (a) spectral resolu- Plan: Fractional Penetration of Paint tion, (b) interferometer signal averaging Overspray Arrestors, Category II,’’ EPA Co- time, (c) detector sensitivity and response, operative Agreement No. CR–817083, July and (d) absorption path length. 1994. 1.2.1 For any optical configuration the analytical range is between the absorbance val- TEST METHOD 320—MEASUREMENT OF VAPOR ues of about .01 (infrared transmittance rel- PHASE ORGANIC AND INORGANIC EMISSIONS ative to the background = 0.98) and 1.0 BY EXTRACTIVE FOURIER TRANSFORM INFRA- (T = 0.1). (For absorbance >1.0 the relation RED (FTIR) SPECTROSCOPY between absorbance and concentration may not be linear.) 1.0 Introduction 1.2.2 The concentrations associated with Persons unfamiliar with basic elements of this absorbance range depend primarily on FTIR spectroscopy should not attempt to the cell path length and the sample tempera- use this method. This method describes sam- ture. An analyte absorbance greater than 1.0, pling and analytical procedures for extrac- can be lowered by decreasing the optical tive emission measurements using Fourier path length. Analyte absorbance increases transform infrared (FTIR) spectroscopy. De- with a longer path length. Analyte detection tailed analytical procedures for interpreting also depends on the presence of other species infrared spectra are described in the ‘‘Pro- exhibiting absorbance in the same analytical tocol for the Use of Extractive Fourier region. Additionally, the estimated lower ab- Transform Infrared (FTIR) Spectrometry in sorbance (A) limit Analyses of Gaseous Emissions from Sta- (A = 0.01) depends on the root mean square tionary Sources,’’ hereafter referred to as deviation (RMSD) noise in the analytical re- the ‘‘Protocol.’’ Definitions not given in this gion.

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1.2.3 The concentration range of this meth- copy and quantitative analysis. A summary od is determined by the choice of optical is given in this section. configuration. 2.1.1 Infrared absorption spectroscopy is 1.2.3.1 The absorbance for a given con- performed by directing an infrared beam centration can be decreased by decreasing through a sample to a detector. The fre- the path length or by diluting the sample. quency-dependent infrared absorbance of the There is no practical upper limit to the sample is measured by comparing this detec- measurement range. tor signal (single beam spectrum) to a signal 1.2.3.2 The analyte absorbance for a given obtained without a sample in the beam path concentration may be increased by increas- (background). ing the cell path length or (to some extent) 2.1.2 Most molecules absorb infrared radi- using a higher resolution. Both modifica- ation and the absorbance occurs in a char- tions also cause a corresponding increased acteristic and reproducible pattern. The in- absorbance for all compounds in the sample, frared spectrum measures fundamental mo- and a decrease in the signal throughput. For lecular properties and a compound can be this reason the practical lower detection identified from its infrared spectrum alone. range (quantitation limit) usually depends 2.1.3 Within constraints, there is a linear on sample characteristics such as moisture relationship between infrared absorption and content of the gas, the presence of other compound concentration. If this frequency interferants, and losses in the sampling sys- dependent relationship (absorptivity) is tem. known (measured), it can be used to deter- 1.3 Sensitivity. The limit of sensitivity for mine compound concentration in a sample an optical configuration and integration mixture. time is determined using appendix D of the 2.1.4 Absorptivity is measured by pre- Protocol: Minimum Analyte Uncertainty, paring, in the laboratory, standard samples (MAU). The MAU depends on the RMSD of compounds at known concentrations and noise in an analytical region, and on the ab- measuring the FTIR ‘‘reference spectra’’ of sorptivity of the analyte in the same region. these standard samples. These ‘‘reference spectra’’ are then used in sample analysis: (1) 1.4 Data Quality. Data quality shall be de- Compounds are detected by matching sample termined by executing Protocol pre-test pro- absorbance bands with bands in reference cedures in appendices B to H of the protocol spectra, and (2) concentrations are measured and post-test procedures in appendices I and by comparing sample band intensities with J of the protocol. reference band intensities. 1.4.1 Measurement objectives shall be es- 2.1.5 This method is self-validating pro- tablished by the choice of detection limit vided that the results meet the performance (DL ) and analytical uncertainty (AU ) for i i requirement of the QA spike in sections 8.6.2 each analyte. and 9.0 of this method, and results from a 1.4.2 An instrumental configuration shall previous method validation study support be selected. An estimate of gas composition the use of this method in the application. shall be made based on previous test data, 2.2 Sampling and Analysis. In extractive data from a similar source or information sampling a probe assembly and pump are gathered in a pre-test site survey. Spectral used to extract gas from the exhaust of the interferants shall be identified using the se- affected source and transport the sample to lected DL and AU and band areas from ref- i i the FTIR gas cell. Typically, the sampling erence spectra and interferant spectra. The apparatus is similar to that used for single- baseline noise of the system shall be meas- component continuous emission monitor ured in each analytical region to determine (CEM) measurements. the MAU of the instrument configuration for 2.2.1 The digitized infrared spectrum of the each analyte and interferant (MIU ). i sample in the FTIR gas cell is measured and 1.4.3 Data quality for the application shall stored on a computer. Absorbance band in- be determined, in part, by measuring the tensities in the spectrum are related to sam- RMS (root mean square) noise level in each ple concentrations by what is commonly re- analytical spectral region (appendix C of the ferred to as Beer’s Law. Protocol). The RMS noise is defined as the RMSD of the absorbance values in an analyt- = ical region from the mean absorbance value Aabciii (1) in the region. Where:

1.4.4 The MAU is the minimum analyte Ai = absorbance at a given frequency of the concentration for which the AUi can be ith sample component. maintained; if the measured analyte con- ai = absorption coefficient (absorptivity) of centration is less than MAUi then data qual- the ith sample component. ity are unacceptable. b = path length of the cell. ci = concentration of the ith sample compo- 2.0 Summary of Method nent. 2.1 Principle. References 4 through 7 provide 2.2.2 Analyte spiking is used for quality as- background material on infrared spectros- surance (QA). In this procedure (section 8.6.2

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of this method) an analyte is spiked into the 3.4 Concentration. In this method con- gas stream at the back end of the sample centration is expressed as a molar concentra- probe. Analyte concentrations in the spiked tion, in ppm-meters, or in (ppm-meters)/K, samples are compared to analyte concentra- where K is the absolute temperature (Kel- tions in unspiked samples. Since the con- vin). The latter units allow the direct com- centration of the spike is known, this proce- parison of concentrations from systems dure can be used to determine if the sam- using different optical configurations or pling system is removing the spiked sampling temperatures. analyte(s) from the sample stream. 3.5 Interferant. A compound in the sample 2.3 Reference Spectra Availability. Reference matrix whose infrared spectrum overlaps spectra of over 100 HAPs are available in the with part of an analyte spectrum. The most EPA FTIR spectral library on the EMTIC accurate analyte measurements are achieved (Emission Measurement Technical Informa- when reference spectra of interferants are tion Center) computer bulletin board service used in the quantitative analysis with the and at internet address http:// analyte reference spectra. The presence of an info.arnold.af.mil/epa/welcome.htm. Reference interferant can increase the analytical un- spectra for HAPs, or other analytes, may certainty in the measured analyte con- also be prepared according to section 4.6 of centration. the Protocol. 3.6 Gas Cell. A gas containment cell that 2.4 Operator Requirements. The FTIR ana- can be evacuated. It is equipped with the op- lyst shall be trained in setting up the instru- tical components to pass the infrared beam mentation, verifying the instrument is func- through the sample to the detector. Impor- tioning properly, and performing routine tant cell features include: path length (or maintenance. The analyst must evaluate the range if variable), temperature range, mate- initial sample spectra to determine if the rials of construction, and total gas volume. sample matrix is consistent with pre-test as- 3.7 Sampling System. Equipment used to ex- sumptions and if the instrument configura- tract the sample from the test location and tion is suitable. The analyst must be able to transport the sample gas to the FTIR ana- modify the instrument configuration, if nec- lyzer. This includes sample conditioning sys- essary. tems. 2.4.1 The spectral analysis shall be super- 3.8 Sample Analysis. The process of inter- vised by someone familiar with EPA FTIR preting the infrared spectra to obtain sample Protocol procedures. analyte concentrations. This process is usu- 2.4.2 A technician trained in instrumental ally automated using a software routine em- test methods is qualified to install and oper- ploying a classical least squares (cls), partial ate the sampling system. This includes in- least squares (pls), or K- or P-matrix meth- stalling the probe and heated line assembly, od. operating the analyte spike system, and per- 3.9 One hundred percent line. A double beam forming moisture and flow measurements. transmittance spectrum obtained by combining two background single beam spectra. 3.0 Definitions Ideally, this line is equal to 100 percent See appendix A of the Protocol for defini- transmittance (or zero absorbance) at every tions relating to infrared spectroscopy. Addi- frequency in the spectrum. Practically, a tional definitions are given in sections 3.1 zero absorbance line is used to measure the through 3.29. baseline noise in the spectrum. 3.1 Analyte. A compound that this method 3.10 Background Deviation. A deviation from is used to measure. The term ‘‘target 100 percent transmittance in any region of analyte’’ is also used. This method is multi- the 100 percent line. Deviations greater than component and a number of analytes can be ±5 percent in an analytical region are unac- targeted for a test. ceptable (absorbance of 0.021 to ¥0.022). Such 3.2 Reference Spectrum. Infrared spectrum of deviations indicate a change in the instru- an analyte prepared under controlled, document throughput relative to the background mented, and reproducible laboratory condi- single beam. tions according to procedures in section 4.6 3.11 Batch Sampling. A procedure where of the Protocol. A library of reference spec- spectra of discreet, static samples are col- tra is used to measure analytes in gas sam- lected. The gas cell is filled with sample and ples. the cell is isolated. The spectrum is col- 3.3 Standard Spectrum. A spectrum that has lected. Finally, the cell is evacuated to pre- been prepared from a reference spectrum pare for the next sample. through a (documented) mathematical oper- 3.12 Continuous Sampling. A procedure ation. A common example is de-resolving of where spectra are collected while sample gas reference spectra to lower-resolution stand- is flowing through the cell at a measured ard spectra (Protocol, appendix K to the ad- rate. dendum of this method). Standard spectra, 3.13 Sampling resolution. The spectral reso- prepared by approved, and documented, pro- lution used to collect sample spectra. cedures can be used as reference spectra for 3.14 Truncation. Limiting the number of analysis. interferogram data points by deleting points

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farthest from the center burst (zero path dif- spiked and half are not spiked. The length of ference, ZPD). the run is determined by the interval be- 3.15 Zero filling. The addition of points to tween independent samples. the interferogram. The position of each 3.27 Screening. Screening is used when there added point is interpolated from neighboring is little or no available information about a real data points. Zero filling adds no infor- source. The purpose of screening is to deter- mation to the interferogram, but affects line mine what analytes are emitted and to ob- shapes in the absorbance spectrum (and pos- tain information about important sample sibly analytical results). characteristics such as moisture, tempera- 3.16 Reference CTS. Calibration Transfer ture, and interferences. Screening results are Standard spectra that were collected with semi-quantitative (estimated concentra- reference spectra. tions) or qualitative (identification only). 3.17 CTS Standard. CTS spectrum produced Various optical and sampling configurations by applying a de-resolution procedure to a may be used. Sample conditioning systems reference CTS. may be evaluated for their effectiveness in 3.18 Test CTS. CTS spectra collected at the removing interferences. It is unnecessary to sampling resolution using the same optical perform a complete run under any set of configuration as for sample spectra. Test sampling conditions. Spiking is not nec- spectra help verify the resolution, tempera- essary, but spiking can be a useful screening ture and path length of the FTIR system. tool for evaluating the sampling system, es- 3.19 RMSD. Root Mean Square Difference, pecially if a reactive or soluble analyte is defined in EPA FTIR Protocol, appendix A. used for the spike. 3.20 Sensitivity. The noise-limited com- 3.28 Emissions Test. An FTIR emissions test pound-dependent detection limit for the is performed according specific sampling and FTIR system configuration. This is esti- analytical procedures. These procedures, for mated by the MAU. It depends on the RMSD the target analytes and the source, are based in an analytical region of a zero absorbance on previous screening and validation results. line. Emission results are quantitative. A QA 3.21 Quantitation Limit. The lower limit of spike (sections 8.6.2 and 9.2 of this method) is detection for the FTIR system configuration performed under each set of sampling condi- in the sample spectra. This is estimated by tions using a representative analyte. Flow, mathematically subtracting scaled reference gas temperature and diluent data are re- spectra of analytes and interferences from corded concurrently with the FTIR measure- sample spectra, then measuring the RMSD in ments to provide mass emission rates for de- an analytical region of the subtracted spec- tected compounds. trum. Since the noise in subtracted sample 3.29 Surrogate. A surrogate is a compound spectra may be much greater than in a zero that is used in a QA spike procedure (section absorbance spectrum, the quantitation limit 8.6.2 of this method) to represent other com- is generally much higher than the sensi- pounds. The chemical and physical prop- tivity. Removing spectral interferences from erties of a surrogate shall be similar to the the sample or improving the spectral sub- compounds it is chosen to represent. Under traction can lower the quantitation limit to- given sampling conditions, usually a single ward (but not below) the sensitivity. sampling factor is of primary concern for 3.22 Independent Sample. A unique volume measuring the target analytes: for example, of sample gas; there is no mixing of gas be- the surrogate spike results can be represent- tween two consecutive independent samples. ative for analytes that are more reactive, In continuous sampling two independent more soluble, have a lower absorptivity, or samples are separated by at least 5 cell vol- have a lower vapor pressure than the surro- umes. The interval between independent gate itself. measurements depends on the cell volume and the sample flow rate (through the cell). 4.0 Interferences 3.23 Measurement. A single spectrum of flue Interferences are divided into two classi- gas contained in the FTIR cell. fications: analytical and sampling. 3.24 Run. A run consists of a series of meas- 4.1 Analytical Interferences. An analytical urements. At a minimum a run includes 8 interference is a spectral feature that com- independent measurements spaced over 1 plicates (in extreme cases may prevent) the hour. analysis of an analyte. Analytical inter- 3.25 Validation. Validation of FTIR meas- ferences are classified as background or spec- urements is described in sections 13.0 tral interference. through 13.4 of this method. Validation is 4.1.1 Background Interference. This results used to verify the test procedures for meas- from a change in throughput relative to the uring specific analytes at a source. Valida- single beam background. It is corrected by tion provides proof that the method works collecting a new background and proceeding under certain test conditions. with the test. In severe instances the cause 3.26 Validation Run. A validation run con- must be identified and corrected. Potential sists of at least 24 measurements of inde- causes include: (1) Deposits on reflective sur- pendent samples. Half of the samples are faces or transmitting windows, (2) changes in

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detector sensitivity, (3) a change in the in- tem under maximum vacuum and, again, frared source output, or (4) failure in the in- with the system at greater than ambient strument electronics. In routine sampling pressure.) Refer to section 8.2 of this method throughput may degrade over several hours. for leak check procedures. This method does Periodically a new background must be col- not address all of the potential safety risks lected, but no other corrective action will be associated with its use. Anyone performing required. this method must follow safety and health 4.1.2 Spectral Interference. This results from practices consistent with applicable legal re- the presence of interfering compound(s) quirements and with prudent practice for (interferant) in the sample. Interferant spec- each application. tral features overlap analyte spectral features. Any compound with an infrared spec- 6.0 Equipment and Supplies trum, including analytes, can potentially be an interferant. The Protocol measures ab- NOTE: Mention of trade names or specific sorbance band overlap in each analytical re- products does not constitute endorsement by gion to determine if potential interferants the Environmental Protection Agency. shall be classified as known interferants The equipment and supplies are based on (FTIR Protocol, section 4.9 and appendix B). the schematic of a sampling system shown in Water vapor and CO2 are common spectral Figure 1. Either the batch or continuous interferants. Both of these compounds have sampling procedures may be used with this strong infrared spectra and are present in sampling system. Alternative sampling con- many sample matrices at high concentra- figurations may also be used, provided that tions relative to analytes. The extent of in- the data quality objectives are met as deter- terference depends on the (1) interferant con- mined in the post-analysis evaluation. Other centration, (2) analyte concentration, and (3) equipment or supplies may be necessary, de- the degree of band overlap. Choosing an al- pending on the design of the sampling sys- ternate analytical region can minimize or tem or the specific target analytes. avoid the spectral interference. For example, 6.1 Sampling Probe. Glass, stainless steel, or CO2 interferes with the analysis of the 670 other appropriate material of sufficient cm¥1 benzene band. However, benzene can length and physical integrity to sustain ¥ also be measured near 3000 cm 1 (with less heating, prevent adsorption of analytes, and sensitivity). to transport analytes to the infrared gas 4.2 Sampling System Interferences. These pre- cell. Special materials or configurations may vent analytes from reaching the instrument. be required in some applications. For in- The analyte spike procedure is designed to stance, high stack sample temperatures may measure sampling system interference, if require special steel or cooling the probe. any. For very high moisture sources it may be de- 4.2.1 Temperature. A temperature that is sirable to use a dilution probe. too low causes condensation of analytes or 6.2 Particulate Filters. A glass wool plug (op- water vapor. The materials of the sampling tional) inserted at the probe tip (for large system and the FTIR gas cell usually set the particulate removal) and a filter (required) upper limit of temperature. 4.2.2 Reactive Species. Anything that reacts rated for 99 percent removal efficiency at 1- with analytes. Some analytes, like formalde- micron (e.g., Balston’’) connected at the out- hyde, polymerize at lower temperatures. let of the heated probe. 4.2.3 Materials. Poor choice of material for 6.3 Sampling Line/Heating System. Heated probe, or sampling line may remove some (sufficient to prevent condensation) stainless analytes. For example, HF reacts with glass steel, polytetrafluoroethane, or other mate- components. rial inert to the analytes. 4.2.4 Moisture. In addition to being a spec- 6.4 Gas Distribution Manifold. A heated tral interferant, condensed moisture re- manifold allowing the operator to control moves soluble compounds. flows of gas standards and samples directly to the FTIR system or through sample con- 5.0 Safety ditioning systems. Usually includes heated The hazards of performing this method are flow meter, heated valve for selecting and those associated with any stack sampling sending sample to the analyzer, and a by- method and the same precautions shall be pass vent. This is typically constructed of followed. Many HAPs are suspected carcino- stainless steel tubing and fittings, and high- gens or present other serious health risks. temperature valves. Exposure to these compounds should be 6.5 Stainless Steel Tubing. Type 316, appro- avoided in all circumstances. For instruc- priate diameter (e.g., 3⁄8 in.) and length for tions on the safe handling of any particular heated connections. Higher grade stainless compound, refer to its material safety data may be desirable in some applications. sheet. When using analyte standards, always 6.6 Calibration/Analyte Spike Assembly. A ensure that gases are properly vented and three way valve assembly (or equivalent) to that the gas handling system is leak free. introduce analyte or surrogate spikes into (Always perform a leak check with the sys- the sampling system at the outlet of the

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probe upstream of the out-of-stack particu- lution is to lower the sensitivity of the FTIR late filter and the FTIR analytical system. system by decreasing the cell path length, or 6.7 Mass Flow Meter (MFM). These are used to use a short-path cell in conjunction with for measuring analyte spike flow. The MFM a long path cell to measure more than one shall be calibrated in the range of 0 to 5 L/ concentration range. min and be accurate to ±2 percent (or better) of the flow meter span. 7.0 Reagents and Standards 6.8 Gas Regulators. Appropriate for individual gas standards. 7.1 Analyte(s) and Tracer Gas. Obtain a cer- 6.9 Polytetrafluoroethane Tubing. Diameter tified gas cylinder mixture containing all of the analyte(s) at concentrations within ±2 (e.g., 3⁄8 in.) and length suitable to connect cylinder regulators to gas standard manifold. percent of the emission source levels (ex- 6.10 Sample Pump. A leak-free pump (e.g., pressed in ppm-meter/K). If practical, the KNF TM), with by-pass valve, capable of pro- analyte standard cylinder shall also contain ducing a sample flow rate of at least 10 L/ the tracer gas at a concentration which gives min through 100 ft of sample line. If the a measurable absorbance at a dilution factor pump is positioned upstream of the distribu- of at least 10:1. Two ppm SF6 is sufficient for tion manifold and FTIR system, use a heated a path length of 22 meters at 250 °F. pump that is constructed from materials 7.2 Calibration Transfer Standard(s). Select non-reactive to the analytes. If the pump is the calibration transfer standards (CTS) ac- located downstream of the FTIR system, the cording to section 4.5 of the FTIR Protocol. gas cell sample pressure will be lower than Obtain a National Institute of Standards and ambient pressure and it must be recorded at Technology (NIST) traceable gravimetric regular intervals. standard of the CTS (±2 percent). 6.11 Gas Sample Manifold. Secondary mani- 7.3 Reference Spectra. Obtain reference spec- fold to control sample flow at the inlet to tra for each analyte, interferant, surrogate, the FTIR manifold. This is optional, but in- CTS, and tracer. If EPA reference spectra are cludes a by-pass vent and heated rotameter. not available, use reference spectra prepared 6.12 Rotameter. A 0 to 20 L/min rotameter. according to procedures in section 4.6 of the This meter need not be calibrated. EPA FTIR Protocol. 6.13 FTIR Analytical System. Spectrometer and detector, capable of measuring the 8.0 Sampling and Analysis Procedure analytes to the chosen detection limit. The system shall include a personal computer Three types of testing can be performed: (1) with compatible software allowing auto- Screening, (2) emissions test, and (3) valida- mated collection of spectra. tion. Each is defined in section 3 of this 6.14 FTIR Cell Pump. Required for the batch method. Determine the purpose(s) of the sampling technique, capable of evacuating FTIR test. Test requirements include: (a) the FTIR cell volume within 2 minutes. The AUi, DLi, overall fractional uncertainty, pumping speed shall allow the operator to OFUi, maximum expected concentration obtain 8 sample spectra in 1 hour. (CMAXi), and tAN for each, (b) potential 6.15 Absolute Pressure Gauge. Capable of interferants, (c) sampling system factors, measuring pressure from 0 to 1000 mmHg to e.g., minimum absolute cell pressure, (Pmin), within ±2.5 mmHg (e.g., Baratron TM). FTIR cell volume (VSS), estimated sample ab- 6.16 Temperature Gauge. Capable of meas- sorption pathlength, LS′, estimated sample uring the cell temperature to within ±2 °C. pressure, PS′, TS′, signal integration time 6.17 Sample Conditioning. One option is a (tSS), minimum instrumental linewidth, MIL, condenser system, which is used for moisture fractional error, and (d) analytical regions, removal. This can be helpful in the measure- e.g., m = 1 to M, lower wavenumber position, ment of some analytes. Other sample condi- FLm, center wavenumber position, FCm, and tioning procedures may be devised for the re- upper wavenumber position, FUm, plus moval of moisture or other interfering spe- interferants, upper wavenumber position of cies. the CTS absorption band, FFUm, lower 6.17.1 The analyte spike procedure of sec- wavenumber position of the CTS absorption tion 9.2 of this method, the QA spike proce- band, FFLm, wavenumber range FNU to FNL. dure of section 8.6.2 of this method, and the If necessary, sample and acquire an initial validation procedure of section 13 of this spectrum. From analysis of this preliminary method demonstrate whether the sample spectrum determine a suitable operational conditioning affects analyte concentrations. path length. Set up the sampling train as Alternatively, measurements can be made shown in Figure 1 or use an appropriate al- with two parallel FTIR systems; one meas- ternative configuration. Sections 8.1 through uring conditioned sample, the other meas- 8.11 of this method provide guidance on pre- uring unconditioned sample. test calculations in the EPA protocol, sam- 6.17.2 Another option is sample dilution. pling and analytical procedures, and post- The dilution factor measurement must be test protocol calculations. documented and accounted for in the re- 8.1 Pretest Preparations and Evaluations. ported concentrations. An alternative to di- Using the procedure in section 4.0 of the

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FTIR Protocol, determine the optimum sam- analyte, i, and each analytical region, m, de- pling system configuration for measuring pends on the RMS noise. the target analytes. Use available informa- 8.1.7 Analytical Program. See FTIR Pro- tion to make reasonable assumptions about tocol, section 4.10. Prepare computer pro- moisture content and other interferences. gram based on the chosen analytical tech- 8.1.1 Analytes. Select the required detection nique. Use as input reference spectra of all limit (DLi) and the maximum permissible an- target analytes and expected interferants. alytical uncertainty (AUi) for each analyte Reference spectra of additional compounds (labeled from 1 to i). Estimate, if possible, shall also be included in the program if their the maximum expected concentration for presence (even if transient) in the samples is each analyte, CMAXi. The expected measure- considered possible. The program output ment range is fixed by DLi and CMAXi for shall be in ppm (or ppb) and shall be cor- each analyte (i). rected for differences between the reference 8.1.2 Potential Interferants. List the poten- path length, LR, temperature, TR, and pres- tial interferants. This usually includes water sure, PR, and the conditions used for col- vapor and CO2, but may also include some lecting the sample spectra. If sampling is analytes and other compounds. performed at ambient pressure, then any 8.1.3. Optical Configuration. Choose an opti- pressure correction is usually small relative cal configuration that can measure all of the to corrections for path length and tempera- analytes within the absorbance range of .01 ture, and may be neglected. to 1.0 (this may require more than one path 8.2 Leak-Check length). Use Protocol sections 4.3 to 4.8 for 8.2.1 Sampling System. A typical FTIR ex- guidance in choosing a configuration and tractive sampling train is shown in Figure 1. measuring CTS. Leak check from the probe tip to pump out- 8.1.4 Fractional Reproducibility Uncertainty let as follows: Connect a 0-to 250-mL/min (FRUi). The FRU is determined for each rate meter (rotameter or bubble meter) to analyte by comparing CTS spectra taken be- the outlet of the pump. Close off the inlet to fore and after the reference spectra were the probe, and record the leak rate. The leak measured. The EPA para-xylene reference rate shall be ≤200 mL/min. spectra were collected on 10/31/91 and 11/01/91 8.2.2 Analytical System Leak check. Leak with corresponding CTS spectra ‘‘cts1031a,’’ check the FTIR cell under vacuum and under and ‘‘cts1101b.’’ The CTS spectra are used to pressure (greater than ambient). Leak check estimate the reproducibility (FRU) in the connecting tubing and inlet manifold under system that was used to collect the ref- pressure. erences. The FRU must be

Where: 8.3 Detector Linearity. Once an optical con- 50 = 100% divided by the leak-check time of figuration is chosen, use one of the proce- 2 minutes. dures of sections 8.3.1 through 8.3.3 to verify 8.2.2.5 Leak volumes in excess of 4 percent that the detector response is linear. If the detector response is not linear, decrease the of the FTIR system volume VSS are unacceptable. aperture, or attenuate the infrared beam.

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After a change in the instrument configura- 8.5.1 Interference Spectra. If possible, collect tion perform a linearity check until it is spectra of known and suspected major inter- demonstrated that the detector response is ferences using the same optical system that linear. will be used in the field measurements. This 8.3.1 Vary the power incident on the detec- can be done on-site or earlier. A number of tor by modifying the aperture setting. Meas- gases, e.g. CO2, SO2, CO, NH3, are readily ure the background and CTS at three instru- available from cylinder gas suppliers. ment aperture settings: (1) at the aperture 8.5.2 Water vapor spectra can be prepared setting to be used in the testing, (2) at one by the following procedure. Fill a sample half this aperture and (3) at twice the pro- tube with distilled water. Evacuate above posed testing aperture. Compare the three the sample and remove dissolved gasses by CTS spectra. CTS band areas shall agree to alternately freezing and thawing the water within the uncertainty of the cylinder stand- while evacuating. Allow water vapor into the ard and the RMSD noise in the system. If FTIR cell, then dilute to atmospheric pres- test aperture is the maximum aperture, col- sure with nitrogen or dry air. If quantitative lect CTS spectrum at maximum aperture, water spectra are required, follow the ref- then close the aperture to reduce the IR erence spectrum procedure for neat samples throughput by half. Collect a second back- (protocol, section 4.6). Often, interference ground and CTS at the smaller aperture set- spectra need not be quantitative, but for best ting and compare the spectra again. results the absorbance must be comparable 8.3.2 Use neutral density filters to attenu- to the interference absorbance in the sample ate the infrared beam. Set up the FTIR sys- spectra. tem as it will be used in the test measure- 8.6 Pre-Test Calibrations ments. Collect a CTS spectrum. Use a neu- 8.6.1 Calibration Transfer Standard. Evac- tral density filter to attenuate the infrared ≤ beam (either immediately after the source or uate the gas cell to 5 mmHg absolute pressure, and fill the FTIR cell to atmospheric the interferometer) to approximately 1⁄2 its original intensity. Collect a second CTS pressure with the CTS gas. Alternatively, spectrum. Use another filter to attenuate purge the cell with 10 cell volumes of CTS gas. (If purge is used, verify that the CTS the infrared beam to approximately 1⁄4 its original intensity. Collect a third back- concentration in the cell is stable by col- ground and CTS spectrum. Compare the CTS lecting two spectra 2 minutes apart as the spectra. CTS band areas shall agree to with- CTS gas continues to flow. If the absorbance in the uncertainty of the cylinder standard in the second spectrum is no greater than in and the RMSD noise in the system. the first, within the uncertainty of the gas 8.3.3 Observe the single beam instrument standard, then this can be used as the CTS response in a frequency region where the de- spectrum.) Record the spectrum. tector response is known to be zero. Verify 8.6.2 QA Spike. This procedure assumes that the detector response is ‘‘flat’’ and that the method has been validated for at equal to zero in these regions. least some of the target analytes at the 8.4 Data Storage Requirements. All field test source. For emissions testing perform a QA spectra shall be stored on a computer disk spike. Use a certified standard, if possible, of and a second backup copy must stored on a an analyte, which has been validated at the separate disk. The stored information in- source. One analyte standard can serve as a cludes sample interferograms, processed ab- QA surrogate for other analytes which are sorbance spectra, background less reactive or less soluble than the stand- interferograms, CTS sample interferograms ard. Perform the spike procedure of section and CTS absorbance spectra. Additionally, 9.2 of this method. Record spectra of at least documentation of all sample conditions, in- three independent (section 3.22 of this meth- strument settings, and test records must be od) spiked samples. Calculate the spiked recorded on hard copy or on computer me- component of the analyte concentration. If dium. Table 1 gives a sample presentation of the average spiked concentration is within documentation. 0.7 to 1.3 times the expected concentration, 8.5 Background Spectrum. Evacuate the gas then proceed with the testing. If applicable, cell to ≤5 mmHg, and fill with dry nitrogen apply the correction factor from the Method gas to ambient pressure (or purge the cell 301 of this appendix validation test (not the with 10 volumes of dry nitrogen). Verify that result from the QA spike). no significant amounts of absorbing species 8.7 Sampling. If analyte concentrations (for example water vapor and CO2) are vary rapidly with time, continuous sampling present. Collect a background spectrum, is preferable using the smallest cell volume, using a signal averaging period equal to or fastest sampling rate and fastest spectra col- greater than the averaging period for the lection rate possible. Continuous sampling sample spectra. Assign a unique file name to requires the least operator intervention even the background spectrum. Store two copies without an automated sampling system. For of the background interferogram and proc- continuous monitoring at one location over essed single-beam spectrum on separate com- long periods, Continuous sampling is pre- puter disks (one copy is the back-up). ferred. Batch sampling and continuous static

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sampling are used for screening and per- 8.11.1 Inspect the sample spectra imme- forming test runs of finite duration. Either diately after the run to verify that the gas technique is preferred for sampling several matrix composition was close to the ex- locations in a matter of days. Batch sam- pected (assumed) gas matrix. pling gives reasonably good time resolution 8.11.2 Verify that the sampling and in- and ensures that each spectrum measures a strumental parameters were appropriate for discreet (and unique) sample volume. Contin- the conditions encountered. For example, if uous static (and continuous) sampling pro- the moisture is much greater than antici- vide a very stable background over long peri- pated, it may be necessary to use a shorter ods. Like batch sampling, continuous static path length or dilute the sample. sampling also ensures that each spectrum 8.11.3 Compare the pre- and post-test CTS measures a unique sample volume. It is es- spectra. The peak absorbance in pre- and sential that the leak check procedure under post-test CTS must be ±5 percent of the vacuum (section 8.2 of this method) is passed mean value. See appendix E of the FTIR Pro- if the batch sampling procedure is used. It is tocol. essential that the leak check procedure under positive pressure is passed if the con- 9.0 Quality Control tinuous static or continuous sampling proce- Use analyte spiking (sections 8.6.2, 9.2 and dures are used. The sampling techniques are 13.0 of this method) to verify that the sam- described in sections 8.7.1 through 8.7.2 of pling system can transport the analytes this method. from the probe to the FTIR system. 8.7.1 Batch Sampling. Evacuate the absorb- 9.1 Spike Materials. Use a certified stand- ance cell to ≤5 mmHg absolute pressure. Fill ard (accurate to ±2 percent) of the target the cell with exhaust gas to ambient pres- analyte, if one can be obtained. If a certified sure, isolate the cell, and record the spec- standard cannot be obtained, follow the pro- trum. Before taking the next sample, evac- cedures in section 4.6.2.2 of the FTIR Pro- uate the cell until no spectral evidence of tocol. sample absorption remains. Repeat this pro- 9.2 Spiking Procedure. QA spiking (section cedure to collect eight spectra of separate 8.6.2 of this method) is a calibration proce- samples in 1 hour. dure used before testing. QA spiking involves 8.7.2 Continuous Static Sampling. Purge the FTIR cell with 10 cell volumes of sample gas. following the spike procedure of sections Isolate the cell, collect the spectrum of the 9.2.1 through 9.2.3 of this method to obtain at static sample and record the pressure. Before least three spiked samples. The analyte con- measuring the next sample, purge the cell centrations in the spiked samples shall be with 10 more cell volumes of sample gas. compared to the expected spike concentra- 8.8 Sampling QA and Reporting tion to verify that the sampling/analytical 8.8.1 Sample integration times shall be system is working properly. Usually, when sufficient to achieve the required signal-to- QA spiking is used, the method has already noise ratio. Obtain an absorbance spectrum been validated at a similar source for the by filling the cell with N2. Measure the analyte in question. The QA spike dem- RMSD in each analytical region in this ab- onstrates that the validated sampling/ana- sorbance spectrum. Verify that the number lytical conditions are being duplicated. If of scans used is sufficient to achieve the tar- the QA spike fails then the sampling/analyt- get MAU. ical system shall be repaired before testing 8.8.2 Assign a unique file name to each proceeds. The method validation procedure spectrum. (section 13.0 of this method) involves a more 8.8.3 Store two copies of sample extensive use of the analyte spike procedure interferograms and processed spectra on sep- of sections 9.2.1 through 9.2.3 of this method. arate computer disks. Spectra of at least 12 independent spiked and 8.8.4 For each sample spectrum, document 12 independent unspiked samples are re- the sampling conditions, the sampling time corded. The concentration results are ana- (while the cell was being filled), the time the lyzed statistically to determine if there is a spectrum was recorded, the instrumental systematic bias in the method for measuring conditions (path length, temperature, pres- a particular analyte. If there is a systematic sure, resolution, signal integration time), bias, within the limits allowed by Method 301 and the spectral file name. Keep a hard copy of this appendix, then a correction factor of these data sheets. shall be applied to the analytical results. If 8.9 Signal Transmittance. While sampling, the systematic bias is greater than the al- monitor the signal transmittance. If signal lowed limits, this method is not valid and transmittance (relative to the background) cannot be used. changes by 5 percent or more (absorbance = 9.2.1 Introduce the spike/tracer gas at a -.02 to .02) in any analytical spectral region, constant flow rate of ≤10 percent of the total obtain a new background spectrum. sample flow, when possible. 8.10 Post-test CTS. After the sampling run, NOTE: Use the rotameter at the end of the record another CTS spectrum. sampling train to estimate the required 8.11 Post-test QA spike/tracer gas flow rate.

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Use a flow device, e.g., mass flow meter (# constant. Wait for twice the duration of the 2 percent), to monitor the spike flow rate. RT, then collect spectra of two independent Record the spike flow rate every 10 minutes. spiked gas samples. Duplicate analyses of 9.2.2 Determine the response time (RT) of the spiked concentration shall be within 5 the system by continuously collecting spec- percent of the mean of the two measure- tra of the spiked effluent until the spectrum ments. of the spiked component is constant for 5 9.2.3 Calculate the dilution ratio using minutes. The RT is the interval from the the tracer gas as follows: first measurement until the spike becomes

DF = Dilution factor of the spike gas; this absolute pressure (Pm); and the cell final ab- value shall be ≥10. solute temperature (Tf) and absolute pres- SF6(dir) = SF6 (or tracer gas) concentration sure (Pf). Calculate the FTIR cell volume measured directly in undiluted spike gas. VSS, including that of the connecting tub- SF6(spk) = Diluted SF6 (or tracer gas) con- ing, as follows: centration measured in a spiked sample. Spike = Concentration of the analyte in dir Pm the spike standard measured by filling Vm the FTIR cell directly. T V = m (5) CS = Expected concentration of the spiked SS ⎡ ⎤ samples. Pf Pi Unspike = Native concentration of analytes ⎢ − ⎥ in unspiked samples. ⎣Tf Ti ⎦ 10.0 Calibration and Standardization 11.0 Data Analysis and Calculations 10.1 Signal-to-Noise Ratio (S/N). The RMSD in the noise must be less than one tenth of Analyte concentrations shall be measured the minimum analyte peak absorbance in using reference spectra from the EPA FTIR each analytical region. For example if the spectral library. When EPA library spectra minimum peak absorbance is 0.01 at the re- are not available, the procedures in section quired DL, then RMSD measured over the 4.6 of the Protocol shall be followed to pre- entire analytical region must be ≤0.001. pare reference spectra of all the target 10.2 Absorbance Path length. Verify the ab- analytes. sorbance path length by comparing reference 11.1 Spectral De-resolution. Reference spec- CTS spectra to test CTS spectra. See appen- tra can be converted to lower resolution dix E of the FTIR Protocol. standard spectra (section 3.3 of this method) 10.3 Instrument Resolution. Measure the by truncating the original reference sample line width of appropriate test CTS band(s) to and background interferograms. Appendix K verify instrument resolution. Alternatively, of the FTIR Protocol gives specific compare CTS spectra to a reference CTS deresolution procedures. Deresolved spectra spectrum, if available, measured at the shall be transformed using the same nominal resolution. apodization function and level of zero filling 10.4 Apodization Function.In transforming as the sample spectra. Additionally, pre-test the sample interferograms to absorbance FTIR protocol calculations (e.g., FRU, MAU, spectra use the same apodization function FCU) shall be performed using the de-re- that was used in transforming the reference solved standard spectra. spectra. 11.2 Data Analysis. Various analytical pro- 10.5 FTIR Cell Volume. Evacuate the cell grams are available for relating sample ab- to ≤5 mmHg. Measure the initial absolute sorbance to a concentration standard. Cal- temperature (Ti) and absolute pressure (Pi). culated concentrations shall be verified by Connect a wet test meter (or a calibrated dry analyzing residual baselines after mathe- gas meter), and slowly draw room air into matically subtracting scaled reference spec- the cell. Measure the meter volume (Vm), tra from the sample spectra. A full descrip- meter absolute temperature (Tm), and meter tion of the data analysis and calculations is 822

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contained in the FTIR Protocol (sections 4.0, practical, it is preferable to measure sample 5.0, 6.0 and appendices). Correct the cal- temperature directly, by inserting a thermo- culated concentrations in the sample spectra couple into the cell chamber instead of mon- for differences in absorption path length and itoring the cell outer wall temperature. temperature between the reference and sam- 12.2.4 Pressure. Accuracy depends on the ple spectra using equation 6, accuracy of the barometer, but fluctuations in pressure throughout a day may be as ⎛ L ⎞ ⎛ T ⎞ ⎛ P ⎞ much as 2.5 percent due to weather vari- C = ⎜ r ⎟ ⎜ s ⎟ ⎜ r ⎟C (6) ations. corr ⎝ ⎠ ⎝ ⎠ ⎝ ⎠ calc Ls Tr Ps 13.0 Method Validation Procedure Where: This validation procedure, which is based Ccorr = Concentration, corrected for path on EPA Method 301 (40 CFR part 63, appendix length. (A), may be used to validate this method for Ccalc = Concentration, initial calculation the analytes in a gas matrix. Validation at (output of the analytical program de- one source may also apply to another type of signed for the compound). source, if it can be shown that the exhaust Lr = Reference spectra path length. gas characteristics are similar at both Ls = Sample spectra path length. sources. Ts = Absolute temperature of the sample gas, 13.1 Section 6.0 of Method 301 (40 CFR part K. 63, appendix A), the Analyte Spike proce- Tr = Absolute gas temperature of reference dure, is used with these modifications. The spectra, K. statistical analysis of the results follows section 12.0 of EPA Method 301. Section 3 of this Ps = Sample cell pressure. method defines terms that are not defined in Pr = Reference spectrum sample pressure. Method 301. 12.0 Method Performance 13.1.1 The analyte spike is performed dynamically. This means the spike flow is con- 12.1 Spectral Quality. Refer to the FTIR tinuous and constant as spiked samples are Protocol appendices for analytical require- measured. ments, evaluation of data quality, and anal- 13.1.2 The spike gas is introduced at the ysis of uncertainty. back of the sample probe. 12.2 Sampling QA/QC. The analyte spike 13.1.3 Spiked effluent is carried through procedure of section 9 of this method, the QA all sampling components downstream of the spike of section 8.6.2 of this method, and the probe. validation procedure of section 13 of this 13.1.4 A single FTIR system (or more) method are used to evaluate the performance may be used to collect and analyze spectra of the sampling system and to quantify sam- (not quadruplicate integrated sampling pling system effects, if any, on the measured trains). concentrations. This method is self-vali- 13.1.5 All of the validation measurements dating provided that the results meet the are performed sequentially in a single ‘‘run’’ performance requirement of the QA spike in (section 3.26 of this method). sections 9.0 and 8.6.2 of this method and re- 13.1.6 The measurements analyzed statis- sults from a previous method validation tically are each independent (section 3.22 of study support the use of this method in the this method). application. Several factors can contribute 13.1.7 A validation data set can consist of to uncertainty in the measurement of spiked more than 12 spiked and 12 unspiked meas- samples. Factors which can be controlled to urements. provide better accuracy in the spiking proce- 13.2 Batch Sampling. The procedure in sec- dure are listed in sections 12.2.1 through tions 13.2.1 through 13.2.2 may be used for 12.2.4 of this method. stable processes. If process emissions are 12.2.1 Flow meter. An accurate mass flow highly variable, the procedure in section meter is accurate to ±1 percent of its span. If 13.2.3 shall be used. a flow of 1 L/min is monitored with such a 13.2.1 With a single FTIR instrument and MFM, which is calibrated in the range of 0– sampling system, begin by collecting spectra 5 L/min, the flow measurement has an uncer- of two unspiked samples. Introduce the spike tainty of 5 percent. This may be improved by flow into the sampling system and allow 10 re-calibrating the meter at the specific flow cell volumes to purge the sampling system rate to be used. and FTIR cell. Collect spectra of two spiked 12.2.2 Calibration gas. Usually the calibra- samples. Turn off the spike and allow 10 cell tion standard is certified to within ±2 per- volumes of unspiked sample to purge the cent. With reactive analytes, such as HCl, FTIR cell. Repeat this procedure until the 24 the certified accuracy in a commercially (or more) samples are collected. available standard may be no better than ±5 13.2.2 In batch sampling, collect spectra of percent. 24 distinct samples. (Each distinct sample 12.2.3 Temperature. Temperature measure- consists of filling the cell to ambient pres- ments of the cell shall be quite accurate. If sure after the cell has been evacuated.)

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13.2.3 Alternatively, a separate probe as- correction factor (CF). Analytical results of sembly, line, and sample pump can be used the test method are multiplied by the correc- for spiked sample. Verify and document that tion factor, if 0.7 ≤CF ≤1.3. If is determined sampling conditions are the same in both the that the bias is significant and CF >±30 per- spiked and the unspiked sampling systems. cent, then the test method is considered to This can be done by wrapping both sample ‘‘not valid.’’ lines in the same heated bundle. Keep the 13.4.3 If measurements do not pass valida- same flow rate in both sample lines. Measure tion, evaluate the sampling system, instru- samples in sequence in pairs. After two ment configuration, and analytical system spiked samples are measured, evacuate the to determine if improper set-up or a mal- FTIR cell, and turn the manifold valve so function was the cause. If so, repair the sys- that spiked sample flows to the FTIR cell. tem and repeat the validation. Allow the connecting line from the manifold to the FTIR cell to purge thoroughly (the 14.0 Pollution Prevention time depends on the line length and flow The extracted sample gas is vented outside rate). Collect a pair of spiked samples. Re- the enclosure containing the FTIR system peat the procedure until at least 24 measure- and gas manifold after the analysis. In typ- ments are completed. ical method applications the vented sample 13.3 Simultaneous Measurements With volume is a small fraction of the source volu- Two FTIR Systems. If unspiked effluent con- metric flow and its composition is identical centrations of the target analyte(s) vary sig- to that emitted from the source. When nificantly with time, it may be desirable to analyte spiking is used, spiked pollutants perform synchronized measurements of are vented with the extracted sample gas. spiked and unspiked sample. Use two FTIR Approximately 1.6 × 10¥4 to 3.2 × 10¥4 lbs of systems, each with its own cell and sampling a single HAP may be vented to the atmos- system to perform simultaneous spiked and phere in a typical validation run of 3 hours. unspiked measurements. The optical con- (This assumes a molar mass of 50 to 100 g, figurations shall be similar, if possible. The spike rate of 1.0 L/min, and a standard con- sampling configurations shall be the same. centration of 100 ppm). Minimize emissions One sampling system and FTIR analyzer by keeping the spike flow off when not in shall be used to measure spiked effluent. The use. other sampling system and FTIR analyzer shall be used to measure unspiked flue gas. 15.0 Waste Management Both systems shall use the same sampling procedure (i.e., batch or continuous). Small volumes of laboratory gas standards 13.3.1 If batch sampling is used, syn- can be vented through a laboratory hood. chronize the cell evacuation, cell filling, and Neat samples must be packed and disposed collection of spectra. Fill both cells at the according to applicable regulations. Surplus same rate (in cell volumes per unit time). materials may be returned to supplier for 13.3.2 If continuous sampling is used, ad- disposal. just the sample flow through each gas cell so 16.0 References that the same number of cell volumes pass through each cell in a given time (i.e. TC1 = 1. ‘‘Field Validation Test Using Fourier TC2). Transform Infrared (FTIR) Spectrometry To 13.4 Statistical Treatment. The statistical Measure Formaldehyde, Phenol and Meth- procedure of EPA Method 301 of this appen- anol at a Wool Fiberglass Production Facil- dix, section 12.0 is used to evaluate the bias ity.’’ Draft. U.S. Environmental Protection and precision. For FTIR testing a validation Agency Report, EPA Contract No. 68D20163, ‘‘run’’ is defined as spectra of 24 independent Work Assignment I–32, September 1994. samples, 12 of which are spiked with the 2. ‘‘FTIR Method Validation at a Coal- analyte(s) and 12 of which are not spiked. Fired Boiler’’. Prepared for U.S. Environ- 13.4.1 Bias. Determine the bias (defined by mental Protection Agency, Research Tri- EPA Method 301 of this appendix, section angle Park, NC. Publication No.: EPA–454/ 12.1.1) using equation 7: R95–004, NTIS No.: PB95–193199. July, 1993. B=S ¥ CS 3. ‘‘Method 301—Field Validation of Pollut- m ant Measurement Methods from Various Where: Waste Media,’’ 40 CFR part 63, appendix A. B = Bias at spike level. 4. ‘‘Molecular Vibrations; The Theory of Sm = Mean concentration of the analyte Infrared and Raman Vibrational Spectra,’’ E. spiked samples. Bright Wilson, J.C. Decius, and P.C. Cross, CS = Expected concentration of the spiked Dover Publications, Inc., 1980. For a less in- samples. tensive treatment of molecular rotational- 13.4.2 Correction Factor. Use section 6.3.2.2 vibrational spectra see, for example, ‘‘Phys- of Method 301 of this appendix to evaluate ical Chemistry,’’ G.M. Barrow, chapters 12, the statistical significance of the bias. If it is 13, and 14, McGraw Hill, Inc., 1979. determined that the bias is significant, then 5. ‘‘Fourier Transform Infrared Spectrom- use section 6.3.3 of Method 301 to calculate a etry,’’ Peter R. Griffiths and James de

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Haseth, Chemical Analysis, 83, 16–25,(1986), 7. ‘‘Multivariate Least-Squares Methods P.J. Elving, J.;D. Winefordner and I.M. Applied to the Quantitative Spectral Anal- Kolthoff (ed.), John Wiley and Sons. ysis of Multicomponent Mixtures,’’ Applied 6. ‘‘Computer-Assisted Quantitative Infra- Spectroscopy, 39(10), 73–84, 1985. red Spectroscopy,’’ Gregory L. McClure (ed.), ASTM Special Publication 934 (ASTM), 1987.

TABLE 1—EXAMPLE PRESENTATION OF SAMPLING DOCUMENTATION

Sample time Spectrum file name Background file name Sample conditioning Process condition

Sample time Spectrum file Interferogram Resolution Scans Apodization Gain CTS Spectrum

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ADDENDUM TO TEST METHOD 320—PROTOCOL 2.0 Applicability and Analytical Principle FOR THE USE OF EXTRACTIVE FOURIER 2.1 Applicability. This Protocol applies to TRANSFORM INFRARED (FTIR) SPECTROM- the determination of compound-specific con- ETRY FOR THE ANALYSES OF GASEOUS EMIS- centrations in single- and multiple-compo- SIONS FROM STATIONARY SOURCES nent gas phase samples using double-beam 1.0 Introduction absorption spectroscopy in the mid-infrared band. It does not specifically address other The purpose of this addendum is to set gen- FTIR applications, such as single-beam spec- eral guidelines for the use of modern FTIR troscopy, analysis of open-path (non-en- spectroscopic methods for the analysis of gas closed) samples, and continuous measure- samples extracted from the effluent of sta- ment techniques. If multiple spectrometers, tionary emission sources. This addendum absorption cells, or instrumental linewidths outlines techniques for developing and evalu- are used in such analyses, each distinct operating such methods and sets basic require- ational configuration of the system must be ments for reporting and quality assurance evaluated separately according to this Pro- procedures. tocol. 1.1 Nomenclature 2.2 Analytical Principle 1.1.1 Appendix A to this addendum lists 2.2.1 In the mid-infrared band, most mol- definitions of the symbols and terms used in ecules exhibit characteristic gas phase ab- this Protocol, many of which have been sorption spectra that may be recorded by taken directly from American Society for FTIR systems. Such systems consist of a Testing and Materials (ASTM) publication E source of mid-infrared radiation, an inter- 131–90a, entitled ‘‘Terminology Relating to ferometer, an enclosed sample cell of known Molecular Spectroscopy.’’ absorption pathlength, an infrared detector, 1.1.2 Except in the case of background optical elements for the transfer of infrared spectra or where otherwise noted, the term radiation between components, and gas flow ‘‘spectrum’’ refers to a double-beam spec- control and measurement components. Ad- trum in units of absorbance vs. wavenumber junct and integral computer systems are (cm¥1). used for controlling the instrument, proc- 1.1.3 The term ‘‘Study’’ in this addendum essing the signal, and for performing both refers to a publication that has been sub- Fourier transforms and quantitative anal- jected to EPA- or peer-review. yses of spectral data.

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2.2.2 The absorption spectra of pure gases factors define the fundamental limitations of and of mixtures of gases are described by a FTIR measurements for a given system con- linear absorbance theory referred to as figuration. These limitations may be esti- Beer’s Law. Using this law, modern FTIR mated from evaluations of the system before systems use computerized analytical pro- samples are available. For example, the de- grams to quantify compounds by comparing tection limit for the absorbing compound the absorption spectra of known (reference) under a given set of conditions may be esti- gas samples to the absorption spectrum of mated from the system noise level and the the sample gas. Some standard mathe- strength of a particular absorption band. matical techniques used for comparisons are Similarly, the accuracy of measurements classical least squares, inverse least squares, may be estimated from the analysis of the cross-correlation, factor analysis, and par- reference spectra. tial least squares. Reference A describes sev- 3.3.2 Sample-Dependent Factors. Examples eral of these techniques, as well as addi- are spectral interferants (e.g., water vapor tional techniques, such as differentiation and CO2) or the overlap of spectral features methods, linear baseline corrections, and of different compounds and contamination non-linear absorbance corrections. deposits on reflective surfaces or transmitting windows. To maximize the effectiveness 3.0 General Principles of Protocol of the mathematical techniques used in spec- Requirements tral analysis, identification of interferants The characteristics that distinguish FTIR (a standard initial step) and analysis of sam- systems from gas analyzers used in instru- ples (includes effect of other analytical er- mental gas analysis methods (e.g., Methods rors) are necessary. Thus, the Protocol re- 6C and 7E of appendix A to part 60 of this quires post-analysis calculation of measure- chapter) are: (1) Computers are necessary to ment concentration uncertainties for the de- obtain and analyze data; (2) chemical con- tection of these potential sources of meas- centrations can be quantified using pre- urement error. viously recorded infrared reference spectra; 4.0 Pre-Test Preparations and Evaluations and (3) analytical assumptions and results, including possible effects of interfering com- Before testing, demonstrate the suitability pounds, can be evaluated after the quan- of FTIR spectrometry for the desired appli- titative analysis. The following general prin- cation according to the procedures of this ciples and requirements of this Protocol are section. based on these characteristics. 4.1 Identify Test Requirements. Identify and 3.1 Verifiability and Reproducibility of Re- record the test requirements described in sults. Store all data and document data anal- sections 4.1.1 through 4.1.4 of this addendum. ysis techniques sufficient to allow an inde- These values set the desired or required pendent agent to reproduce the analytical goals of the proposed analysis; the descrip- results from the raw interferometric data. tion of methods for determining whether 3.2 Transfer of Reference Spectra. To deter- these goals are actually met during the anal- mine whether reference spectra recorded ysis comprises the majority of this Protocol. under one set of conditions (e.g., optical 4.1.1 Analytes (specific chemical species) bench, instrumental linewidth, absorption of interest. Label the analytes from i = 1 to pathlength, detector performance, pressure, I. and temperature) can be used to analyze 4.1.2 Analytical uncertainty limit (AUi). sample spectra taken under a different set of The AUi is the maximum permissible frac- th conditions, quantitatively compare ‘‘cali- tional uncertainty of analysis for the i bration transfer standards’’ (CTS) and ref- analyte concentration, expressed as a frac- erence spectra as described in this Protocol. tion of the analyte concentration in the sample. NOTE: The CTS may, but need not, include 4.1.3 Required detection limit for each analytes of interest). To effect this, record analyte (DLi, ppm). The detection limit is the absorption spectra of the CTS (a) imme- the lowest concentration of an analyte for diately before and immediately after record- which its overall fractional uncertainty ing reference spectra and (b) immediately (OFU ) is required to be less than its analyt- after recording sample spectra. i ical uncertainty limit (AUi). 3.3 Evaluation of FTIR Analyses. The appli- 4.1.4 Maximum expected concentration of cability, accuracy, and precision of FTIR each analyte (CMAXi, ppm). measurements are influenced by a number of 4.2 Identify Potential Interferants. Consid- interrelated factors, which may be divided ering the chemistry of the process or results into two classes: of previous studies, identify potential 3.3.1 Sample-Independent Factors. Exam- interferants, i.e., the major effluent con- ples are system configuration and perform- stituents and any relatively minor effluent ance (e.g., detector sensitivity and infrared constituents that possess either strong ab- source output), quality and applicability of sorption characteristics or strong structural reference absorption spectra, and type of similarities to any analyte of interest. Label mathematical analyses of the spectra. These them 1 through Nj, where the subscript ‘‘j’’ 827

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pertains to potential interferants. Estimate 4.5.4 For each analytical region, specify the concentrations of these compounds in the upper and lower wavenumber positions the effluent (CPOTj, ppm). (FFUm and FFLm, respectively) that bracket 4.3 Select and Evaluate the Sampling Sys- the CTS absorption band or bands for the as- tem. Considering the source, e.g., tempera- sociated analytical region. Specify the ture and pressure profiles, moisture content, wavenumber range, FNU to FNL, containing analyte characteristics, and particulate con- the absorption band that meets the criterion centration), select the equipment for ex- of section 4.5.3 of this addendum. tracting gas samples. Recommended are a 4.5.5 Associate, whenever possible, a sin- particulate filter, heating system to main- gle set of CTS gas cylinders with a set of ref- tain sample temperature above the dew point erence spectra. Replacement CTS gas cyl- for all sample constituents at all points inders shall contain the same compounds at within the sampling system (including the concentrations within 5 percent of that of filter), and sample conditioning system (e.g., the original CTS cylinders; the entire ab- coolers, water-permeable membranes that sorption spectra (not individual spectral seg- remove water or other compounds from the ments) of the replacement gas shall be scaled sample, and dilution devices) to remove spec- by a factor between 0.95 and 1.05 to match tral interferants or to protect the sampling the original CTS spectra. and analytical components. Determine the 4.6 Prepare Reference Spectra minimum absolute sample system pressure NOTE: Reference spectra are available in a (Pmin, mmHg) and the infrared absorption cell permanent soft copy from the EPA spectral volume (VSS, liter). Select the techniques library on the EMTIC (Emission Measure- and/or equipment for the measurement of ment Technical Information Center) com- sample pressures and temperatures. puter bulletin board; they may be used if ap- 4.4 Select Spectroscopic System. Select a plicable. spectroscopic configuration for the applica- 4.6.1 Select the reference absorption tion. Approximate the absorption pathlength pathlength (L ) of the cell. (L ′, meter), sample pressure (P ′, kPa), abso- R S S 4.6.2 Obtain or prepare a set of chemical lute sample temperature T ′, and signal inte- S standards for each analyte, potential and gration period (t , seconds) for the analysis. SS known spectral interferants, and CTS. Select Specify the nominal minimum instrumental the concentrations of the chemical standards linewidth (MIL) of the system. Verify that to correspond to the top of the desired range. the fractional error at the approximate val- 4.6.2.1 Commercially-Prepared Chemical ues P ′ and T ′ is less than one half the S S Standards. Chemical standards for many smallest value AU (see section 4.1.2 of this i compounds may be obtained from inde- addendum). pendent sources, such as a specialty gas 4.5 Select Calibration Transfer Standards manufacturer, chemical company, or com- (CTS’s). Select CTS’s that meet the criteria mercial laboratory. These standards (accu- listed in sections 4.5.1, 4.5.2, and 4.5.3 of this rate to within ±2 percent) shall be prepared addendum. according to EPA Traceability Protocol (see NOTE: It may be necessary to choose pre- Reference D) or shall be traceable to NIST liminary analytical regions (see section 4.7 standards. Obtain from the supplier an esti- of this addendum), identify the minimum mate of the stability of the analyte con- analyte linewidths, or estimate the system centration. Obtain and follow all of the sup- noise level (see section 4.12 of this adden- plier’s recommendations for recertifying the dum) before selecting the CTS. More than analyte concentration. one compound may be needed to meet the 4.6.2.2 Self-Prepared Chemical Standards. criteria; if so, obtain separate cylinders for Chemical standards may be prepared by di- each compound. luting certified commercially prepared 4.5.1 The central wavenumber position of chemical gases or pure analytes with ultra- each analytical region shall lie within 25 per- pure carrier (UPC) grade nitrogen according cent of the wavenumber position of at least to the barometric and volumetric techniques one CTS absorption band. generally described in Reference A, section 4.5.2 The absorption bands in section 4.5.1 A4.6. of this addendum shall exhibit peak 4.6.3 Record a set of the absorption spec- absorbances greater than ten times the value tra of the CTS {R1}, then a set of the ref- RMSEST (see section 4.12 of this addendum) erence spectra at two or more concentra- but less than 1.5 absorbance units. tions in duplicate over the desired range (the 4.5.3 At least one absorption CTS band top of the range must be less than 10 times within the operating range of the FTIR in- that of the bottom), followed by a second set strument shall have an instrument-inde- of CTS spectra {R2}. (If self-prepared stand- pendent linewidth no greater than the nar- ards are used, see section 4.6.5 of this adden- rowest analyte absorption band. Perform and dum before disposing of any of the stand- document measurements or cite Studies to ards.) The maximum accepted standard con- determine analyte and CTS compound centration-pathlength product (ASCPP) for linewidths. each compound shall be higher than the

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maximum estimated concentration- in accordance with section 4.6 of this adden- pathlength products for both analytes and dum are not valid for the application. known interferants in the effluent gas. For 4.9 Identify Known Interferants. Using ap- each analyte, the minimum ASCPP shall be pendix B of this addendum, determine which no greater than ten times the concentration- potential interferants affect the analyte con- pathlength product of that analyte at its re- centration determinations. Relabel these po- quired detection limit. tential interferant as ‘‘known’’ interferants, 4.6.4 Permanently store the background and designate these compounds from k = 1 to and interferograms in digitized form. Docu- K. Appendix B to this addendum also pro- ment details of the mathematical process for vides criteria for determining whether the generating the spectra from these selected analytical regions are suitable. interferograms. Record the sample pressure 4.10 Prepare Computerized Analytical (PR), sample temperature (TR), reference ab- Programs sorption pathlength (LR), and interferogram 4.10.1 Choose or devise mathematical signal integration period (tSR). Signal inte- techniques (e.g, classical least squares, in- gration periods for the background verse least squares, cross-correlation, and interferograms shall be ≥tSR. Values of PR, factor analysis) based on equation 4 of Ref- LR, and tSR shall not deviate by more than ±1 erence A that are appropriate for analyzing percent from the time of recording [R1] to spectral data by comparison with reference that of recording [R2]. spectra. 4.6.5 If self-prepared chemical standards 4.10.2 Following the general recommenda- are employed and spectra of only two con- tions of Reference A, prepare a computer centrations are recorded for one or more program or set of programs that analyzes all compounds, verify the accuracy of the dilu- of the analytes and known interferants, tion technique by analyzing the prepared based on the selected analytical regions (sec- standards for those compounds with a section 4.7 of this addendum) and the prepared ondary (non-FTIR) technique in accordance reference spectra (section 4.6 of this adden- with sections 4.6.5.1 through 4.6.5.4 of this ad- dum). Specify the baseline correction tech- dendum. nique (e.g., determining the slope and inter- 4.6.5.1 Record the response of the sec- cept of a linear baseline contribution in each ondary technique to each of the four stand- analytical region) for each analytical region, ards prepared. including all relevant wavenumber positions. 4.6.5.2 Perform a linear regression of the 4.10.3 Use programs that provide as out- response values (dependant variable) versus put [at the reference absorption pathlength the accepted standard concentration (ASC) (LR), reference gas temperature (TR), and ref- values (independent variable), with the re- erence gas pressure (PR)] the analyte con- gression constrained to pass through the centrations, the known interferant con- zero-response, zero ASC point. centrations, and the baseline slope and inter- 4.6.5.3 Calculate the average fractional cept values. If the sample absorption difference between the actual response val- pathlength (LS), sample gas temperature ues and the regression-predicted values (TS), or sample gas pressure (PS) during the (those calculated from the regression line actual sample analyses differ from LR, TR, using the four ASC values as the independent and PR, use a program or set of programs variable). that applies multiplicative corrections to 4.6.5.4 If the average fractional difference the derived concentrations to account for value calculated in section 4.6.5.3 of this ad- these variations, and that provides as output dendum is larger for any compound than the both the corrected and uncorrected values. corresponding AUi, the dilution technique is Include in the report of the analysis (see sec- not sufficiently accurate and the reference tion 7.0 of this addendum) the details of any spectra prepared are not valid for the anal- transformations applied to the original ref- ysis. erence spectra (e.g., differentiation), in such 4.7 Select Analytical Regions. Using the a fashion that all analytical results may be general considerations in section 7 of Ref- verified by an independent agent from the erence A and the spectral characteristics of reference spectra and data spectra alone. the analytes and interferants, select the ana- 4.11 Determine the Fractional Calibration lytical regions for the application. Label Uncertainty. Calculate the fractional calibra- them m = 1 to M. Specify the lower, center tion uncertainty for each analyte (FCUi) ac- and upper wavenumber positions of each ana- cording to appendix F of this addendum, and lytical region (FLm, FCm, and FUm, respec- compare these values to the fractional un- tively). Specify the analytes and interferants certainty limits (AUi; see section 4.1.2 of this which exhibit absorption in each region. addendum). If FCUi >AUi, either the ref- 4.8 Determine Fractional Reproducibility erence spectra or analytical programs for Uncertainties. Using appendix E of this adden- that analyte are unsuitable. dum, calculate the fractional reproducibility 4.12 Verify System Configuration Suitability. uncertainty for each analyte (FRUi) from a Using appendix C of this addendum, measure comparison of [R1] and [R2]. If FRUi >AUi for or obtain estimates of the noise level any analyte, the reference spectra generated (RMSEST, absorbance) of the FTIR system. 829

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Alternatively, construct the complete spec- 5.5 Quantify Analyte Concentrations. Cal- trometer system and determine the values culate the unscaled analyte concentrations RMSSm using appendix G of this addendum. RUAi and unscaled interferant concentra- Estimate the minimum measurement uncer- tions RUIK using the programs developed in tainty for each analyte (MAUi, ppm) and section 4 of this addendum. To correct for known interferant (MIUk, ppm) using appen- pathlength and pressure variations between dix D of this addendum. Verify that (a) MAUi the reference and sample spectra, calculate <(AUi)(DLi), FRUi

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that these transformations lead to accept- (B) The Coblentz Society Specifications for able calculated concentration uncertainties Evaluation of Research Quality Analytical in all analytical regions. Infrared Reference Spectra (Class II); Anal. Chemistry 47, 945A (1975); Appl. Spectroscopy 6.0 Post-Analysis Evaluations 444, pp. 211–215, 1990. Estimate the overall accuracy of the anal- (C) Standard Practices for General Tech- yses performed in accordance with sections niques for Qualitative Infrared Analysis, 5.1 through 5.6 of this addendum using the American Society for Testing and Materials, procedures of sections 6.1 through 6.3 of this Designation E 1252–88. addendum. (D) ‘‘EPA Traceability Protocol for Assay 6.1 Qualitatively Confirm the Assumed Ma- and Certification of Gaseous Calibration trix. Examine each analytical region of the Standards,’’ U.S. Environmental Protection sample spectrum for spectral evidence of un- Agency Publication No. EPA/600/R–93/224, De- expected or unidentified interferants. If cember 1993. found, identify the interfering compounds APPENDIX A TO ADDENDUM TO METHOD 320— (see Reference C for guidance) and add them DEFINITIONS OF TERMS AND SYMBOLS to the list of known interferants. Repeat the procedures of section 4 of this addendum to A.1 Definitions of Terms. All terms used in include the interferants in the uncertainty this method that are not defined below have calculations and analysis procedures. Verify the meaning given to them in the CAA and that the MAU and FCU values do not in- in subpart A of this part. crease beyond acceptable levels for the appli- Absorption band means a contiguous cation requirements. Re-calculate the wavenumber region of a spectrum (equiva- analyte concentrations (section 5.5 of this lently, a contiguous set of absorbance spec- addendum) in the affected analytical re- trum data points) in which the absorbance gions. passes through a maximum or a series of 6.2 Quantitatively Evaluate Fractional maxima. Model Uncertainty (FMU). Perform the proce- Absorption pathlength means the distance in dures of either section 6.2.1 or 6.2.2 of this ad- a spectrophotometer, measured in the direc- dendum: tion of propagation of the beam of radiant 6.2.1 Using appendix I of this addendum, energy, between the surface of the specimen determine the fractional model error (FMU) on which the radiant energy is incident and for each analyte. the surface of the specimen from which it is 6.2.2 Provide statistically determined un- emergent. certainties FMU for each analyte which are Analytical region means a contiguous equivalent to two standard deviations at the wavenumber region (equivalently, a contig- 95 percent confidence level. Such determina- uous set of absorbance spectrum data points) tions, if employed, must be based on mathe- used in the quantitative analysis for one or matical examinations of the pertinent sam- more analytes. ple spectra (not the reference spectra alone). NOTE: The quantitative result for a single Include in the report of the analysis (see sec- analyte may be based on data from more tion 7.0 of this addendum) a complete de- than one analytical region. scription of the determination of the con- means modification of the ILS centration uncertainties. Apodization function by multiplying the interferogram 6.3 Estimate Overall Concentration Uncer- by a weighing function whose magnitude tainty (OCU). Using appendix J of this adden- varies with retardation. dum, determine the overall concentration Background spectrum means the single uncertainty (OCU) for each analyte. If the beam spectrum obtained with all system OCU is larger than the required accuracy for components without sample present. any analyte, repeat sections 4 and 6 of this addendum. Baseline means any line drawn on an absorption spectrum to establish a reference 7.0 Reporting Requirements point that represents a function of the radiant power incident on a sample at a given [Documentation pertaining to virtually all wavelength. the procedures of sections 4, 5, and 6 will be Beers’s law means the direct proportion- required. Software copies of reference spec- ality of the absorbance of a compound in a tra and sample spectra will be retained for homogeneous sample to its concentration. some minimum time following the actual Calibration transfer standard (CTS) gas testing.] means a gas standard of a compound used to achieve and/or demonstrate suitable quan- 8.0 References titative agreement between sample spectra (A) Standard Practices for General Tech- and the reference spectra; see section 4.5.1 of niques of Infrared Quantitative Analysis this addendum. (American Society for Testing and Mate- Compound means a substance possessing a rials, Designation E 168–88). distinct, unique molecular structure.

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Concentration (c) means the quantity of a Interferometer means device that divides a compound contained in a unit quantity of beam of radiant energy into two or more sample. The unit ‘‘ppm’’ (number, or mole, paths, generates an optical path difference basis) is recommended. between the beams, and recombines them in Concentration-pathlength product means the order to produce repetitive interference mathematical product of concentration of maxima and minima as the optical retarda- the species and absorption pathlength. For tion is varied. reference spectra, this is a known quantity; Linewidth means the full width at half for sample spectra, it is the quantity di- maximum of an absorption band in units of rectly determined from Beer’s law. The units wavenumbers (cm¥1). ‘‘centimeters-ppm’’ or ‘‘meters-ppm’’ are Mid-infrared means the region of the elec- recommended. tromagnetic spectrum from approximately Derivative absorption spectrum means a plot 400 to 5000 cm¥1. of rate of change of absorbance or of any Reference spectra means absorption spectra function of absorbance with respect to wave- of gases with known chemical compositions, length or any function of wavelength. recorded at a known absorption pathlength, Double beam spectrum means a transmission which are used in the quantitative analysis or absorbance spectrum derived by dividing of gas samples. the sample single beam spectrum by the Retardation, s means optical path dif- background spectrum. ference between two beams in an interferometer; also known as ‘‘optical path difference’’ NOTE: The term ‘‘double-beam’’ is used or ‘‘optical retardation.’’ elsewhere to denote a spectrum in which the Scan means digital representation of the sample and background interferograms are detector output obtained during one com- collected simultaneously along physically plete motion of the interferometer’s moving distinct absorption paths. Here, the term de- assembly or assemblies. notes a spectrum in which the sample and Scaling means application of a multiplica- background interferograms are collected at tive factor to the absorbance values in a different times along the same absorption spectrum. path. Single beam spectrum means Fourier-trans- Fast Fourier transform (FFT) means a meth- formed interferogram, representing the de- od of speeding up the computation of a dis- tector response vs. wavenumber. crete FT by factoring the data into sparse NOTE: The term ‘‘single-beam’’ is used else- matrices containing mostly zeros. where to denote any spectrum in which the Flyback means interferometer motion dur- sample and background interferograms are ing which no data are recorded. recorded on the same physical absorption Fourier transform (FT) means the mathe- path; such usage differentiates such spectra matical process for converting an amplitude- from those generated using interferograms time spectrum to an amplitude-frequency recorded along two physically distinct ab- spectrum, or vice versa. sorption paths (see ‘‘double-beam spectrum’’ Fourier transform infrared (FTIR) spectrom- above). Here, the term applies (for example) eter means an analytical system that em- to the two spectra used directly in the cal- ploys a source of mid-infrared radiation, an culation of transmission and absorbance interferometer, an enclosed sample cell of spectra of a sample. known absorption pathlength, an infrared detector, optical elements that transfer in- Standard reference material means a ref- frared radiation between components, and a erence material, the composition or prop- computer system. The time-domain detector erties of which are certified by a recognized response (interferogram) is processed by a standardizing agency or group. Fourier transform to yield a representation NOTE: The equivalent ISO term is ‘‘cer- of the detector response vs. infrared fre- tified reference material.’’ quency. Transmittance, T means the ratio of radiant NOTE: When FTIR spectrometers are inter- power transmitted by the sample to the radi- faced with other instruments, a slash should ant power incident on the sample. Estimated be used to denote the interface; e.g., GC/ in FTIR spectroscopy by forming the ratio of FTIR; HPCL/FTIR, and the use of FTIR the single-beam sample and background should be explicit; i.e., FTIR not IR. spectra. Wavenumber, v¯ means the number of waves Frequency, v means the number of cycles per unit length. per unit time. Infrared means the portion of the electro- NOTE: The usual unit of wavenumber is the ¥ magnetic spectrum containing wavelengths reciprocal centimeter, cm 1. The from approximately 0.78 to 800 microns. wavenumber is the reciprocal of the wave- λ λ Interferogram, I(s) means record of the length, , when is expressed in centimeters. modulated component of the interference Zero-filling means the addition of zero-val- signal measured as a function of retardation ued points to the end of a measured by the detector. interferogram.

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NOTE: Performing the FT of a zero-filled (16) FFUm = upper wavenumber position of interferogram results in correctly inter- the CTS absorption band associated with the polated points in the computed spectrum. mth analytical region. A.2 Definitions of Mathematical Symbols. (17) FLm = lower wavenumber position of The symbols used in equations in this pro- the mth analytical region. tocol are defined as follows: (18) FMUi, fractional model uncertainty = (1) A, absorbance = the logarithm to the calculated uncertainty in the measured con- th base 10 of the reciprocal of the transmittance centration of the i analyte because of er- (T). rors in the absorption model employed. (19) FNL = lower wavenumber position of ⎛ 1 ⎞ the CTS spectrum containing an absorption A = log =− log T band at least as narrow as the analyte ab- 10⎝ T⎠ 10 sorption bands. (20) FNU = upper wavenumber position of th (2) AAIim = band area of the i analyte in the CTS spectrum containing an absorption the mth analytical region, at the concentra- band at least as narrow as the analyte ab- tion (CLi) corresponding to the product of its sorption bands. required detection limit (DLi) and analytical (21) FRUi, fractional reproducibility uncer- uncertainty limit (AUi) . tainty = calculated uncertainty in the meas- th (3) AAVim = average absorbance of the i ured concentration of the ith analyte because analyte in the mth analytical region, at the of errors in the reproducibility of spectra concentration (CLi) corresponding to the from the FTIR system. product of its required detection limit (DL ) i (22) FUm = upper wavenumber position of and analytical uncertainty limit (AUi). the mth analytical region. (4) ASC, accepted standard concentration = th (23) IAIjm = band area of the j potential the concentration value assigned to a chem- interferant in the mth analytical region, at ical standard. its expected concentration (CPOTj). th (5) ASCPP, accepted standard concentra- (24) IAVim = average absorbance of the i tion-pathlength product = for a chemical analyte in the mth analytical region, at its standard, the product of the ASC and the expected concentration (CPOTj). sample absorption pathlength. The units (25) ISCiork, indicated standard concentra- ‘‘centimeters-ppm’’ or ‘‘meters-ppm’’ are tion = the concentration from the computer- recommended. ized analytical program for a single-com- (6) AUi, analytical uncertainty limit = the pound reference spectrum for the ith analyte maximum permissible fractional uncertainty or kth known interferant. of analysis for the ith analyte concentration, (26) kPa = kilo-Pascal (see Pascal). expressed as a fraction of the analyte con- (27) LS′ = estimated sample absorption centration determined in the analysis. pathlength. (7) AVTm = average estimated total absorb- (28) LR = reference absorption pathlength. th ance in the m analytical region. (29) LS = actual sample absorption (8) CKWNk = estimated concentration of pathlength. th the k known interferant. (30) MAUi = mean of the MAUim over the (9) CMAXi = estimated maximum con- appropriate analytical regions. th centration of the i analyte. (31) MAUim, minimum analyte uncertainty (10) CPOTj = estimated concentration of = the calculated minimum concentration for th the j potential interferant. which the analytical uncertainty limit (AUi) th (11) DLi, required detection limit = for the in the measurement of the i analyte, based ith analyte, the lowest concentration of the on spectral data in the mth analytical region, analyte for which its overall fractional un- can be maintained. certainty (OFUi) is required to be less than (32) MIUj = mean of the MIUjm over the ap- the analytical uncertainty limit (AUi). propriate analytical regions. (12) FCm = center wavenumber position of (33) MIUjm, minimum interferant uncer- the mth analytical region. tainty = the calculated minimum concentra- (13) FAUi, fractional analytical uncer- tion for which the analytical uncertainty th tainty = calculated uncertainty in the meas- limit CPOTj/20 in the measurement of the j ured concentration of the ith analyte because interferant, based on spectral data in the mth of errors in the mathematical comparison of analytical region, can be maintained. reference and sample spectra. (34) MIL, minimum instrumental linewidth = the minimum linewidth from the FTIR (14) FCUi, fractional calibration uncertainty = calculated uncertainty in the meas- system, in wavenumbers. ured concentration of the ith analyte because NOTE: The MIL of a system may be deter- of errors in Beer’s law modeling of the ref- mined by observing an absorption band erence spectra concentrations. known (through higher resolution examina- (15) FFLm = lower wavenumber position of tions) to be narrower than indicated by the the CTS absorption band associated with the system. The MIL is fundamentally limited mth analytical region. by the retardation of the interferometer, but

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is also affected by other operational param- power transmitted by the absorption cell and eters (e.g., the choice of apodization). transfer optics from the interferometer to the detector. (35) Ni = number of analytes. (36) Nj = number of potential interferants. (56) VSS = volume of the infrared absorption (37) Nk = number of known interferants. cell, including parts of attached tubing. (38) Nscan = the number of scans averaged to (57) Wik = weight used to average over ana- obtain an interferogram. lytical regions k for quantities related to the (39) OFUi = the overall fractional uncer- analyte i; see appendix D of this addendum. tainty in an analyte concentration deter- APPENDIX B TO ADDENDUM TO METHOD 320— mined in the analysis (OFUi = MAX[FRUi, IDENTIFYING SPECTRAL INTERFERANTS FCUi, FAUi, FMUi]). (40) Pascal (Pa) = metric unit of static pressure, equal to one Newton per square B.1 General meter; one atmosphere is equal to 101,325 Pa; B.1.1 Assume a fixed absorption 1/760 atmosphere (one Torr, or one milli- pathlength equal to the value LS′. meter Hg) is equal to 133.322 Pa. B.1.2 Use band area calculations to com- (41) Pmin = minimum pressure of the sam- pare the relative absorption strengths of the pling system during the sampling procedure. analytes and potential interferants. In the (42) P ′ = estimated sample pressure. th S m analytical region (FLm to FUm), use ei- (43) PR = reference pressure. ther rectangular or trapezoidal approxima- (44) PS = actual sample pressure. tions to determine the band areas described (45) RMSSm = measured noise level of the below (see Reference A, sections A.3.1 FTIR system in the mth analytical region. through A.3.3). Document any baseline cor- (46) RMSD, root mean square difference = a rections applied to the spectra. measure of accuracy determined by the fol- B.1.3 Use the average total absorbance of lowing equation: the analytes and potential interferants in each analytical region to determine whether n the analytical region is suitable for analyte = ⎛ 1⎞ 2 RMSD ⎝ ⎠∑ ei concentration determinations. n i=1 NOTE: The average absorbance in an ana- Where: lytical region is the band area divided by the width of the analytical region in n = the number of observations for which the wavenumbers. The average total absorbance accuracy is determined. in an analytical region is the sum of the av- ei = the difference between a measured value erage absorbances of all analytes and poten- of a property and its mean value over the tial interferants. n observations. NOTE: The RMSD value ‘‘between a set of n B.2 Calculations contiguous absorbance values (Ai) and the B.2.1 Prepare spectral representations of mean of the values’’ (AM) is defined as each analyte at the concentration CLi = n (DLi)(AUi), where DLi is the required detec- ⎛ 1⎞ 2 = ()− tion limit and AUi is the maximum permis- RMSD ⎝ ⎠ ∑ AAiM sible analytical uncertainty. For the mth an- n i−1 alytical region, calculate the band area (AAI ) and average absorbance (AAV ) from (47) RSAi = the (calculated) final con- im im centration of the ith analyte. these scaled analyte spectra. (48) RSIk = the (calculated) final concentra- B.2.2 Prepare spectral representations of tion of the kth known interferant. each potential interferant at its expected th (49) tscan, scan time = time used to acquire concentration (CPOTj). For the m analyt- a single scan, not including flyback. ical region, calculate the band area (IAIjm) (50) tS, signal integration period = the pe- and average absorbance (IAVjm) from these riod of time over which an interferogram is scaled potential interferant spectra. averaged by addition and scaling of indi- B.2.3 Repeat the calculation for each ana- vidual scans. In terms of the number of scans lytical region, and record the band area re- Nscan and scan time tscan, tS = Nscantscan. sults in matrix form as indicated in Figure (51) tSR = signal integration period used in B.1. recording reference spectra. B.2.4 If the band area of any potential (52) tSS = signal integration period used in interferant in an analytical region is greater recording sample spectra. than the one-half the band area of any (53) TR = absolute temperature of gases analyte (i.e., IAIjm >0.5 AAIim for any pair ij used in recording reference spectra. and any m), classify the potential (54) TS = absolute temperature of sample interferant as a known interferant. Label the gas as sample spectra are recorded. known interferants k = 1 to K. Record the re- (55) TP, Throughput = manufacturer’s esti- sults in matrix form as indicated in Figure mate of the fraction of the total infrared B.2.

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B.2.5 Calculate the average total absorb- trix described in Figure B.2. Any analytical

ance (AVTm) for each analytical region and region where AVTm >2.0 is unsuitable. record the values in the last row of the ma-

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APPENDIX C TO ADDENDUM TO METHOD 320— C.1.3.1 RMSMAN, the noise level of the sys- ESTIMATING NOISE LEVELS tem (in absorbance units), without the absorption cell and transfer optics, under those C.1 General conditions necessary to yield the specified minimum instrumental linewidth, e.g., Jacquinot C.1.1 The root-mean-square (RMS) noise stop size. level is the standard measure of noise in this C.1.3.2 tMAN, the manufacturer’s signal in- addendum. The RMS noise level of a contig- tegration time used to determine RMS . uous segment of a spectrum is defined as the MAN C.1.3.3 tSS, the signal integration time for RMS difference (RMSD) between the absorb- the analyses. ance values which form the segment and the C.1.3.4 TP, the manufacturer’s estimate of mean value of that segment (see appendix A the fraction of the total infrared power of this addendum). transmitted by the absorption cell and trans- C.1.2 The RMS noise value in double-beam fer optics from the interferometer to the de- absorbance spectra is assumed to be in- tector. versely proportional to: (a) the square root of the signal integration period of the sample C.2 Calculations single beam spectra from which it is formed, C.2.1 Obtain the values of RMSMAN, tMAN, and (b) the total infrared power transmitted and TP from the manufacturers of the equip- through the interferometer and absorption ment, or determine the noise level by direct cell. measurements with the completely con- C.1.3 Practically, the assumption of C.1.2 structed system proposed in section 4 of this allows the RMS noise level of a complete addendum. system to be estimated from the quantities C.2.2 Calculate the noise value of the sys- described in sections C.1.3.1 through C.1.3.4: tem (RMSEST) using equation C.1.

= tss RMSEST RMS MAN TP (C.1) t MAN

APPENDIX D TO ADDENDUM TO METHOD 320— area is equal to the product of the analytical ESTIMATING MINIMUM CONCENTRATION region width (in wavenumbers) and the noise MEASUREMENT UNCERTAINTIES (MAU AND level of the system (in absorbance units). If MIU) data from more than one analytical region are used in the determination of an analyte D.1 General concentration, the MAU or MIU is the mean Estimate the minimum concentration of the separate MAU or MIU values cal- measurement uncertainties for the ith culated for each analytical region. th analyte (MAUi) and j interferant (MIUj) based on the spectral data in the mth analyt- D.2 Calculations ical region by comparing the analyte band D.2.1 For each analytical region, set RMS area in the analytical region (AAIim) and es- = RMSSM if measured (appendix G of this ad- timating or measuring the noise level of the dendum), or set RMS = RMSEST if estimated system (RMSEST or RMSSM). (appendix C of this addendum). NOTE: For a single analytical region, the D.2.2 For each analyte associated with MAU or MIU value is the concentration of the analytical region, calculate MAUim using the analyte or interferant for which the band equation D.1,

()FU− FL = () mm MAUim RMS ()() DL i AU i (D.1) AAIim

th D.2.3 If only the m analytical region is analyte, set MAUi equal to the weighted th used to calculate the concentration of the i mean of the appropriate MAUim values cal- analyte, set MAUi = MAUim. culated above; the weight for each term in D.2.4 If more than one analytical region is the mean is equal to the fraction of the total used to calculate the concentration of the ith wavenumber range used for the calculation

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represented by each analytical region. Math- ematically, if the set of analytical regions = MAUik∑ W MAUik (D.2) ′ employed is [m ], then the MAU for each ana- km∈{}′ lytical region is given by equation D.2. where the weight Wik is defined for each term in the sum as

⎛ ⎞ −1 =− − WFMFLik() k k ⎜ ∑ [] FMFLpp⎟ (D.3) ⎝ pm∈{}′ ⎠

D.2.5 Repeat sections D.2.1 through D.2.4 denoted by S2i, i = 1, N. Each Ski is the spec- of this appendix to calculate the analogous trum of a single compound, where i denotes values MIUj for the interferants j = 1 to J. the compound and k denotes the set {} of Replace the value (AUi) (DLi) in equation D.1 which Ski is a member. Form the spectra S3 with CPOTj/20; replace the value AAIim in according to S3i = S2i¥S1i for each i. Form equation D.1 with IAI . jm the spectra S4 according to S4i = [S2i + S1i]/2 for each i. APPENDIX E TO ADDENDUM TO METHOD 320— DETERMINING FRACTIONAL REPRODUCIBILITY E.2.2 Each analytical region m is associ- UNCERTAINTIES (FRU) ated with a portion of the CTS spectra S2i and S1i, for a particular i, with lower and E.1 General upper wavenumber limits FFLm and FFUm, respectively. To estimate the reproducibility of the spectroscopic results of the system, compare E.2.3 For each m and the associated i, cal- the CTS spectra recorded before and after culate the band area of S4i in the preparing the reference spectra. Compare the wavenumber range FFUm to FFLm. Follow difference between the spectra to their aver- the guidelines of section B.1.2 of this adden- age band area. Perform the calculation for dum for this band area calculation. Denote each analytical region on the portions of the the result by BAVm. CTS spectra associated with that analytical E.2.4 For each m and the associated i, cal- region. culate the RMSD of S3i between the absorbance values and their mean in the E.2 Calculations wavenumber range FFUm to FFLm. Denote E.2.1 The CTS spectra {R1} consist of N the result by SRMSm. spectra, denoted by S1i, i = 1, N. Similarly, E.2.5 For each analytical region m, cal- the CTS spectra {R2} consist of N spectra, culate FMm using equation E.1,

=− FMmmmmm SRMS() FFU FFL BAV (E.1)

E.2.6 If only the mth analytical region is APPENDIX F OF ADDENDUM TO METHOD 320— used to calculate the concentration of the ith DETERMINING FRACTIONAL CALIBRATION UN-

analyte, set FRUi = FMm. CERTAINTIES (FCU) E.2.7 If a number pi of analytical regions are used to calculate the concentration of F.1 General th the i analyte, set FRUi equal to the weight- F.1.1 The concentrations yielded by the ed mean of the appropriate FMm values cal- computerized analytical program applied to culated according to section E.2.5. Mathe- each single-compound reference spectrum matically, if the set of analytical regions are defined as the indicated standard con- employed is {m′}, then FRUi is given by centrations (ISC’s). The ISC values for a sin- equation E.2, gle compound spectrum should ideally equal the accepted standard concentration (ASC) = for one analyte or interferant, and should FRUi ∑ Wik FM k (E.2) ideally be zero for all other compounds. Vari- km∈{}′ ations from these results are caused by er- where the Wik are calculated as described in rors in the ASC values, variations from the appendix D of this addendum. Beer’s law (or modified Beer’s law) model

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used to determine the concentrations, and F.2 Calculations noise in the spectra. When the first two effects dominate, the systematic nature of the F.2.1 Apply each analytical program to errors is often apparent and the analyst shall each reference spectrum. Prepare a similar take steps to correct them. table to that in Figure F.1 to present the ISC F.1.2 When the calibration error appears and ASC values for each analyte and non-systematic, apply the procedures of sec- interferant in each reference spectrum. tions F.2.1 through F.2.3 of this appendix to Maintain the order of reference file names estimate the fractional calibration uncer- and compounds employed in preparing Fig- tainty (FCU) for each compound. The FCU is ure F.1. defined as the mean fractional error between F.2.2 For all reference spectra in Figure the ASC and the ISC for all reference spectra F.1, verify that the absolute values of the with non-zero ASC for that compound. The ISC’s are less than the compound’s MAU (for FCU for each compound shall be less than analytes) or MIU (for interferants). the required fractional uncertainty specified F.2.3 For each analyte reference spec- in section 4.1 of this addendum. F.1.3 The computerized analytical pro- trum, calculate the quantity (ASC-ISC)/ASC. grams shall also be required to yield accept- For each analyte, calculate the mean of th ably low concentrations for compounds with these values (the FCUi for the i analyte) ISC = 0 when applied to the reference spec- over all reference spectra. Prepare a similar tra. The ISC of each reference spectrum for table to that in Figure F.2 to present the each analyte or interferant shall not exceed FCUi and analytical uncertainty limit (AUi) that compound’s minimum measurement un- for each analyte. certainty (MAU or MIU).

FIGURE F.1—PRESENTATION OF ACCEPTED STANDARD CONCENTRATIONS (ASC’S) AND INDICATED STANDARD CONCENTRATIONS (ISC’S)

Compound name Reference ASC ISC (ppm) spectrum file (ppm) name Analytes Interferants i = 1 I j = 1 J

FIGURE F.2—PRESENTATION OF FRACTIONAL CALIBRATION UNCERTAINTIES (FCU’S) AND ANALYTICAL UNCERTAINTIES (AU’S)

Analyte name FCU (%) AU (%)

APPENDIX G TO ADDENDUM TO METHOD 320— G.2 Calculations MEASURING NOISE LEVELS G.2.1 Evacuate the absorption cell or fill G.1 General it with UPC grade nitrogen at approximately one atmosphere total pressure. The root-mean-square (RMS) noise level is G.2.2 Record two single beam spectra of the standard measure of noise. The RMS signal integration period t . noise level of a contiguous segment of a SS spectrum is the RMSD between the absorb- G.2.3 Form the double beam absorption ance values that form the segment and the spectrum from these two single beam spec- mean value of the segment (see appendix A tra, and calculate the noise level RMSSm in of this addendum). the M analytical regions.

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APPENDIX H OF ADDENDUM TO METHOD 320— recording the sample spectra, based on band DETERMINING SAMPLE ABSORPTION areas of the spectra in the CTS absorbance PATHLENGTH (LS) AND FRACTIONAL ANALYT- band associated with each analyte. ICAL UNCERTAINTY (FAU) H.2 Calculations H.1 General H.2.1 Absorption Pathlength Determination. Reference spectra recorded at absorption Perform and document separate linear base- pathlength (LR), gas pressure (PR), and gas line corrections to each analytical region in absolute temperature (TR) may be used to de- the spectral sets {R1} and {R3}. Form a one- termine analyte concentrations in samples dimensional array AR containing the absorb- whose spectra are recorded at conditions dif- ance values from all segments of {R1} that ferent from that of the reference spectra, are associated with the analytical regions; i.e., at absorption pathlength (LS), absolute the members of the array are ARi, i = 1, n. temperature (TS), and pressure (PS). This ap- Form a similar one-dimensional array AS pendix describes the calculations for esti- from the absorbance values in the spectral mating the fractional uncertainty (FAU) of set {R3}; the members of the array are ASi, i this practice. It also describes the calcula- = 1, n. Based on the model AS = rAR + E, de- tions for determining the sample absorption termine the least-squares estimate of r, the pathlength from comparison of CTS spectra, value of r which minimizes the square error and for preparing spectra for further instru- E2. Calculate the sample absorption mental and procedural checks. pathlength, LS, using equation H.1, H.1.1 Before sampling, determine the sample absorption pathlength using least = LrTTLssRR'() (H.1) squares analysis. Determine the ratio LS/LR by comparing the spectral sets {R1} and H.2.2 Fractional Analysis Uncertainty. Per- {R3}, which are recorded using the same CTS form and document separate linear baseline at LS and LR, and TS and TR, but both at PR. corrections to each analytical region in the H.1.2 Determine the fractional analysis spectral sets {R1} and {R4}. Form the arrays uncertainty (FAU) for each analyte by com- AS and AR as described in section H.2.1 of this paring a scaled CTS spectral set, recorded at appendix, using values from {R1} to form AR, LS, TS, and PS, to the CTS reference spectra and values from {R4} to form AS. Calculate of the same gas, recorded at LR, TR, and PR. NRMSE and IAAV using equations H.2 and Perform the quantitative comparison after H.3,

n ⎡ ⎛ T ⎞⎛ L ⎞⎛ P ⎞ ⎤ NRMS=−∑ ⎢ A ⎜ R ⎟⎜ S ⎟⎜ S ⎟ A ⎥ (H.2) ESi⎝ ⎠⎝ ⎠⎝ ⎠ Ri i=1 ⎣⎢ TS L R PR ⎦⎥

1 n ⎡ ⎛ T ⎞⎛ L ⎞⎛ P ⎞ ⎤ IA=+∑ ⎢ A ⎜ R ⎟⎜ S ⎟⎜ S ⎟ A ⎥ (H.3) AV Si ⎝ ⎠⎝ ⎠⎝ ⎠ Ri 2 i=1 ⎣⎢ TS L R PR ⎦⎥

The fractional analytical uncertainty, lated spectra consist of the sum of single FAU, is given by equation H.4, compound reference spectra scaled to represent their contributions to the sample ab- = NRMSE sorbance spectrum; scaling factors are based FAU (H.4) on the indicated standard concentrations IA AV (ISC) and measured (sample) analyte and interferant concentrations, the sample and APPENDIX I TO ADDENDUM TO METHOD 320— reference absorption pathlengths, and the DETERMINING FRACTIONAL MODEL UNCER- sample and reference gas pressures. No band- TAINTIES (FMU) shape correction for differences in the temperature of the sample and reference spectra I.1 General gases is made; such errors are included in the To prepare analytical programs for FTIR FMU estimate. The actual and simulated analyses, the sample constituents must first sample spectra are quantitatively compared be assumed. The calculations in this appen- to determine the fractional model uncer- dix, based upon a simulation of the sample tainty; this comparison uses the reference spectrum, shall be used to verify the appro- priateness of these assumptions. The simu-

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spectra band areas and residuals in the dif- Form the spectra SICk by scaling each SIk by ference spectrum formed from the actual and the factor RIk. simulated sample spectra. I.2.3 For each analytical region, determine by visual inspection which of the spec- I.2 Calculations tra SACi and SICk exhibit absorbance bands I.2.1 For each analyte (with scaled con- within the analytical region. Subtract each

centration RSAi), select a reference spec- spectrum SACi and SICk exhibiting absorb- trum SA with indicated standard concentra- i ance from the sample spectrum SS to form tion ISC . Calculate the scaling factors, RA , i i the spectrum SUBS. To save analysis time using equation I.1, and to avoid the introduction of unwanted T L P RSA noise into the subtracted spectrum, it is rec- = R S S i ommended that the calculation be made (1) RAi (I.1) only for those spectral data points within TPSR L R ISC i the analytical regions, and (2) for each ana- Form the spectra SACi by scaling each SAi lytical region separately using the original

by the factor RAi. spectrum SS. I.2.2 For each interferant, select a ref- I.2.4 For each analytical region m, cal- erence spectrum SIk with indicated standard culate the RMSD of SUBS between the ab- concentration ISCk. Calculate the scaling sorbance values and their mean in the region factors, RIk, using equation I.2, FFUm to FFLm. Denote the result by RMSSm. T L P RSI I.2.5 For each analyte i, calculate FMm, = RSS k using equation I.3, RI k (I.2) TSRR L P ISC k

RMSS() FFU− FFL AU DL = mm mii FM m (I.3) AAIii RSA

for each analytical region associated with uncertainty (FRU, FCU, FAU, or FMU) and the analyte. the measured concentration of an analyte I.2.6 If only the mth analytical region is exceeds the MAU for the analyte, then the used to calculate the concentration of the ith OCU is this product. In mathematical terms, analyte, set FMUi = FMm. set OFUi = MAX{FRUi, FCUi, FAUi, FMUi} I.2.7 If a number of analytical regions are and OCUi = MAX{RSAi*OFUi, MAUi}. used to calculate the concentration of the ith analyte, set FMi equal to the weighted mean TEST METHOD 321—MEASUREMENT OF GAS- of the appropriate FMm values calculated EOUS HYDROGEN CHLORIDE EMISSIONS AT using equation I–3. Mathematically, if the PORTLAND CEMENT KILNS BY FOURIER set of analytical regions employed is {m′}, TRANSFORM INFRARED (FTIR) SPECTROS- then the fractional model uncertainty, FMU, COPY is given by equation I.4, 1.0 Introduction = This method should be performed by those FMUiikk∑ W FM (I.4) persons familiar with the operation of Fou- km∈{}' rier Transform Infrared (FTIR) instrumenta- where Wik is calculated as described in appen- tion in the application to source sampling. dix D of this addendum. This document describes the sampling procedures for use in the application of FTIR spec- APPENDIX J OF ADDENDUM TO METHOD 320— trometry for the determination of vapor DETERMINING OVERALL CONCENTRATION UN- phase hydrogen chloride (HCl) concentra- CERTAINTIES (OCU) tions both before and after particulate mat- The calculations in this addendum esti- ter control devices installed at portland ce- mate the measurement uncertainties for var- ment kilns. A procedure for analyte spiking ious FTIR measurements. The lowest pos- is included for quality assurance. This meth- sible overall concentration uncertainty od is considered to be self validating pro- (OCU) for an analyte is its MAU value, which vided that the requirements listed in section is an estimate of the absolute concentration 9 of this method are followed. The analytical uncertainty when spectral noise dominates procedures for interpreting infrared spectra the measurement error. However, if the prod- from emission measurements are described uct of the largest fractional concentration in the ‘‘Protocol For The Use of Extractive

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Fourier Transform Infrared (FTIR) Spec- centrations in portland cement kiln emis- trometry in Analyses of Gaseous Emissions sions. From Stationary Industrial Sources’’, included as an addendum to proposed Method 1.2 Applicability 320 of this appendix (hereafter referred to as This method applies to the measurement of the ‘‘FTIR Protocol)’’. References 1 and 2 de- HCl [CAS No. 7647–01–0]. This method can be scribe the use of FTIR spectrometry in field applied to the determination of HCl con- measurements. Sample transport presents centrations both before and after particulate the principal difficulty in directly measuring matter control devices installed at portland HCl emissions. This identical problem must cement manufacturing facilities. This meth- be overcome by any extractive measurement od applies to either continuous flow through method. HCl is reactive and water soluble. measurement (with isolated sample analysis) The sampling system must be adequately de- or grab sampling (batch analysis). HCl is signed to prevent sample condensation in the measured using the mid-infrared spectral re- system. gion for analysis (about 400 to 4000 cm¥1 or 25 1.1 Scope and Application to 2.5 μm). Table 1 lists the suggested analyt- This method is specifically designed for ical region for quantification of HCl taking the application of FTIR Spectrometry in ex- the interference from water vapor into con- tractive measurements of gaseous HCl con- sideration.

TABLE 1—EXAMPLE ANALYTICAL REGION FOR HCL

Analytical Compound region Potential ¥ interferants (cm 1)

Hydrogen chloride ...... 2679–2840 Water.

1.3 Method Range and Sensitivity a discussion of the relationship between the 1.3.1 The analytical range is determined RMSD, lower detection limit, DLi, and ana- by the instrumental design and the composi- lytical uncertainty, AUi. It is important to tion of the gas stream. For practical pur- consider the target analyte quantification poses there is no upper limit to the range be- limit when performing testing with FTIR in- cause the pathlength may be reduced or the strumentation, and to optimize the system sample may be diluted. The lower detection to achieve the desired detection limit. range depends on (1) the absorption coeffi- 1.4.2 Data quality is determined by meas- cient of the compound in the analytical fre- uring the root mean square (RMS) noise quency region, (2) the spectral resolution, (3) level in each analytical spectral region (ap- the interferometer sampling time, (4) the de- pendix C of the FTIR Protocol). The RMS tector sensitivity and response, and (5) the noise is defined as the root mean square de- absorption pathlength. viation (RMSD) of the absorbance values in 1.3.2 The practical lower quantification an analytical region from the mean absorb- range is usually higher than that indicated ance value in the same region. Appendix D of by the instrument performance in the lab- the FTIR Protocol defines the minimum oratory, and is dependent upon (1) the pres- analyte uncertainty (MAU), and how the ence of interfering species in the exhaust gas RMSD is used to calculate the MAU. The (notably H O), (2) the optical alignment of 2 MAUim is the minimum concentration of the the gas cell and transfer optics, and (3) the ith analyte in the mth analytical region for quality of the reflective surfaces in the cell which the analytical uncertainty limit can (cell throughput). Under typical test condi- be maintained. Table 2 presents example val- tions (moisture content of up to 30 percent, ues of AU and MAU using the analytical re- 10 meter absorption path length, liquid ni- gion presented in Table 1. trogen-cooled IR detector, 0.5 cm¥1 resolution, and an interferometer sampling time of TABLE 2—EXAMPLE PRE-TEST PROTOCOL 60 seconds) a typical lower quantification CALCULATIONS FOR HYDROGEN CHLORIDE range for HCl is 0.1 to 1.0 ppm. 1.4 Data Quality Objectives HCl 1.4.1 In designing or configuring the analytical system, data quality is determined by Reference concentration (ppm-meters)/K ...... 11.2 measuring of the root mean square deviation Reference Band area ...... 2.881 (RMSD) of the absorbance values within a DL (ppm-meters)/K ...... 0.1117 chosen spectral (analytical) region. The AU ...... 0.2 CL (DL × AU) ...... 0.02234 RMSD provides an indication of the signal- FL (cm¥1) ...... 2679.83 to-noise ratio (S/N) of the spectral baseline. FU (cm¥1) ...... 2840.93 Appendix D of the FTIR Protocol (the adden- FC (cm¥1) ...... 2760.38 dum to Method 320 of this appendix) presents AAI (ppm-meters)/K ...... 0.06435

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TABLE 2—EXAMPLE PRE-TEST PROTOCOL CAL- ple where the moisture concentration is CULATIONS FOR HYDROGEN CHLORIDE—Con- close to that in the kiln gas. tinued 4.2 Sampling System Interferences. The principal sampling system interferant for meas- HCl uring HCl is water vapor. Steps must be taken to ensure that no condensation forms RMSD ...... 2.28E–03 anywhere in the probe assembly, sample MAU (ppm-meters)/K ...... 1.28E–01 lines, or analytical instrumentation. Cold MAU ppm at 22 meters and 250 °F ...... 0.2284 spots anywhere in the sampling system must be avoided. The extent of sampling system 2.0 Summary of Method bias in the FTIR analysis of HCl depends on 2.1 Principle concentrations of potential interferants, See Method 320 of this appendix. HCl can moisture content of the gas stream, tem- also undergo rotation transitions by absorb- perature of the gas stream, temperature of ing energy in the far-infrared spectral re- sampling system components, sample flow gion. The rotational transitions are super- rate, and reactivity of HCl with other species imposed on the vibrational fundamental to in the gas stream (e.g., ammonia). For meas- give a series of lines centered at the funda- uring HCl in a wet gas stream the tempera- mental vibrational frequency, 2885 cm-1. The tures of the gas stream, sampling compo- frequencies of absorbance and the pattern of nents, and the sample flow rate are of pri- rotational/vibrational lines are unique to mary importance. Analyte spiking with HCl HCl. When this distinct pattern is observed is performed to demonstrate the integrity of in an infrared spectrum of an unknown sam- the sampling system for transporting HCl ple, it unequivocally identifies HCl as a com- vapor in the flue gas to the FTIR instru- ponent of the mixture. The infrared spec- ment. See section 9 of this method for a com- trum of HCl is very distinctive and cannot be plete description of analyte spiking. confused with the spectrum of any other compound. See Reference 6. 5.0 Safety 2.2 Sampling and Analysis. See Method 320 5.1 Hydrogen chloride vapor is corrosive of this appendix. and can cause irritation or severe damage to 2.3 Operator Requirements. The analyst respiratory system, eyes and skin. Exposure must have knowledge of spectral patterns to to this compound should be avoided. choose an appropriate absorption path length or determine if sample dilution is 5.2 This method may involve sampling at necessary. The analyst should also under- locations having high positive or negative stand FTIR instrument operation well pressures, or high concentrations of haz- enough to choose instrument settings that ardous or toxic pollutants, and can not ad- are consistent with the objectives of the dress all safety problems encountered under analysis. these diverse sampling conditions. It is the responsibility of the tester(s) to ensure prop- 3.0 Definitions er safety and health practices, and to determine the applicability of regulatory limita- See appendix A of the FTIR Protocol. tions before performing this test method. 4.0 Interferences Leak-check procedures are outlined in section 8.2 of Method 320 of this appendix. This method will not measure HCl under conditions: (1) where the sample gas stream 6.0 Equipment and Supplies can condense in the sampling system or the OTE: Mention of trade names or specific instrumentation, or (2) where a high mois- N products does not constitute endorsement by ture content sample relative to the analyte the Environmental Protection Agency. concentrations imparts spectral interference due to the water vapor absorbance bands. 6.1 FTIR Spectrometer and Detector. An For measuring HCl the first (sampling) con- FTIR Spectrometer system (interferometer, sideration is more critical. Spectral inter- transfer optics, gas cell and detector) having ference from water vapor is not a significant the capability of measuring HCl to the pre- problem except at very high moisture levels determined minimum detectable level re- and low HCl concentrations. quired (see section 4.1.3 of the FTIR Pro- 4.1 Analytical Interferences. See Method 320 tocol). The system must also include an ac- of this appendix. curate means to control and/or measure the 4.1.1 Background Interferences. See Method temperature of the FTIR gas analysis cell, 320 of this appendix. and a personal computer with compatible 4.1.2 Spectral interferences. Water vapor software that provides real-time updates of can present spectral interference for FTIR the spectral profile during sample and spec- gas analysis of HCl. Therefore, the water tral collection. vapor in the spectra of kiln gas samples 6.2 Pump. Capable of evacuating the FTIR must be accounted for. This means preparing cell volume to 1 Torr (133.3 Pascals) within at least one spectrum of a water vapor sam- two minutes (for batch sample analysis).

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6.3 Mass Flow Meters/Controllers. To accu- materials non-reactive to HCl. The sampling rately measure analyte spike flow rate, hav- system and FTIR measurement system shall ing the appropriate calibrated range and a allow the operator to obtain at least six sam- stated accuracy of ±2 percent of the absolute ple spectra during a one-hour period. measurement value. This device must be 6.13 Barometer. For measurement of baro- calibrated with the major component of the metric pressure. calibration/spike gas (e.g., nitrogen) using an 6.14 Gas Sample Manifold. A distribution NIST traceable bubble meter or equivalent. manifold having the capabilities listed in Single point calibration checks should be sections 6.14.1 through 6.14.4; performed daily in the field. When spiking 6.14.1 Delivery of calibration gas directly HCl, the mass flow meter/controller should to the analytical instrumentation; be thoroughly purged before and after intro- 6.14.2 Delivery of calibration gas to the duction of the gas to prevent corrosion of the sample probe (system calibration or analyte interior parts. spike) via a heated traced sample line; 6.4 Polytetrafluoroethane tubing. Diameter and length suitable to connect cylinder regu- 6.14.3 Delivery of sample gas (kiln gas, lators. spiked kiln gas, or system calibrations) to 6.5 Stainless Steel tubing. Type 316 of ap- the analytical instrumentation; propriate length and diameter for heated 6.14.4 Delivery (optional) of a humidified connections. nitrogen sample stream. 6.6 Gas Regulators. Purgeable HCl regu- 6.15 Flow Measurement Device. Type S lator. Pitot tube (or equivalent) and Magnahelic 6.7 Pressure Gauge. Capable of measuring set for measurement of volumetric flow rate. pressure from 0 to 1000 Torr (133.3 Pa = 1 Torr) within ±5 percent. 7.0 Reagents and Standards 6.8 Sampling Probe. Glass, stainless steel HCl can be purchased in a standard com- or other appropriate material of sufficient pressed gas cylinder. The most stable HCl length and physical integrity to sustain cylinder mixture available has a concentra- heating, prevent adsorption of analytes and tion certified at ±5 percent. Such a cylinder capable of reaching gas sampling point. is suitable for performing analyte spiking ° ° 6.9 Sampling Line. Heated 180 C (360 F) because it will provide reproducible samples. and fabricated of either stainless steel, The stability of the cylinder can be mon- polytetrafluoroethane or other material that itored over time by periodically performing prevents adsorption of HCl and transports ef- direct FTIR analysis of cylinder samples. It fluent to analytical instrumentation. The is recommended that a 10–50 ppm cylinder of extractive sample line must have the capa- HCl be prepared having from 2–5 ppm SF6 as bility to transport sample gas to the analyt- a tracer compound. (See sections 7.1 through ical components as well as direct heated 7.3 of Method 320 of this appendix for a com- calibration spike gas to the calibration as- plete description of the use of existing HCl sembly located at the sample probe. It is im- reference spectra. See section 9.1 of Method portant to minimize the length of heated 320 of this appendix for a complete discussion sample line. of standard concentration selection.) 6.10 Particulate Filters. A sintered stainless steel filter rated at 20 microns or greater 8.0 Sample Collection, Preservation and may be placed at the inlet of the probe (for Storage removal of large particulate matter). A heated filter (Balston or equivalent) rated at 1 See also Method 320 of this appendix. micron is necessary for primary particulate 8.1 Pretest. A screening test is ideal for ob- matter removal, and shall be placed imme- taining proper data that can be used for pre- diately after the heated probe. The filter/fil- paring analytical program files. Information ter holder temperature should be maintained from literature surveys and source personnel at 180 °C (360 °F). is also acceptable. Information about the 6.11 Calibration/Analyte Spike Assembly. A sampling location and gas stream composi- heated three-way valve assembly (or equiva- tion is required to determine the optimum lent) to introduce surrogate spikes into the sampling system configuration for meas- sampling system at the outlet of the probe uring HCl. Determine the percent moisture before the primary particulate filter. of the kiln gas by Method 4 of appendix A to 6.12 Sample Extraction Pump. A leak-free part 60 of this chapter or by performing a heated head pump (KNF Neuberger or equiv- wet bulb/dry bulb measurement. Perform a alent) capable of extracting sample effluent preliminary traverse of the sample duct or through entire sampling system at a rate stack and select the sampling point(s). Ac- which prevents analyte losses and minimizes quire an initial spectrum and determine the analyzer response time. The pump should optimum operational pathlength of the in- have a heated by-pass and may be placed ei- strument. ther before the FTIR instrument or after. If 8.2 Leak-Check. See Method 320 of this ap- the sample pump is located upstream of the pendix, section 8.2 for direction on per- FTIR instrument, it must be fabricated from forming leak-checks.

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8.3 Background Spectrum. See Method 320 10 spectra with each spectrum being of a sep- of this appendix, section 8.5 for direction in arate cell volume of flue gas. Sampling in background spectral acquisition. this manner may only be performed if the 8.4 Pre-Test Calibration Transfer Standard native source analyte concentrations do not (Direct Instrument Calibration). See Method affect the test results. 320 of this appendix, section 8.3 for direction 8.7 Sample Conditioning in CTS spectral acquisition. 8.7.1 High Moisture Sampling. Kiln gas 8.5 Pre-Test System Calibration. See Method emitted from wet process cement kilns may 320 of this appendix, sections 8.6.1 through contain 3- to 40 percent moisture. Zinc sele- 8.6.2 for direction in performing system cali- nide windows or the equivalent should be bration. used when attempting to analyze hot/wet 8.6 Sampling kiln gas under these conditions to prevent 8.6.1 Extractive System. An extractive sys- dissolution of water soluble window mate- ° ° tem maintained at 180 C (360 F) or higher rials (e.g., KBr). which is capable of directing a total flow of 8.7.2 Sample Dilution. The sample may be at least 12 L/min to the sample cell is re- diluted using an in-stack dilution probe, or quired (References 1 and 2). Insert the probe an external dilution device provided that the into the duct or stack at a point rep- sample is not diluted below the instrument’s resenting the average volumetric flow rate quantification range. As an alternative to and 25 percent of the cross sectional area. using a dilution probe, nitrogen may be dy- Co-locate an appropriate flow monitoring de- namically spiked into the effluent stream in vice with the sample probe so that the flow the same manner as analyte spiking. A con- rate is recorded at specified time intervals stant dilution rate shall be maintained during emission testing (e.g., differential throughout the measurement process. It is pressure measurements taken every 10 min- critical to measure and verify the exact dilu- utes during each run). tion ratio when using a dilution probe or the 8.6.2 Batch Samples. Evacuate the absorbance cell to 5 Torr (or less) absolute pressure nitrogen spiking approach. Calibrating the before taking first sample. Fill the cell with system with a calibration gas containing an kiln gas to ambient pressure and record the appropriate tracer compound will allow de- infrared spectrum, then evacuate the cell termination of the dilution ratio for most until there is no further evidence of infrared measurement systems. The tester shall absorption. Repeat this procedure, collecting specify the procedures used to determine the a total of six separate sample spectra within dilution ratio, and include these calibration a 1-hour period. results in the report. 8.6.3 Continuous Flow Through Sampling. 8.8 Sampling QA, Data Storage and Report- Purge the FTIR cell with kiln gas for a time ing. See the FTIR Protocol. Sample integra- period sufficient to equilibrate the entire tion times shall be sufficient to achieve the sampling system and FTIR gas cell. The required signal-to-noise ratio, and all sample time required is a function of the mechanical spectra should have unique file names. Two response time of the system (determined by copies of sample interferograms and proc- performing the system calibration with the essed spectra will be stored on separate com- CTS gas or equivalent), and by the chemical puter media. For each sample spectrum the reactivity of the target analytes. If the efflu- analyst must document the sampling condi- ent target analyte concentration is not vari- tions, the sampling time (while the cell was able, observation of the spectral up-date of being filled), the time the spectrum was re- the flowing gas sample should be performed corded, the instrumental conditions (path until equilibration of the sample is achieved. length, temperature, pressure, resolution, in- Isolate the gas cell from the sample flow by tegration time), and the spectral file name. directing the purge flow to vent. Record the A hard copy of these data must be main- spectrum and pressure of the sample gas. tained until the test results are accepted. After spectral acquisition, allow the sample 8.9 Signal Transmittance. Monitor the sig- gas to purge the cell with at least three vol- nal transmittance through the instrumental umes of kiln gas. The time required to ade- system. If signal transmittance (relative to quately purge the cell with the required vol- the background) drops below 95 percent in ume of gas is a function of (1) cell volume, (2) any spectral region where the sample does flow rate through the cell, and (3) cell de- not absorb infrared energy, then a new back- sign. It is important that the gas introduc- ground spectrum must be obtained. tion and vent for the FTIR cell provides a 8.10 Post-test CTS. After the sampling run complete purge through the cell. completion, record the CTS spectrum. Anal- 8.6.4 Continuous Sampling. In some cases it ysis of the spectral band area used for quan- is possible to collect spectra continuously tification from pre- and post-test CTS spec- while the FTIR cell is purged with sample tra should agree to within ±5 percent or cor- gas. The sample integration time, tss, the rective action must be taken. sample flow rate through the gas cell, and 8.11 Post-test QA. The sample spectra shall the sample integration time must be chosen be inspected immediately after the run to so that the collected data consist of at least verify that the gas matrix composition was

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close to the assumed gas matrix, (this is nec- 9.1.1 An HCl standard of approximately 50 essary to account for the concentrations of ppm in a balance of ultra pure nitrogen is the interferants for use in the analytical recommended. The SF6 (tracer) concentra- analysis programs), and to confirm that the tion shall be 2 to 5 ppm depending upon the sampling and instrumental parameters were measurement pathlength. The spike ratio appropriate for the conditions encountered. (spike flow/total flow) shall be no greater than 1:10, and an ideal spike concentration 9.0 Quality Control should approximate the native effluent concentration. Use analyte spiking to verify the effective- 9.1.2 The ideal spike concentration may ness of the sampling system for the target not be achieved because the target con- compounds in the actual kiln gas matrix. QA centration cannot be accurately predicted spiking shall be performed before and after prior to the field test, and limited calibra- each sample run. QA spiking shall be per- tion standards will be available during test- formed after the pre- and post-test CTS di- ing. Therefore, practical constraints must be rect and system calibrations. The system bi- applied that allow the tester to spike at an ases calculated from the pre- and post-test anticipated concentration. For these tests, ± dynamic analyte spiking shall be within 30 the analyte concentration contributed by percent for the spiked surrogate analytes for the HCl standard spike should be 1 to 5 ppm the measurements to be considered valid. or should more closely approximate the na- See sections 9.3.1 through 9.3.2 for the req- tive concentration if it is greater. uisite calculations. Measurement of the un- 9.2 Spike Procedure diluted spike (direct-to-cell measurement) 9.2.1 A spiking/sampling apparatus is involves sending dry, spike gas to the FTIR shown in Figure 2. Introduce the spike/tracer cell, filling the cell to 1 atmosphere and ob- gas mixture at a constant flow (±2 percent) taining the spectrum of this sample. The di- rate at approximately 10 percent of the total rect-to-cell measurement should be per- sample flow. (For example, introduce the formed before each analyte spike so that the surrogate spike at 1 L/min 20 cc/min, into a recovery of the dynamically spiked analytes total sample flow rate of 10 L/min). The may be calculated. Analyte spiking is only spike must be pre-heated before introduction effective for assessing the integrity of the into the sample matrix to prevent a localized sampling system when the concentration of condensation of the gas stream at the spike HCl in the source does not vary substan- introduction point. A heated sample trans- tially. Any attempt to quantify an analyte port line(s) containing multiple transport recovery in a variable concentration matrix tubes within the heated bundle may be used will result in errors in the expected con- to spike gas up through the sampling system centration of the spiked sample. If the kiln to the spike introduction point. Use a cali- gas target analyte concentrations vary by brated flow device (e.g., mass flow meter/ more than ±5 percent (or 5 ppm, whichever is controller), to monitor the spike flow as in- greater) in the time required to acquire a dicated by a calibrated flow meter or con- sample spectrum, it may be necessary to: (1) troller, or alternately, the SF6 tracer ratio Use a dual sample probe approach, (2) use may be calculated from the direct measure- two independent FTIR measurement sys- ment and the diluted measurement. It is tems, (3) use alternate QA/QC procedures, or often desirable to use the tracer approach in (4) postpone testing until stable emission calculating the spike/total flow ratio be- concentrations are achieved. (See section cause of the difficulty in accurately meas- 9.2.3 of this method). It is recommended that uring hot/wet total flow. The tracer tech- a laboratory evaluation be performed before nique has been successfully used in past vali- attempting to employ this method under ac- dation efforts (Reference 1). tual field conditions. The laboratory evalua- 9.2.2 Perform a direct-to-cell measure- tion shall include (1) performance of all ap- ment of the dry, undiluted spike gas. Intro- plicable calculations in section 4 of the FTIR duce the spike directly to the FTIR cell, by- Protocol; (2) simulated analyte spiking ex- passing the sampling system. Fill cell to 1 periments in dry (ambient) and humidified atmosphere and collect the spectrum of this sample matrices using HCl; and (3) perform- sample. Ensure that the spike gas has equili- ance of bias (recovery) calculations from brated to the temperature of the measure- analyte spiking experiments. It is not nec- ment cell before acquisition of the spectra. essary to perform a laboratory evaluation Inspect the spectrum and verify that the gas before every field test. The purpose of the is dry and contains negligible CO2. Repeat laboratory study is to demonstrate that the the process to obtain a second direct-to-cell actual instrument and sampling system con- measurement. Analysis of spectral band figuration used in field testing meets the re- areas for HCl from these duplicate measure- quirements set forth in this method. ments should agree to within ±5 percent of 9.1 Spike Materials. Perform analyte spik- the mean. ing with an HCl standard to demonstrate the 9.2.3 Analyte Spiking. Determine whether integrity of the sampling system. the kiln gas contains native concentrations

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of HCl by examination of preliminary spec- gas temperature before it is introduced to tra. Determine whether the concentration the kiln gas stream. varies significantly with time by observing a 9.2.3.3.2 The spike flow rate must be con- continuously up-dated spectrum of sample stant and accurately measured. gas in the flow-through sampling mode. If 9.2.3.3.3 The total flow must also be meas- the concentration varies by more than ±5 ured continuously and reliably or the dilu- percent during the period of time required to tion ratio must otherwise be verified before acquire a spectra, then an alternate ap- and after a run by introducing a spike of a proach should be used. One alternate ap- non-reactive, stable compound (i.e., tracer). proach uses two sampling lines to convey 9.2.3.3.4 The tracer must be inert to the sample to the gas distribution manifold. One sampling system components, not contained of the sample lines is used to continuously in the effluent gas, and readily detected by extract unspiked kiln gas from the source. the analytical instrumentation. Sulfur The other sample line serves as the analyte hexafluoride (SF6) has been used successfully spike line. One FTIR system can be used in (References 1 and 2) for this purpose. this arrangement. Spiked or unspiked sam- 9.3 Calculations ple gas may be directed to the FTIR system 9.3.1 Recovery. Calculate the percent re- from the gas distribution manifold, with the covery of the spiked analytes using equa- need to purge only the components between tions 1 and 2. the manifold and the FTIR system. This approach minimizes the time required to ac- SS−−()1 DF quire an equilibrated sample of spiked or %()R =×100 mu 1 unspiked kiln gas. If the source varies by × DF Cs more than ±5 percent (or 5 ppm, whichever is greater) in the time it takes to switch from Sm = Mean concentration of the analyte the unspiked sample line to the spiked sam- spiked effluent samples (observed). ple line, then analyte spiking may not be a =×+ − feasible means to determine the effective- CDFCSesu()12 DF () ness of the sampling system for the HCl in Ce = Expected concentration of the spiked the sample matrix. A second alternative is to samples (theoretical). use two completely independent FTIR meas- DF = Dilution Factor (Total flow/Spike urement systems. One system would measure flow). Total flow = spike flow plus efflu- unspiked samples while the other system ent flow. would measure the spiked samples. As a last Cs = cylinder concentration of spike gas. option, (where no other alternatives can be Su = native concentration of analytes in used) a humidified nitrogen stream may be unspiked samples. generated in the field which approximates The spike dilution factor may be confirmed the moisture content of the kiln gas. by measuring the total flow and the spike Analyte spiking into this humidified stream can be employed to assure that the sampling flow directly. Alternately, the spike dilution system is adequate for transporting the HCl can be verified by comparing the concentra- to the FTIR instrumentation. tion of the tracer compound in the spiked 9.2.3.1 Adjust the spike flow rate to ap- samples (diluted) to the tracer concentration proximately 10 percent of the total flow by in the direct (undiluted) measurement of the metering spike gas through a calibrated spike gas. mass flowmeter or controller. Allow spike If SF6 is the tracer gas, then flow to equilibrate within the sampling sys- = tem before analyzing the first spiked kiln Df[SF66 ] spike / [SF ] direct (3) gas samples. A minimum of two consecutive [SF6]spike = the diluted SF6 concentration spikes are required. Analysis of the spectral measured in a spiked sample. band area used for quantification should [SF6]direct = the SF6 concentration measured agree to within ±5 percent or corrective ac- directly. tion must be taken. 9.3.2 Bias. The bias may be determined by 9.2.3.2 After QA spiking is completed, the the difference between the observed spike sampling system components shall be purged value and the expected response (i.e., the with nitrogen or dry air to eliminate traces equivalent concentration of the spiked mate- of the HCl compound from the sampling sys- rial plus the analyte concentration adjusted tem components. Acquire a sample spectra of for spike dilution). Bias is defined by section the nitrogen purge to verify the absence of 6.3.1 of EPA Method 301 of this appendix the calibration mixture. (Reference 8) as, 9.2.3.3 Analyte spiking procedures must be carefully executed to ensure that mean- =− ingful measurements are achieved. The re- BSme C (4) quirements of sections 9.2.3.3.1 through Where: 9.2.3.3.4 shall be met. B = Bias at spike level. 9.2.3.3.1 The spike must be in the vapor Sm = Mean concentration of the analyte phase, dry, and heated to (or above) the kiln spiked samples.

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Ce = Expected concentration of the analyte Any mathematical transformations must be in spiked samples. documented and reproducible. Reference 9 Acceptable recoveries for analyte spiking are provides additional information about FTIR ±30 percent. Application of correction factors instrumentation. to the data based upon bias and recovery cal- 11.0 Analytical Procedure culations is subject to the approval of the Administrator. A full description of the analytical procedures is given in sections 4.6–4.11, sections 5, 10.0 Calibration and Standardization 6, and 7, and the appendices of the FTIR Pro- 10.1 Calibration transfer standards (CTS). tocol. Additional description of quantitative The EPA Traceability Protocol gases or spectral analysis is provided in References 10 NIST traceable standards, with a minimum and 11. accuracy of ±2 percent shall be used. For 12.0 Data Analysis and Calculations other requirements of the CTS, see the FTIR Protocol section 4.5. Data analysis is performed using appro- 10.2 Signal-to-Noise Ratio (S/N). The S/N priate reference spectra whose concentra- shall be less than the minimum acceptable tions can be verified using CTS spectra. Var- measurement uncertainty in the analytical ious analytical programs (References 10 and regions to be used for measuring HCl. 11) are available to relate sample absorbance 10.3 Absorbance Pathlength. Verify the ab- to a concentration standard. Calculated con- sorbance path length by comparing CTS centrations should be verified by analyzing spectra to reference spectra of the calibra- spectral baselines after mathematically sub- tion gas(es). tracting scaled reference spectra from the 10.4 Instrument Resolution. Measure the sample spectra. A full description of the data line width of appropriate CTS band(s) to analysis and calculations may be found in verify instrumental resolution. the FTIR Protocol (sections 4.0, 5.0, 6.0 and 10.5 Apodization Function. Choose the ap- appendices). propriate apodization function. Determine 12.1 Calculated concentrations in sample any appropriate mathematical trans- spectra are corrected for differences in ab- formations that are required to correct in- sorption pathlength between the reference strumental errors by measuring the CTS. and sample spectra by

= × × CLLTTCcorr() r s() s r() calc ()5

Where: intensities between reference spectra and the sample spectra. Ccorr = The pathlength corrected concentration. 13.0 Method Performance Ccalc = The initial calculated concentration (output of the multicomponent analysis A description of the method performance program designed for the compound). may be found in the FTIR Protocol. This method is self validating provided the re- Lr = The pathlength associated with the reference spectra. sults meet the performance specification of the QA spike in sections 9.0 through 9.3 of Ls = The pathlength associated with the sample spectra. this method. Ts = The absolute temperature (K) of the 14.0 Pollution Prevention sample gas.

Tr = The absolute temperature (K) at which This is a gas phase measurement. Gas is reference spectra were recorded. extracted from the source, analyzed by the instrumentation, and discharged through the 12.2 The temperature correction in equa- instrument vent. tion 5 is a volumetric correction. It does not account for temperature dependence of rota- 15.0 Waste Management tional-vibrational relative line intensities. Whenever possible, the reference spectra Gas standards of HCl are handled according used in the analysis should be collected at a to the instructions enclosed with the mate- temperature near the temperature of the rial safety data sheet. FTIR cell used in the test to minimize the 16.0 References calculated error in the measurement (FTIR Protocol, appendix D). Additionally, the ana- 1. ‘‘Laboratory and Field Evaluation of a lytical region chosen for the analysis should Methodology for Determination of Hydrogen be sufficiently broad to minimize errors Chloride Emissions From Municipal and Haz- caused by small differences in relative line ardous Waste Incinerators,’’ S.C.

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Steinsberger and J.H. Margeson. Prepared national Incineration Conference, Houston, for U.S. Environmental Protection Agency, TX. May 10, 1994. Research Triangle Park, NC. NTIS Report 6. ‘‘Molecular Vibrations; The Theory of No. PB89–220586. (1989). Infrared and Raman Vibrational Spectra,’’ E. 2. ‘‘Evaluation of HCl Measurement Tech- Bright Wilson, J.C. Decius, and P.C. Cross, niques at Municipal and Hazardous Waste In- Dover Publications, Inc., 1980. For a less incinerators,’’ S.A. Shanklin, S.C. tensive treatment of molecular rotational- Steinsberger, and L. Cone, Entropy, Inc. Pre- vibrational spectra see, for example, ‘‘Phys- pared for U.S. Environmental Protection ical Chemistry,’’ G.M. Barrow, chapters 12, Agency, Research Triangle Park, NC. NTIS 13, and 14, McGraw Hill, Inc., 1979. Report No. PB90–221896. (1989). 7. ‘‘Laboratory and Field Evaluations of Ammonium Chloride Interference in Method 3. ‘‘Fourier Transform Infrared (FTIR) 26,’’ U.S. Environmental Protection Agency Method Validation at a Coal Fired-Boiler,’’ Report, Entropy, Inc., EPA Contract No. Entropy, Inc. Prepared for U.S. Environ- 68D20163, Work Assignment No. I–45. mental Protection Agency, Research Tri- 8. 40 CFR 63, appendix A. Method 301—Field angle Park, NC. EPA Publication No. EPA– Validation of Pollutant Measurement Meth- 454/R95–004. NTIS Report No. PB95–193199. ods from Various Waste Media. (1993). 9. ‘‘Fourier Transform Infrared Spectrom- 4. ‘‘Field Validation Test Using Fourier etry,’’ Peter R. Griffiths and James de Transform Infrared (FTIR) Spectrometry To Haseth, Chemical Analysis, 83, 16–25, (1986), Measure Formaldehyde, Phenol and Meth- P.J. Elving, J.D. Winefordner and I.M. anol at a Wool Fiberglass Production Facil- Kolthoff (ed.), John Wiley and Sons. ity.’’ Draft. U.S. Environmental Protection 10. ‘‘Computer-Assisted Quantitative Infra- Agency Report, Entropy, Inc., EPA Contract red Spectroscopy,’’ Gregory L. McClure (ed.), No. 68D20163, Work Assignment I–32. ASTM Special Publication 934 (ASTM), 1987. 5. Kinner, L.L., Geyer, T.G., Plummer, 11. ‘‘Multivariate Least-Squares Methods G.W., Dunder, T.A., Entropy, Inc. ‘‘Applica- Applied to the Quantitative Spectral Anal- tion of FTIR as a Continuous Emission Mon- ysis of Multicomponent Mixtures,’’ Applied itoring System.’’ Presentation at 1994 Inter- Spectroscopy, 39(10), 73–84, 1985.

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METHOD 323—MEASUREMENT OF FORMALDE- present when combusting natural gas. Acet- HYDE EMISSIONS FROM NATURAL GAS-FIRED aldehyde has been reported to be a signifi- STATIONARY SOURCES—ACETYL ACETONE cant interference only when present at con- DERIVITIZATION METHOD centrations above 50 ppmv. However, GRI re- 1.0 Introduction. This method describes ports that the concentration of acetaldehyde the sampling and analysis procedures of the from gas-fired sources is very low (typically acetyl acetone colorimetric method for below the FTIR detection limit of around 0.5 measuring formaldehyde emissions in the ex- ppmv); therefore, the potential positive bias haust of natural gas-fired, stationary com- due to acetaldehyde interference is expected bustion sources. This method, which was pre- to be negligible. pared by the Gas Research Institute (GRI), is 5.0 Safety based on the Chilled Impinger Train Method for Methanol, Acetone, Acetaldehyde, Meth- 5.1 Prior to applying the method in the yl Ethyl Ketone, and Formaldehyde (Tech- field, a site-specific Health and Safety Plan nical Bulletin No. 684) developed and pub- should be prepared. General safety pre- lished by the National Council of the Paper cautions include the use of steel-toed boots, Industry for Air and Stream Improvement, safety glasses, hard hats, and work gloves. In Inc. (NCASI). However, this method has been certain cases, facility policy may require the prepared specifically for formaldehyde and use of fire-resistant clothing while on-site. does not include specifications (e.g., equip- Since the method involves testing at high- ment and supplies) and procedures (e.g., sam- temperature sampling locations, precautions pling and analytical) for methanol, acetone, must be taken to limit the potential for ex- acetaldehyde, and methyl ethyl ketone. To posure to high-temperature gases and sur- obtain reliable results, persons using this faces while inserting or removing the sample method should have a thorough knowledge of probe. In warm locations, precautions must at least Methods 1 and 2 of 40 CFR part 60, also be taken to avoid dehydration. appendix A–1; Method 3 of 40 CFR part 60, ap- 5.2 Potential chemical hazards associated pendix A–2; and Method 4 of 40 CFR part 60, with sampling include formaldehyde, nitro- appendix A–3. gen oxides (NOX), and carbon monoxide (CO). Formalin solution, used for field spiking, is 1.1 Scope and Application an aqueous solution containing formalde- 1.1.1 Analytes. The only analyte measured hyde and methanol. Formaldehyde is a skin, by this method is formaldehyde (CAS Num- eye, and respiratory irritant and a car- ber 50–00–0). cinogen, and should be handled accordingly. 1.1.2 Applicability. This method is for Eye and skin contact and inhalation of form- analyzing formaldehyde emissions from un- aldehyde vapors should be avoided. Natural controlled and controlled natural gas-fired, gas-fired combustion sources can potentially stationary combustion sources. emit CO at toxic concentrations. Care should 1.1.3 Data Quality Objectives. If you ad- be taken to minimize exposure to the sample here to the quality control and quality as- gas while inserting or removing the sample surance requirements of this method, then probe. If the work area is enclosed, personal you and future users of your data will be CO monitors should be used to insure that able to assess the quality of the data you ob- the concentration of CO in the work area is tain and estimate the uncertainty in the maintained at safe levels. measurements. 5.3 Potential chemical hazards associated 2.0 Summary of Method. An emission with the analytical procedures include ace- sample from the combustion exhaust is tyl acetone and glacial acetic acid. Acetyl drawn through a midget impinger train con- acetone is an irritant to the skin and res- taining chilled reagent water to absorb form- piratory system, as well as being moderately aldehyde. The formaldehyde concentration toxic. Glacial acetic acid is highly corrosive in the impinger is determined by reaction and is an irritant to the skin, eyes, and res- with acetyl acetone to form a colored deriva- piratory system. Eye and skin contact and tive which is measured colorimetrically. inhalation of vapors should be avoided. Ace- tyl acetone and glacial acetic acid have flash 3.0 Definitions points of 41 °C (105.8 °F) and 43 °C (109.4 °F), [Reserved] respectively. Exposure to heat or flame 4.0 Interferences. The presence of acetal- should be avoided. dehyde, amines, polymers of formaldehyde, 6.0 Equipment and Supplies periodate, and sulfites can cause interferences with the acetyl acetone procedure 6.1 Sampling Probe. Quartz glass probe which is used to determine the formaldehyde with stainless steel sheath or stainless steel concentration. However, based on experience probe. gained from extensive testing of natural gas- 6.2 Teflon Tubing. Teflon tubing to con- fired combustion sources using FTIR to nect the sample probe to the impinger train. measure a variety of compounds, GRI ex- A heated sample line is not needed since the pects only acetaldehyde to be potentially sample transfer system is rinsed to recover

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condensed formaldehyde and the rinsate 8.0 Sample Collection, Preservation, Storage, combined with the impinger contents prior and Transport to sample analysis. 6.3 Midget Impingers. Three midget 8.1 Pre-test impingers are required for sample collection. 8.1.1 Collect information about the site The first impinger serves as a moisture characteristics such as exhaust pipe diame- knockout, the second impinger contains 20 ter, gas flow rates, port location, access to mL of reagent water, and the third impinger ports, and safety requirements during a pre- contains silica gel to remove residual mois- test site survey. You should then decide the ture from the sample prior to the dry gas sample collection period per run and the tar- meter. get sample flow rate based on your best esti- 6.4 Vacuum Pump. Vacuum pump capable mate of the formaldehyde concentration of delivering a controlled extraction flow likely to be present. You want to assure that rate between 0.2 and 0.4 L/min. sufficient formaldehyde is captured in the 6.5 Flow Measurement Device. A rotam- impinger solution so that it can be measured precisely by the spectrophotometer. You eter or other flow measurement device is re- may use Equation 323–1 to design your test quired to indicate consistent sample flow. program. As a guideline for optimum per- 6.6 Dry Gas Meter. A dry gas meter is formance, if you can, design your test so used to measure the total sample volume that the liquid concentration (Cl) is approxi- collected. The dry gas meter must be suffi- mately 10 times the assumed spectrophotom- ciently accurate to measure the sample vol- eter detection limit of 0.2 μg/mL. However, ume to within 2 percent, calibrated at the se- since actual detection limits are instrument lected flow rate and conditions actually en- specific, we also suggest that you confirm countered during sampling, and equipped that the laboratory equipment can meet or with a temperature sensor (dial thermom- exceed this detection limit. eter, or equivalent) capable of measuring 8.1.2 Prepare and then weigh the midget temperature accurately to within 3 °C (5.4 impingers prior to configuring the sampling °F). train. The first impinger is initially dry. The 6.7 Spectrophotometer. A spectrophotom- second impinger contains 20 mL of reagent eter is required for formaldehyde analysis, water, and the third impinger contains silica and must be capable of measuring absorb- gel that is added before weighing the im- ance at 412 nm. pinger. Each prepared impinger is weighed and the pre-sampling weight is recorded to 7.0 Reagents and Standards the nearest 0.5 gm. 8.1.3 Assemble the sampling train (see 7.1 Sampling Reagents Figure 1). Ice is packed around the impingers in order to keep them cold during sample 7.1.1 Reagent water. Deionized, distilled, collection. A small amount of water may be organic-free water. This water is used as the added to the ice to improve thermal transfer. capture solution, for rinsing the sample 8.1.4 Perform a sampling system leak probe, sample line, and impingers at the check (from the probe tip to the pump out- completion of the sampling run, in reagent let) as follows: Connect a rotameter to the dilutions, and in blanks. outlet of the pump. Close off the inlet to the 7.1.2 Ice. Ice is necessary to pack around probe and observe the leak rate. The leak the impingers during sampling in order to rate must be less than 2 percent of the keep the impingers cold. Ice is also needed planned sampling rate of 0.2 or 0.4 L/min. for sample transport and storage. 8.1.5 Source gas temperature and static pressure should also be considered prior to 7.2 Analysis field sampling to ensure adequate safety pre- 7.2.1 Acetyl acetone Reagent. Prepare the cautions during sampling. acetyl acetone reagent by dissolving 15.4 g of 8.2 Sample Collection ammonium acetate in 50 mL of reagent water in a 100-mL volumetric flask. To this 8.2.1 Set the sample flow rate between 0.2– solution, add 0.20 mL of acetyl acetone and 0.4 L/min, depending upon the anticipated 0.30 mL of glacial acetic acid. Mix the solu- concentration of formaldehyde in the engine tion thoroughly, then dilute to 100 mL with exhaust. (You may have to refer to published reagent water. The solution can be stored in data for anticipated concentration levels— a brown glass bottle in the refrigerator, and see References 5 and 6.) If no information is is stable for at least two weeks. available for the anticipated levels of form- 7.2.2 Formaldehyde. Reagent grade. aldehyde, use the higher sampling rate of 0.4 7.2.3 Ammonium Acetate L/min. 7.2.4 Glacial Acetic Acid 8.2.2 Record the sampling flow rate every 5 to 10 minutes during the sample collection period.

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NOTE: It is critical that you do not sample bined rinse volumes should not exceed 10 mL. at a flow rate higher than 0.4 L/min. Sam- However, in cases where a long, flexible ex- pling at higher flow rates may reduce form- tension line must be used to connect the aldehyde collection efficiency resulting in sample probe to the sample box, sufficient measured formaldehyde concentrations that water must be used to rinse the connecting are less than the actual concentrations. line to insure that any sample that may 8.2.3 Monitor the amount of ice sur- have collected there is recovered. The vol- rounding the impingers and add ice as nec- ume of the rinses during sample recovery essary to maintain the proper impinger tem- should not be excessive as this may result in perature. Remove excess water as needed to your having to use a larger VOA bottle. This maintain an adequate amount of ice. in turn would raise the detection limit of the 8.2.4 Record measured leak rate, begin- method since after combining the rinses with ning and ending times and dry gas meter the impinger catches in the VOA bottle, the readings for each sampling run, impinger bottle should be filled with reagent water to weights before and after sampling, and sam- eliminate the headspace in the sample vial. pling flow rates and dry gas meter exhaust Keep the sample bottles over ice until ana- temperature every 5 to 10 minutes during the lyzed on-site or received at the laboratory. run, in a signed and dated notebook. Samples should be analyzed as soon as pos- 8.2.5 If possible, monitor and record the sible to minimize possible sample degrada- fuel flow rate to the engine and the exhaust tion. Based on a limited number of previous oxygen concentration during the sampling analyses, samples held in refrigerated condi- period. This data can be used to estimate the tions showed some sample degradation over engine exhaust flow rate based on the Meth- time. od 19 approach. This approach, if accurate fuel flow rates can be determined, is pre- 8.4 Quality Control Samples ferred for reciprocating IC engine exhaust 8.4.1 Field Duplicates. During at least one flow rate estimation due to the pulsating na- run, a pair of samples should be collected ture of the engine exhaust. The F–Factor concurrently and analyzed as separate sam- procedures described in Method 19 may be ples. Results of the field duplicate samples used based on measurement of fuel flow rate should be identified and reported with the and exhaust oxygen concentration. One ex- sample results. The percent difference in example equation is Equation 323–2. haust (stack) concentration indicated by 8.3 Post-test. Perform a sampling system field duplicates should be within 20 percent leak-check (from the probe tip to pump out- of their mean concentration. Data are to be let). Connect a rotameter to the outlet of the flagged as suspect if the duplicates do not pump. Close off the inlet to the probe and ob- meet the acceptance criteria. serve the leak rate. The leak rate must be 8.4.2 Spiked Samples. An aliquot of one less than 2 percent of the sampling rate. sample from each source sample set should Weigh and record each impinger imme- be spiked at 2 to 3 times the formaldehyde diately after sampling to determine the level found in the unspiked sample. It is also moisture weight gain. The impinger weights recommended that a second aliquot of the are measured before transferring the im- same sample be spiked at around half the pinger contents, and before rinsing the sam- level of the first spike; however, the second ple probe and sample line. The moisture con- spike is not mandatory. The results are ac- tent of the exhaust gas is determined by ceptable if the measured spike recovery is 80 measuring the weight gain of the impinger to 120 percent. Use Equation 323–4. Data are solutions and volume of gas sampled as de- to be flagged as suspect if the spike recovery scribed in Method 4. Rinse the sample probe do not meet the acceptance criteria. and sample line with reagent water. Transfer 8.4.3 Field Blank. A field blank consisting the impinger catch to an amber 40-mL VOA of reagent water placed in a clean impinger bottle with a Teflon-lined cap. If there is a train, taken to the test site but not sampled, small amount of liquid in the dropout im- then recovered and analyzed in the same pinger (<10 mL), the impinger catches can be manner as the other samples, should be col- combined in one 40 mL VOA bottle. If there lected with each set of source samples. The is a larger amount of liquid in the dropout field blank results should be less than 50 per- impinger, use a larger VOA bottle to com- cent of the lowest calibration standard used bine the impinger catches. Rinse the in the sample analysis. If this criteria is not impingers and combine the rinsings from the met, the data should be flagged as suspect. sample probe, sample line, and impingers with the impinger catch. In general, com- 9.0 Quality Control

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QA/QC Acceptance Frequency Corrective action

Leak-check—Sections 8.1.4, <2% of Sampling rate Pre- and Post-sampling ...... Pre-sampling: Repair leak 8.3. and recheck Post-sampling: Flag data and repeat run if for regulatory compliance. Sample flow rate ...... Between 0.2 and 0.4 L/min Throughout sampling ...... Adjust. VOA vial headspace ...... No headspace ...... After sample recovery ...... Flag data. Sample preservation ...... Maintain on ice ...... After sample recovery ...... Flag data. Sample hold time ...... 14 day maximum ...... After sample recovery ...... Flag data. Field Duplicates—Section Within 20% of mean of origi- One duplicate per source Flag data. 8.4.1. nal and duplicate sample. sample set. Spiked Sample—Section 8.4.2 Recovery between 80 and One spike per source sample Flag data. 120%. set. Field Blank—Section 8.4.3 ...... <50% of the lowest calibration One blank per source sample Flag data. standard. set. Calibration Linearity—Section Correlation coefficient of 0.99 Per source sample set ...... Repeat calibration proce- 10.1. or higher. dures. Calibration Check Standard— Within 10% of theoretical One calibration check per Repeat check, remake stand- Section 10.3. value. source sample set. ard and repeat, repeat calibration. Lab Duplicates—Section Within 10% of mean of origi- One duplicate per 10 samples Flag data. 11.2.1. nal and duplicate sample analysis. Analytical Blanks—Section <50% of the lowest calibration One blank per source sample Clean glassware/analytical 11.2.2. standard. set. equipment and repeat.

10.0 Calibration and Standardization still unacceptable, a new calibration curve must be prepared using freshly prepared 10.1 Spectrophotometer Calibration. Pre- standards. pare a stock solution of 10 μg/mL formaldehyde. Prepare a series of calibration stand- 11.0 Analytical Procedure ards from the stock solution by adding 0, 0.1, 11.1 Sample Analysis. A 2.0-mL aliquot of 0.3, 0.7, 1.0, and 1.5 mL of stock solution (cor- the impinger catch/rinsate is transferred to a responding to 0, 1.0, 3.0, 7.0, 10.0, and 15.0 μg screw-capped vial. Two mL of the acetyl ace- formaldehyde, respectively) to screw-capped tone reagent are added and the solution is vials. Adjust each vial’s volume to 2.0 mL thoroughly mixed. Once mixed, the vial is with reagent water. At this point the con- placed in a water bath (or heating block) at centration of formaldehyde in the standards 60 °C for 10 minutes. Remove the vial and μ is 0.0, 0.5, 1.5, 3.5, 5.0, and 7.5 g/mL, respec- allow to cool to room temperature. Transfer tively. Add 2.0 mL of acetyl acetone reagent, the solution to a cuvette and measure the thoroughly mix the solution, and place the absorbance using the spectrophotometer at vials in a water bath (or heating block) at 60 412 nm. The quantity of formaldehyde ° C for 10 minutes. Remove the vials and present is determined by comparing the sam- allow to cool to room temperature. Transfer ple response to the calibration curve. Use each solution to a cuvette and measure the Equation 323–5. If the sample response is out absorbance at 412 nm using the spectro- of the calibration range, the sample must be photometer. Develop a calibration curve diluted and reanalyzed. Such dilutions must from the analytical results of these stand- be performed on another aliquot of the origi- ards. The acceptance criteria for the spectro- nal sample before the addition of the acetyl photometer calibration is a correlation coef- acetone reagent. The full procedure is re- ficient of 0.99 or higher. If this criteria is not peated with the diluted sample. met, the calibration procedures should be re- 11.2 Analytical Quality Control peated. 11.2.1 Laboratory Duplicates. Two 10.2 Spectrophotometer Zero. The spec- aliquots of one sample from each source trophotometer should be zeroed with reagent sample set should be prepared and analyzed water when analyzing each set of samples. (with a minimum of one pair of aliquots for 10.3 Calibration Checks. Calibration every 10 samples). The percent difference be- checks consisting of analyzing a standard tween aliquot analysis should be within 10 separate from the calibration standards percent of their mean. Use Equation 323–3. must be performed with each set of samples. Data are flagged if the laboratory duplicates The calibration check standard should not be do not meet this criteria. prepared from the calibration stock solution. 11.2.2 Analytical blanks. Blank samples The result of the check standard must be (reagent water) should be incorporated into within 10 percent of the theoretical value to each sample set to evaluate the possible be acceptable. If the acceptance criteria are presence of any cross-contamination. The ac- not met, the standard must be reanalyzed. If ceptance criteria for the analytical blank is

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less than 50 percent of the lowest calibration m = mass of formaldehyde in liquid sample, standard. If the analytical blank does not mg meet this criteria, the glassware/analytical Pstd = Standard pressure, 760 mm Hg (29.92 equipment should be cleaned and the analyt- in.Hg) ical blank repeated. Pbar = Barometric pressure, mm Hg (in.Hg) PD = Percent Difference 12.0 Calculations and Data Analysis Qe = exhaust flow rate, dscf per minute 12.1 Nomenclature Qg = natural gas fuel flow rate, scf per A = measured absorbance of 2 mL aliquot minute ° B = estimated sampling rate, Lpm Tm = Average DGM absolute temperature, K (°R). Cl = target concentration in liquid, μg/mL D = estimated stack formaldehyde con- Tstd = Standard absolute temperature, 293 °K centration (ppmv) (528 °R). E = estimated liquid volume, normally 40 mL t = sample time (minutes) (the size of the VOA used) Vm = Dry gas volume as measured by the cform = formaldehyde concentration in gas DGM, dcm (dcf). stream, ppmvd Vm(std) = Dry gas volume measured by the cform @15%02 = formaldehyde concentration in DGM, corrected to standard conditions of gas stream corrected to 15% oxygen, 1 atmosphere and 20 °C, dscm (dscf). ppmvd Vt = actual total volume of impinger catch/ Csm = measured concentration of formalde- rinsate, mL hyde in the spiked aliquot Va = volume (2.0) of aliquot analyzed, mL Cu = measured concentration of formalde- X1 = first value hyde in the unspiked aliquot of the same X2 = second value sample O2d = oxygen concentration measured, per- Cs = calculated concentration of formalde- cent by volume, dry basis hyde spiking solution added to the %R = percent recovery of spike spiked aliquot Zu = volume fraction of unspiked (native) F = dilution factor, 1 unless dilution of the sample contained in the final spiked ali- sample was needed to reduce the absorb- quot [e.g., Vu/(Vu + Vs), where Vu + Vs ance into the calibration range should = 2.0 mL] Fd = dry basis F-factor from Method 19, dscf Zs = volume fraction of spike solution con- per million btu GCVg = Gross calorific tained in the final spiked aliquot [e.g., value (or higher heating value), btu per Vs/(Vu + Vs)] scf R = 0.02405 dscm per g-mole, for metric units Kc = spectrophotometer calibration factor, at standard conditions of 1 atmosphere slope of the least square regression line, and 20 °C μg/absorbance (Note: Most spreadsheets Y = Dry Gas Meter calibration factor are capable of calculating a least squares 12.2 Pretest Design line.) K1 = 0.3855°K/mm Hg for metric units, ° BtD∗∗ ∗30 (17.65 R/in.Hg for English units.) C = Eq. 323-1 MW = molecular weight, 30 g/g-mole, for 1 ∗ formaldehyde 24.05 = mole specific vol- 24. 05 E ume constant, liters per g-mole 12.3 Exhaust Flow Rate

FQGCV ⎡ 20.9 ⎤ Q= dg g⎢ ⎥ Eq. 323-2 6 − 10 ⎣20.9 O2d ⎦

12.4 Percent Difference—(Applicable to Field and Lab Duplicates) ()CZC− %R= sm u u ∗ 100 Eq. 323-4 ()XX− ZC PD = 1 2 ∗100 Eq. 323-3 ss ⎛ XX+ ⎞ 12.6 Mass of Formaldehyde in Liquid Sam- ⎜ 1 2 ⎟ ple ⎝ 2 ⎠ 12.5 Percent Recovery of Spike

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⎛ ⎞⎛ ⎞ =∗∗Vt 1 mg mKc AF⎜ ⎟⎜ ⎟ Eq. 323-5 ⎝Va ⎠⎝1000 …g ⎠

12.7 Dry Gas Sample Volume Corrected to 12.8 Formaldehyde Concentration in gas Standard Conditions Stream ()VYTP = m std bar Vmstd() Eq. 323-6 TPmstd KYV P = i m bar Tm

⎛ ⎞ R m ⎛ 1 g ⎞ c = ⎜ ⎟ ()1×106 ppmv Eq. 3233-7 form ⎜ ⎟⎜ ⎟ MW ⎝Vmstd()⎠⎝1000 mg ⎠

12.9 Formaldehyde Concentration Cor- rected to 15% Oxygen

13.0 Method Performance aliquots of the original sample before rea- nalysis. 13.1 Precision. Based on a Method 301 vali- 13.4 Sample Stability. Based on a sample dation using quad train arrangement with stability study conducted in conjunction post sampling spiking study of the method with the method validation, sample degrada- at a natural gas-fired IC engine, the relative tion for 7- and 14-day hold times does not ex- standard deviation of six pairs of unspiked ceed 2.3 and 4.6 percent, respectively, based samples was 11.2 percent at a mean stack gas on a 95 percent level of confidence. There- concentration of 16.7 ppmvd. fore, the recommended maximum sample 13.2 Bias. No bias correction is allowed. holding time for the underivatized impinger The single Method 301 validation study of catch/rinsings is 14 days, where projected the method at a natural gas-fired IC engine, sample degradation is below 5 percent. indicated a bias correction factor of 0.91 for that set of data. An earlier spiking study got 14.0 Pollution Prevention similar average percent spike recovery when spiking into a blank sample. This data set is Sample gas from the combustion source ex- too limited to justify using a bias correction haust is vented to the atmosphere after pass- factor for future tests at other sources. ing through the chilled impinger sampling 13.3 Range. The range of this method for train. Reagent solutions and samples should formaldehyde is 0.2 to 7.5 μg/mL in the liquid be collected for disposal as aqueous waste. phase. (This corresponds to a range of 0.27 to 15.0 Waste Management 10 ppmv in the engine exhaust if sampling at a rate of 0.4 Lpm for 60 minutes and using a Standards of formaldehyde and the analyt- 40-mL VOA bottle.) If the liquid sample con- ical reagents should be handled according to centration is above this range, perform the the Material Safety Data Sheets. appropriate dilution for accurate measurement. Any dilutions must be taken from new

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16.0 References hyde in Air Using Acetyl Acetone.’’ Revision 0, September 1986. 1. National Council of the Paper Industry for Air and Stream Improvement, Inc. 5. Shareef, G.S., et al. ‘‘Measurement of Air ‘‘Volatile Organic Emissions from Pulp and Toxic Emissions from Natural Gas-Fired In- Paper Mill Sources, Part X—Test Methods, ternal Combustion Engines at Natural Gas Quality Assurance/Quality Control Proce- Transmission and Storage Facilities.’’ Re- dures, and Data Analysis Protocols.’’ Tech- port No. GRI–96/0009.1, Gas Research Insti- nical Bulletin No. 684, December 1994. tute, Chicago, Illinois, February 1996. 2. National Council of the Paper Industry 6. Gundappa, M., et al. ‘‘Characteristics of for Air and Stream Improvement, Inc., Formaldehyde Emissions from Natural Gas- ‘‘Field Validation of a Source Sampling Fired Reciprocating Internal Combustion Method for Formaldehyde, Methanol, and Engines in Gas Transmission. Volume I: Phenol at Wood Products Mills.’’ 1997 TAPPI Phase I Predictive Model for Estimating International Environmental Conference. Formaldehyde Emissions from 2–Stroke En- 3. Roy F. Weston, Inc. ‘‘Formaldehyde gines.’’ Report No. GRI–97/0376.1, Gas Re- Sampling Method Field Evaluation and search Institute, Chicago, Illinois, Sep- Emission Test Report for Georgia-Pacific tember 1997. Resins, Inc., Russellville, South Carolina.’’ August 1996. 17.0 Tables, Diagrams, Flowcharts, and 4. Hoechst Celanese Method CL 8–4. Validation Data ‘‘Standard Test Method for Free Formalde-

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METHOD 325A—VOLATILE ORGANIC COMPOUNDS combination with Method 325B. Companion FROM FUGITIVE AND AREA SOURCES: Method 325B (Sampler Preparation and Anal- ysis) describes preparation of sampling Sampler Deployment and VOC Sample tubes, shipment and storage of exposed sam- Collection pling tubes, and analysis of sampling tubes collected using either this passive sampling 1.0 SCOPE AND APPLICATION procedure or alternative active (pumped) 1.1 This method describes collection of sampling methods. volatile organic compounds (VOCs) at or in- 1.2 This method may be used to determine side a facility property boundary or from fu- the average concentration of the select VOCs gitive and area emission sources using pas- using the corresponding uptake rates listed sive (diffusive) tube samplers (PS). The con- in Method 325B, Table 12.1. Additional com- centration of airborne VOCs at or near these pounds or alternative sorbents must be eval- potential fugitive- or area-emission sources uated as described in Addendum A of Method may be determined using this method in 325B or by one of the following national/

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international standard methods: ISO 16017– chromatograph (GC) equipped with a 2:2003(E), ASTM D6196–03 (Reapproved 2009), chromatographic column to separate the or BS EN 14662–4:2005 (all incorporated by VOCs and a detector to determine the quan- reference—see § 63.14), or reported in the tity of target VOCs. peer-reviewed open literature. 2.1.5 Gaseous or liquid calibration stand- 1.3 Methods 325A and 325B are valid for ards loaded onto the sampling ends of clean the measurement of benzene. Supporting lit- sorbent tubes must be used to calibrate the erature (References 1–8) indicates that ben- analytical equipment. zene can be measured by flame ionization de- 2.1.6 This method requires the use of field tection or mass spectrometry over a con- blanks to ensure sample integrity associated centration range of approximately 0.5 with shipment, collection, and storage of the micrograms per cubic meter (μg/m3) to at passive samples. It also requires the use of μ 3 least 500 g/m when industry standard (3.5 field duplicates to validate the sampling × inch long 0.25 inch outside diameter (o.d.) process. × 5 mm inner diameter (i.d.)) inert-coated 2.1.7 At the end of each sampling period, stainless steel sorbent tubes packed with the passive samples are collected, sealed, and CarbographTM 1 TD, CarbopackTM B, or shipped to a laboratory for analysis of target CarbopackTM X or equivalent are used and VOCs by thermal desorption gas chroma- when samples are accumulated over a period tography, as described in Method 325B. of 14 days. 1.4 This method may be applied to screen- 2.2 APPLICATION OF DIFFUSIVE SAMPLING ing average airborne VOC concentrations at facility property boundaries or monitoring 2.2.1 This method requires deployment of perimeters over an extended period of time passive sampling tubes on a monitoring pe- using multiple sampling periods (e.g., 26 × 14- rimeter encompassing all known emission day sampling periods). The duration of each sources at a facility and collection of local sampling period is normally 14 days. meteorological data. It may be used to deter- 1.5 This method requires the collection of mine average concentration of VOC at a fa- local meteorological data (wind speed and di- cility’s ‘‘fenceline’’ using time integrated rection, temperature, and barometric pres- passive sampling (Reference 2). sure). Although local meteorology is a com- 2.2.2 Collecting samples and meteorolog- ponent of this method, non-regulatory appli- ical data at progressively higher frequencies cations of this method may use regional me- may be employed to resolve shorter term teorological data. Such applications risk concentration fluctuations and wind condi- that the results may not identify the precise tions that could introduce interfering emis- source of the emissions. sions from other sources. 2.2.3 This passive sampling method pro- 2.0 SUMMARY OF THE METHOD vides a low cost approach to screening of fu- 2.1 PRINCIPLE OF THE METHOD gitive or area emissions compared to active sampling methods that are based on pumped The diffusive passive sampler collects VOC sorbent tubes or time weighted average can- from air for a measured time period at a rate ister sampling. that is proportional to the concentration of 2.2.3.1 Additional passive sampling tubes vapor in the air at that location. may be deployed at different distances from 2.1.1 This method describes the deploy- the facility property boundary or from the ment of prepared passive samplers, including geometric center of the fugitive emission determination of the number of passive sam- source. plers needed for each survey and placement 2.2.3.2 Additional meteorological meas- of samplers along or inside the facility prop- urements may also be collected as needed to erty boundary depending on the size and perform preliminary gradient-based assess- shape of the site or linear length of the ment of the extent of the pollution plume at boundary. ground level and the effect of ‘‘background’’ 2.1.2 The rate of sampling is specific to sources contributing to airborne VOC con- each compound and depends on the diffusion centrations at the location. constants of that VOC and the sampler di- 2.2.4 Time-resolved concentration meas- mensions/characteristics as determined by urements coupled with time-resolved mete- prior calibration in a standard atmosphere orological monitoring may be used to gen- (Reference 1). erate data needed for source apportionment 2.1.3 The gaseous VOC target compounds procedures and mass flux calculations. migrate through a constant diffusion barrier (e.g., an air gap of fixed dimensions) at the 3.0 DEFINITIONS sampling end of the diffusion sampling tube and adsorb onto the sorbent. (See also Section 3.0 of Method 325B.) 2.1.4 Heat and a flow of inert carrier gas 3.1 Fenceline means the property boundary are then used to extract (desorb) the re- of a facility or internal monitoring perim- tained VOCs back from the sampling end of eter established in accordance with the re- the tube and transport/transfer them to a gas quirements in Section 8.2 of this method.

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3.2 Passive sampler (PS) means a specific meteorological information, particularly type of sorbent tube (defined in this method) wind direction and speed, is required to be that has a fixed dimension air (diffusion) gap collected throughout the monitoring period. at the sampling end and is sealed at the Interfering sources can include neighboring other end. industrial facilities, transportation facili- 3.3 Passive sampling refers to the activity ties, fueling operations, combustion sources, of quantitatively collecting VOC on sorbent short-term transient sources, residential tubes using the process of diffusion. sources, and nearby highways or roads. As 3.4 PSi is the annual average for all PS PS data are evaluated, the location of poten- concentration results from location i. tial interferences with respect to PS loca- 3.5 PSi3 is the set of annual average con- tions and local wind conditions should be centration results for PSi and two sorbent considered, especially when high PS con- tubes nearest to the PS location i. centration values are observed. 3.6 PSip is the concentration from the sorbent tube at location i for the test period or 4.3 TUBE HANDLING episode p. You must protect the PS tubes from gross 3.7 Sampling period is the length of time external contamination during field sam- each passive sampler is exposed during field pling. Analytical thermal desorption equip- monitoring. The sampling period for this ment used to analyze PS tubes must desorb method is 14 days. organic compounds from the interior of PS 3.8 Sorbent tube (Also referred to as tube, tubes and exclude contamination from exter- PS tube, adsorbent tube, and sampling tube) nal sampler surfaces in the analytical/sam- is an inert coated stainless steel tube. Stand- ple flow path. If the analytical equipment ard PS tube dimensions for this method are does not comply with this requirement, you × 3.5-inch (89 mm) long 0.25-inch (6.4 mm) o.d. must wear clean, white, cotton or powder- with an i.d. of 5 mm, a cross-sectional area of free nitrile gloves to handle sampling tubes 2 19.6 mm and an air gap of 15 mm. The cen- to prevent contamination of the external tral portion of the tube is packed with solid sampler surfaces. Sampling tubes must be × adsorbent material contained between 2 capped with two-piece, brass, 0.25 inch, long- 100-mesh stainless steel gauzes and termi- term storage caps fitted with combined poly- nated with a diffusion cap at the sampling tetrafluoroethylene ferrules (see Section 6.1 end of the tube. These axial passive samplers and Method 325B) to prevent ingress of air- are installed under a protective hood during borne contaminants outside the sampling pe- field deployment. riod. When not being used for field moni- NOTE: Glass and glass- (or fused silica-) toring, the capped tubes must be stored in a lined stainless steel sorbent tubes (typically clean, air-tight, shipping container to pre- 4 mm i.d.) are also available in various vent the collection of VOCs (see Section 6.4.2 lengths to suit different makes of thermal of Method 325B). desorption equipment, but these are rarely used for passive sampling because it is more 4.4 LOCAL WEATHER CONDITIONS AND difficult to adequately define the diffusive AIRBORNE PARTICULATES air gap in glass or glass-line tubing. Such tubes are not recommended for this method. Although air speeds are a constraint for many forms of passive samplers, axial tube 4.0 SAMPLING INTERFERENCES PS devices have such a slow inherent uptake rate that they are largely immune to these 4.1 GENERAL INTERFERENCES effects (References 4,5). Passive samplers Passive tube samplers should be sited at a must nevertheless be deployed under non- distance beyond the influence of possible ob- emitting weatherproof hoods to moderate structions such as trees, walls, or buildings the effect of local weather conditions such as at the monitoring site. Complex topography solar heating and rain. The cover must not and physical site obstructions, such as bod- impede the ingress of ambient air. Sampling ies of water, hills, buildings, and other struc- tubes should also be orientated vertically tures that may prevent access to a planned and pointing downwards, to minimize accu- PS location must be taken into consider- mulation of particulates. ation. You must document and report siting interference with the results of this method. 4.5 TEMPERATURE The normal working range for field sam- 4.2 BACKGROUND INTERFERENCE pling for sorbent packing is 0–40 °C (Ref- Nearby or upwind sources of target emis- erences 6,7). Note that most published pas- sions outside the facility being tested can sive uptake rate data for sorbent tubes is contribute to background concentrations. quoted at 20 °C. Note also that, as a rough Moreover, because passive samplers measure guide, an increase in temperature of 10 °C continuously, changes in wind direction can will reduce the collection capacity for a cause variation in the level of background given analyte on a given sorbent packing by concentrations from interfering sources dur- a factor of 2, but the uptake rate will not ing the monitoring period. This is why local change significantly (Reference 4).

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5.0 SAFETY standard passive sampling tubes for monitoring additional target compound(s) once This method does not purport to include their uptake rate and performance has been all safety issues or procedures needed when demonstrated following procedures in Adden- deploying or collecting passive sampling dum A to Method 325B. Guidance on sorbent tubes. Precautions typical of field air sam- selection can also be obtained from relevant pling projects are required. Tripping, falling, national and international standard methods electrical, and weather safety considerations such as ASTM D6196–03 (Reapproved 2009) must all be included in plans to deploy and (Reference 14) and ISO 16017–2:2003(E) (Ref- collect passive sampling tubes. erence 13) (both incorporated by reference— see § 63.14). 6.0 SAMPLING EQUIPMENT AND SUPPLIES, AND PRE-DEPLOYMENT PLANNING 6.2 PASSIVE OR DIFFUSIVE SAMPLING CAP This section describes the equipment and One diffusive sampling cap is required per supplies needed to deploy passive sampling PS tube. The cap fits onto the sampling end monitoring equipment at a facility property of the tube during air monitoring. The other boundary. Details of the passive sampling end of the tube remains sealed with the long- tubes themselves and equipment required for term storage cap. Each diffusive sampling subsequent analysis are described in Method cap is fitted with a stainless steel gauze, 325B. which defines the outer limit of the diffusion air gap. 6.1 PASSIVE SAMPLING TUBES The industry standard PS tubes used in 6.3 SORBENT TUBE PROTECTION COVER this method must meet the specific configu- A simple weatherproof hood, suitable for ration and preparation requirements de- protecting passive sampling tubes from the scribed in Section 3.0 of this method and Sec- worst of the weather (see Section 4.4) con- tion 6.1 of Method 325B. sists of an inverted cone/funnel constructed NOTE: The use of PS tubes packed with var- of an inert, non-outgassing material that fits ious sorbent materials for monitoring a wide over the diffusive tube, with the open (sam- variety of organic compounds in ambient air pling) end of the tube projecting just below has been documented in the literature (Ref- the cone opening. An example is shown in erences 4–10). Other sorbents may be used in Figure 6.1 (Adapted from Reference 13).

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6.4 THERMAL DESORPTION APPARATUS sorbents, gas and liquid phase standards, preloaded standard tubes, and carrier gases are If the analytical thermal desorber that will covered in Section 7 of Method 325B. subsequently be used to analyze the passive sampling tubes does not meet the require- 8.0 SAMPLE DEPLOYMENT, RECOVERY, AND ment to exclude outer surface contaminants STORAGE from the sample flow path (see Section 6.6 of Method 325B), then clean, white, cotton or Pre-deployment and planning steps are re- powder-free nitrile gloves must be used for quired before field deployment of passive handling the passive sampling tubes during sampling tubes. These activities include but field deployment. are not limited to conducting a site visit, determining suitable and required monitoring 6.5 SORBENT SELECTION locations, and determining the monitoring Sorbent tube configurations, sorbents or frequency to be used. other VOC not listed in this method must be 8.1 CONDUCTING THE SITE VISIT evaluated according to Method 325B, Adden- dum A or ISO 16017–2:2003(E) (Reference 13) 8.1.1 Determine the size and shape of the (incorporated by reference—see § 63.14). The facility footprint in order to determine the supporting evaluation and verification data required number of monitoring locations. described in Method 325B, Addendum A for 8.1.2 Identify obstacles or obstructions configurations or compounds different from (buildings, roads, fences), hills and other ter- the ones described in this method must meet rain issues (e.g., bodies of water or swamp the performance requirements of Method land) that could interfere with air parcel 325A/B and must be submitted with the test flow to the sampler or that prevent reason- plan for your measurement program. able access to the location. You may use the general guidance in Section 4.1 of this meth- 7.0 REAGENTS AND STANDARDS od during the site visit to identify sampling No reagents or standards are needed for locations. You must evaluate the placement the field deployment and collection of pas- of each passive sampler to determine if the sive sampling tubes. Specifications for conditions in this section are met.

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8.1.3 Identify to the extent possible and instrumentation. A comparison of the pollut- record potential off-site source interferences ant concentrations measured with the PS to (e.g., neighboring industrial facilities, trans- concentrations measured by site instrumen- portation facilities, fueling operations, com- tation may be used as an optional data qual- bustion sources, short-term transient ity indicator to assess the accuracy of PS resources, residential sources, nearby high- sults. ways). 8.2.1.1 The monitoring perimeter may be 8.1.4 Identify the closest available mete- located between the property boundary and orological station. Identify potential loca- any potential emission source near the prop- tions for one or more on-site or near-site me- erty boundary, as long as the distance from teorological station(s) following the guid- the source to the monitoring perimeter is at ance in EPA–454/B–08–002 (Reference 11) (in- least 50 meters (162 feet). If a potential emis- corporated by reference—see § 63.14). sions source is within 50 meters (162 feet) of the property boundary, the property bound- 8.2 DETERMINING SAMPLING LOCATIONS ary shall be used as the monitoring perim- (REFERENCES 2, 3) eter near that source. 8.2.1 The number and placement of the 8.2.1.2 Samplers need only be placed passive samplers depends on the size, the around the monitoring perimeter and not shape of the facility footprint or the linear along internal roads or other right of ways distance around the facility, and the prox- that may bisect the facility. imity of emission sources near the property 8.2.1.3 An extra sampler must be placed boundaries. Aerial photographs or site maps near known sources of VOCs if potential may be used to determine the size (acreage) emission sources are within 50 meters (162 and shape of the facility or the length of the feet) of the boundary and the source or monitoring perimeter. Place passive sam- sources are located between two monitors. plers on an internal monitoring perimeter on Measure the distance (x) between the two or inside the facility boundary encompassing monitors and place another monitor approxi- all emission sources at the facility at dif- mately halfway between (x/2 ±10 percent) the ferent angles circling the geometric center two monitors. Only one extra sampler is re- of the facility or at different distances based quired between two monitors to account for on the monitoring perimeter length of the known sources of VOCs. For example, in Fig- facility. ure 8.1, the facility added three additional NOTE: In some instances, permanent air monitors (i.e., light shaded sampler loca- monitoring stations may already be located tions), and in Figure 8.2, the facility added in close proximity to the facility. These sta- two additional monitors to provide sufficient tions may be operated and maintained by the coverage of all area sources. site, or local or state regulatory agencies. If access to the station is possible, a PS may be FIGURE 8.1. FACILITY WITH A REGULAR SHAPE deployed adjacent to other air monitoring BETWEEN 750 AND 1,500 ACRES IN AREA

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8.2.2 Option 1 for Determining Sampling 8.2.2.1 For facilities with a regular (cir- Locations. cular, triangular, rectangular, or square)

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shape, determine the geographic center of degrees from the center point for a total of the facility. twenty-four 15 degree measurements evenly 8.2.2.1.1 For facilities with an area of less spaced (±1 degree). than or equal to 750 acres, measure angles of 8.2.2.1.4 Locate each sampling point where 30 degrees from the center point for a total the measured angle intersects the outer of twelve 30 degree measurements evenly monitoring perimeter. spaced (±1 degree). 8.2.2.2 For irregularly shaped facilities, 8.2.2.1.2 For facilities covering an area divide the area into a set of connecting sub- greater than 750 acres but less than or equal to 1,500 acres, measure angles of 20 degrees area circles, triangles or rectangles to deter- from the center point for a total of eighteen mine sampling locations. The subareas must 20 degree measurements evenly spaced (±1 de- be defined such that a circle can reasonably gree). Figure 8.1 shows the monitor place- encompass the subarea. Then determine the ment around the property boundary of a fa- geometric center point of each of the sub- cility with an area between 750 and 1,500 areas. acres. Monitor placements are represented 8.2.2.2.1 If a subarea is less than or equal with black dots along the property bound- to 750 acres (e.g., Figure 8.3), measure angles ary. of 30 degrees from the center point for a 8.2.2.1.3 For facilities covering an area total of twelve 30 degree measurements (±1 greater than 1,500 acres, measure angles of 15 degree).

8.2.2.2.2 If a subarea is greater than 750 monitoring perimeter. Sampling points need acres but less than or equal to 1,500 acres not be placed closer than 152 meters (500 feet) (e.g., Figure 8.4), measure angles of 20 de- apart (or 76 meters (250 feet) if known grees from the center point for a total of sources are within 50 meters (162 feet) of the eighteen 20 degree measurements (±1 degree). monitoring perimeter), as long as a min- 8.2.2.2.3 If a subarea is greater than 1,500 imum of 3 monitoring locations are used for acres, measure angles of 15 degrees from the each subarea. center for a total of twenty-four 15 degree 8.2.2.2.5 Sampling sites are not needed at measurements (±1 degree). the intersection of an inner boundary with 8.2.2.2.4 Locate each sampling point where an adjacent subarea. The sampling location the measured angle intersects the outer must be sited where the measured angle

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intersects the subarea’s outer monitoring perimeter.

8.2.3 Option 2 for Determining Sampling portant considerations for siting of meteoro- Locations. logical stations are detailed below. 8.2.3.1 For facilities with a monitoring pe- 8.3.1 Place meteorological stations in lo- rimeter length of less than 7,315 meters cations that represent conditions affecting (24,000 feet), a minimum of twelve sampling the transport and dispersion of pollutants in locations evenly spaced ±10 percent of the lo- the area of interest. Complex terrain may re- cation interval is required. quire the use of more than one meteorolog- 8.2.3.2 For facilities with a monitoring pe- ical station. rimeter length greater than or equal to 7,315 8.3.2 Deploy wind instruments over level, meters (24,000 feet), sampling locations are open terrain at a height of 10 meters (33 spaced 610 ± 76 meters (2,000 ± 250 feet) apart. feet). If possible, locate wind instruments at 8.2.3.3 Unless otherwise specified in an ap- a distance away from nearby structures that plicable regulation, permit or other require- is equal to at least 10 times the height of the structure. ment, for small disconnected subareas with known sources within 50 meters (162 feet) of 8.3.3 Protect meteorological instruments the monitoring perimeter, sampling points from thermal radiation and adequately ven- need not be placed closer than 152 meters (500 tilate them using aspirated shields. The temperature sensor must be located at a dis- feet) apart as long as a minimum of 3 moni- tance away from any nearby structures that toring locations are used for each subarea. is equal to at least four times the height of 8.3 SITING A METEOROLOGICAL STATION the structure. Temperature sensors must be located at least 30 meters (98 feet) from large A meteorological station is required at or paved areas. near the facility you are monitoring. A num- 8.3.4 Collect and record meteorological ber of commercially available meteorolog- data, including wind speed, wind direction, ical stations can be used. Information on me- temperature and barometric pressure on an teorological instruments can be found in hourly basis. Calculate average unit vector EPA–454/R–99–005 (Reference 11) (incor- wind direction, sigma theta, temperature porated by reference—see § 63.14). Some im- and barometric pressure per sampling period

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to enable calculation of concentrations at 8.5.6 Protect the PS from rain and exces- standard conditions. Supply this information sive wind velocity by placing them under the to the laboratory. type of protective hood described in Section 8.3.5 Identify and record the location of 6.1.3 or equivalent. the meteorological station by its GPS co- 8.5.7 Remove the storage cap on the sam- ordinate. pling end of the tube and replace it with a diffusive sampling cap at the start of the 8.4 MONITORING FREQUENCY sampling period. Make sure the diffusion cap is properly seated and store the removed 8.4.1 Sample collection may be performed storage caps in the empty tube shipping con- for periods up to 14 days. tainer. 8.4.2 A site screening protocol that meets 8.5.8 Record the start time and location method requirements may be performed by details for each sampler on the field sample collecting samples for a year where each PS data sheet (see example in Section 17.0.). accumulates VOC for a 14-day sampling pe- 8.5.9 Expose the sampling tubes for the re- riod. Study results are accumulated for the quired sampling period-normally 14-days. sampling periods (typically 26) over the 8.5.10 Field blank tubes (see Section 9.3 of course of one calendar year. To the extent Method 325B) are stored outside the shipping practical, sampling tubes should be changed container at representative sampling loca- at approximately the same time of day at tions around the site, but with both long- each of the monitoring sites. term storage caps kept in place throughout 8.4.3 When extenuating circumstances do the monitoring exercise. Collect at least two not permit safe deployment or retrieval of field blanks sorbent samples per sampling passive samplers (e.g., extreme weather, period to ensure sample integrity associated power failure), sampler placement or re- with shipment, collection, and storage. trieval earlier or later than the prescribed schedule is allowed but must occur as soon 8.6 SORBENT TUBE RECOVERY AND as safe access to sampling sites is possible. METEOROLOGICAL DATA COLLECTION

8.5 PASSIVE SAMPLER DEPLOYMENT Recover deployed sampling tubes and field blanks as follows: 8.5.1 Clean (conditioned) sorbent tubes 8.6.1 After the sampling period is com- must be prepared and packaged by the lab- plete, immediately replace the diffusion end oratory as described in Method 325B and cap on each sampled tube with a long-term must be deployed for sampling within 30 days storage end cap. Tighten the seal securely by of conditioning. hand and then tighten an additional quarter 8.5.2 Allow the tubes to equilibrate with turn with an appropriate tool. Record the ambient temperature (approximately 30 min- stop date and time and any additional rel- utes to 1 hour) at the monitoring location evant information on the sample data sheet. before removing them from their storage/ 8.6.2 Place the sampled tubes, together shipping container for sample collection. with the field blanks, in the storage/shipping 8.5.3 If there is any risk that the analyt- container. Label the storage container, but ical equipment will not meet the require- do not use paints, markers, or adhesive la- ment to exclude contamination on outer bels to identify the tubes. TD-compatible tube surfaces from the sample flow path (see electronic (radio frequency identification Section 6.6 of Method 325B), sample handlers (RFID)) tube labels are available commer- must wear clean, white, cotton or powder- cially and are compatible with some brands free nitrile gloves during PS deployment and of thermal desorber. If used, these may be collection and throughout any other tube programmed with relevant tube and sample handling operations. information, which can be read and auto- 8.5.4 Inspect the sampling tubes imme- matically transcribed into the sequence re- diately prior to deployment. Ensure that port by the TD system. they are intact, securely capped, and in good NOTE: Sampled tubes must not be placed in condition. Any suspect tubes (e.g., tubes that the same shipping container as clean condi- appear to have leaked sorbent) should be re- tioned sampling tubes. moved from the sampling set. 8.6.3 Sampled tubes may be shipped at 8.5.5 Secure passive samplers so the bot- ambient temperature to a laboratory for tom of the diffusive sampling cap is 1.5 to 3 sample analysis. meters (4.9 to 9.8 feet) above ground using a 8.6.4 Specify whether the tubes are field pole or other secure structure at each sam- blanks or were used for sampling and docu- pling location. Orient the PS vertically and ment relevant information for each tube with the sampling end pointing downward to using a Chain of Custody form (see example avoid ingress of particulates. in Section 17.0) that accompanies the sam- NOTE: Duplicate sampling assemblies must ples from preparation of the tubes through be deployed in at least one monitoring loca- receipt for analysis, including the following tion for every 10 monitoring locations during information: Unique tube identification each field monitoring period. numbers for each sampled tube; the date,

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time, and location code for each PS place- toring location, the episode can be ascribed ment; the date, time, and location code for to transient contamination and the data in each PS recovery; the GPS reference for each question must be flagged for potential elimi- sampling location; the unique identification nation from the dataset. number of the duplicate sample (if applicable); and problems or anomalies encountered. 9.3 DUPLICATES AND FIELD BLANKS 8.6.5 If the sorbent tubes are supplied with 9.3.1 Collect at least one co-located/dupli- electronic (e.g., RFID) tags, it is also pos- cate sample for every 10 field samples to de- sible to allocate a sample identifier to each termine precision of the measurements. PS tube. In this case, the recommended for- 9.3.2 Collect at least two field blanks sor- mat for the identification number of each bent samples per sampling period to ensure sampled tube is AA–BB–CC–DD–VOC, where: sample integrity associated with shipment, AA = Sequence number of placement on collection, and storage. You must use the en- route (01, 02, 03 . . .) tire sampling apparatus for field blanks in- BB = Sampling location code (01, 02, 03 . . .) cluding unopened sorbent tubes mounted in CC = 14-day sample period number (01 to 26) protective sampling hoods. The tube closures DD = Sample code (SA = sample, DU = dupli- must not be removed. Field blanks must be cate, FB = field blank) placed in two different quadrants (e.g., 90° VOC = 3-letter code for target compound(s) and 270°) and remain at the sampling loca- (e.g., BNZ for benzene or BTX for ben- tion for the sampling period. zene, toluene, and xylenes) 10.0 CALIBRATION AND STANDARDIZATION NOTE: Sampling start and end times/dates can also be logged using RFID tube tags. Follow the calibration and standardization procedures for meteorological measurements 9.0 QUALITY CONTROL in EPA–454/B–08–002 March 2008 (Reference 9.1 Most quality control checks are car- 11) (incorporated by reference—see § 63.14). ried out by the laboratory and associated re- Refer to Method 325B for calibration and quirements are in Section 9.0 of Method 325B, standardization procedures for analysis of including requirements for laboratory the passive sampling tubes. blanks, field blanks, and duplicate samples. 11.0 ANALYTICAL PROCEDURES 9.2 Evaluate for potential outliers the laboratory results for neighboring sampling Refer to Method 325B, which provides de- tubes collected over the same time period. A tails for the preparation and analysis of sam- potential outlier is a result for which one or pled passive monitoring tubes (preparation more PS tube does not agree with the trend of sampling tubes, shipment and storage of in results shown by neighboring PS tubes— exposed sampling tubes, and analysis of sam- particularly when data from those locations pling tubes). have been more consistent during previous sampling periods. Accidental contamination 12.0 DATA ANALYSIS, CALCULATIONS AND by the sample handler must be documented DOCUMENTATION before any result can be eliminated as an 12.1 CALCULATE ANNUAL AVERAGE outlier. Rare but possible examples of con- FENCELINE CONCENTRATION. tamination include loose or missing storage caps or contaminated storage/shipping con- After a year’s worth of sampling at the fa- tainers. Review data from the same and cility fenceline (for example, 26 14-day sam- neighboring monitoring locations for the ples), the average (PSi) may be calculated for subsequent sampling periods. If the anoma- any specified period at each PS location lous result is not repeated for that moni- using Equation 12.1.

Where: N = The number of sampling periods in the year (e.g., for 14-day sampling periods, PSi = Annual average for location i. from 1 to 26). PSip = Sampling period specific concentration from Method 325B. NOTE: PSip is a function of sampling loca- i = Location of passive sampler (0 to 360°). tion-specific factors such as the contribution p = The sampling period. from facility sources, unusual localized meteorological conditions, contribution from nearby interfering sources, the background

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caused by integrated far-field sources and tions—Part 4: Diffusive sampling fol- measurement error due to deployment, han- lowed by thermal desorption and gas dling, siting, or analytical errors. chromatography, BS EN 14662–4:2005. 2. Thoma, E.D., Miller, C.M., Chung, K.C., 12.2 IDENTIFY SAMPLING LOCATIONS OF Parsons, N.L. and Shine, B.C. Facility INTEREST Fence Line Monitoring using Passive If data from neighboring sampling loca- Samplers, J. Air & Waste Mange. Assoc. tions are significantly different, then you 2011, 61:834–842. may add extra sampling points to isolate 3. Quality Assurance Handbook for Air Pol- background contributions or identify facil- lution C Systems, Volume II: Ambient ity-specific ‘‘hot spots.’’ Air Quality Monitoring Program, EPA– 454/B–13–003, May 2013. Available at http:// 12.3 EVALUATE TRENDS www.epa.gov/ttnamti1/files/ambient/pm25/qa/ QA-Handbook-Vol-II.pdf. You may evaluate trends and patterns in 4. Brown, R.H., Charlton, J. and Saunders, the PS data over multiple sampling periods K.J.: The development of an improved to determine if elevated concentrations of diffusive sampler. Am. Ind. Hyg. Assoc. target compounds are due to operations on J. 1981, 42(12): 865–869. the facility or if contributions from back- 5. Brown, R. H. Environmental use of diffu- ground sources are significant. sive samplers: evaluation of reliable dif- 12.3.1 Obtain meteorological data includ- fusive uptake rates for benzene, toluene ing wind speed and wind direction or unit and xylene. J. Environ. Monit. 1999, 1 (1), vector wind data from the on-site meteoro- 115–116. logical station. Use this meteorological data 6. Ballach, J.; Greuter, B.; Schultz, E.; to determine the prevailing wind direction Jaeschke, W. Variations of uptake rates and speed during the periods of elevated con- in benzene diffusive sampling as a func- centrations. tion of ambient conditions. Sci. Total 12.3.2 As an option you may perform pre- Environ. 1999, 244, 203–217. liminary back trajectory calculations (http:// 7. Brown, R. H. Monitoring the ambient envi- ready.arl.noaa.gov/HYSPLIT.php) to aid in ronment with diffusive samplers: theory identifying the source of the background and practical considerations. J Environ. contribution to elevated target compound Monit. 2000, 2 (1), 1–9. concentrations. 8. Buzica, D.; Gerboles, M.; Plaisance, H. The 12.3.3 Information on published or docu- equivalence of diffusive samplers to ref- mented events on- and off-site may also be erence methods for monitoring O3, ben- included in the associated sampling period zene and NO2 in ambient air. J. Environ. report to explain elevated concentrations if Monit. 2008, 10 (9), 1052–1059. relevant. For example, you would describe if 9. Woolfenden, E. Sorbent-based sampling there was a chemical spill on site, or an acci- methods for volatile and semi-volatile dent on an adjacent road. organic compounds in air. Part 2. Sor- 12.3.4 Additional monitoring for shorter bent selection and other aspects of opti- periods (See section 8.4) may be necessary to mizing air monitoring methods. J. allow better discrimination/resolution of Chromatogr. A 2010, 1217, (16), 2685–94. contributing emission sources if the meas- 10. Pfeffer, H. U.; Breuer, L. BTX measure- ured trends and associated meteorology do ments with diffusive samplers in the vi- not provide a clear assessment of facility cinity of a cokery: Comparison between contribution to the measured fenceline con- ORSA-type samplers and pumped sam- centration. pling. J. Environ. Monit. 2000, 2 (5), 483– 12.3.5 Additional records necessary to cal- 486. culate sampling period average target com- 11. US EPA. 2000. Meteorological Monitoring pound concentration can be found in Section Guidance for Regulatory Modeling Appli- 12.1 of Method 325B. cations. EPA–454/R–99–005. Office of Air Quality Planning and Standards, Re- 13.0 METHOD PERFORMANCE search Triangle Park, NC. February 2000. Method performance requirements are de- Available at http://www.epa.gov/scram001/ scribed in Method 325B. guidance/met/mmgrma.pdf. 12. Quality Assurance Handbook for Air Pol- 14.0 POLLUTION PREVENTION lution Measurement Systems. Volume [Reserved] IV: Meteorological Measurements Version 2.0 Final, EPA–454/B–08–002 15.0 WASTE MANAGEMENT March 2008. Available at http:// www.epa.gov/ttnamti1/files/ambient/met/ [Reserved] Volume%20IVlMeteorologicall Measurements.pdf. 16.0 REFERENCES 13. ISO 16017–2:2003(E), Indoor, ambient and 1. Ambient air quality—Standard method for workplace air—Sampling and analysis of measurement of benzene concentra- volatile organic compounds by sorbent

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tube/thermal desorption/capillary gas sampling, and thermal desorption anal- chromatography. Part 2: Diffusive sam- ysis procedures for volatile organic com- pling. pounds in air. 14. ASTM D6196–03 (Reapproved 2009): Stand- 17.0 TABLES, DIAGRAMS, FLOWCHARTS AND ard practice for selection of sorbents, VALIDATION DATA

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METHOD 325B—VOLATILE ORGANIC COMPOUNDS not suitable for this analysis method include FROM FUGITIVE AND AREA SOURCES: particulate pollutants, (i.e., fumes, aerosols, and dusts), compounds too labile (reactive) SAMPLER PREPARATION AND ANALYSIS for conventional GC analysis, and VOCs that are more volatile than propane. 1.0 SCOPE AND APPLICATION 1.1 This method describes thermal 2.0 SUMMARY OF METHOD desorption/gas chromatography (TD/GC) 2.1 This method provides procedures for analysis of volatile organic compounds the preparation, conditioning, blanking, and (VOCs) from fugitive and area emission shipping of sorbent tubes prior to sample col- sources collected onto sorbent tubes using lection. passive sampling. It could also be applied to 2.2 Laboratory and field personnel must the TD/GC analysis of VOCs collected using have experience of sampling trace-level active (pumped) sampling onto sorbent VOCs using sorbent tubes (References 2,5) tubes. The concentration of airborne VOCs and must have experience operating thermal at or near potential fugitive- or area-emis- desorption/GC/multi-detector instrumenta- sion sources may be determined using this tion. method in combination with Method 325A. 2.3 Key steps of this method as imple- Companion Method 325A (Sampler Deploy- mented for each sample tube include: Strin- ment and VOC Sample Collection) describes gent leak testing under stop flow, recording procedures for deploying the sorbent tubes ambient temperature conditions, adding in- and passively collecting VOCs. ternal standards, purging the tube, ther- 1.2 The preferred GC detector for this mally desorbing the sampling tube, re- method is a mass spectrometer (MS), but focusing on a focusing trap, desorbing and flame ionization detectors (FID) may also be transferring/injecting the VOCs from the sec- used. Other conventional GC detectors such ondary trap into the capillary GC column for as electron capture (ECD), photoionization separation and analysis. (PID), or flame photometric (FPD) may also 2.4 Water management steps incorporated be used if they are selective and sensitive to the target compound(s) and if they meet the into this method include: (a) Selection of hy- method performance criteria provided in this drophobic sorbents in the sampling tube; (b) method. optional dry purging of sample tubes prior to 1.3 There are 97 VOCs listed as hazardous analysis; and (c) additional selective elimi- air pollutants in Title III of the Clean Air nation of water during primary (tube) Act Amendments of 1990. Many of these VOC desorption (if required) by selecting trapping are candidate compounds for this method. sorbents and temperatures such that target Compounds with known uptake rates for compounds are quantitatively retained while CarbographTM 1 TD, CarbopackTM B, or water is purged to vent. CarbopackTM X are listed in Table 12.1. This 3.0 DEFINITIONS method provides performance criteria to demonstrate acceptable performance of the (See also Section 3.0 of Method 325A). method (or modifications of the method) for 3.1 Blanking is the desorption and con- monitoring one or more of the compounds firmatory analysis of conditioned sorbent listed Table 12.1. If standard passive sam- tubes before they are sent for field sampling. pling tubes are packed with other sorbents 3.2 Breakthrough volume and associated re- or used for other analytes than those listed lation to passive sampling. Breakthrough vol- in Table 12.1, then method performance and umes, as applied to active sorbent tube sam- relevant uptake rates should be verified ac- pling, equate to the volume of air containing cording to Addendum A to this method or by a constant concentration of analyte that one of the following national/international may be passed through a sorbent tube at a standard methods: ISO 16017–2:2003(E), ASTM given temperature before a detectable level D6196–03 (Reapproved 2009), or BS EN 14662– (5 percent) of the input analyte concentra- 4:2005 (all incorporated by reference—see tion elutes from the tube. Although break- § 63.14), or reported in the peer-reviewed open through volumes are directly related to ac- literature. tive rather than passive sampling, they pro- 1.4 The analytical approach using TD/GC/ vide a measure of the strength of the sor- MS is based on previously published EPA bent-sorbate interaction and therefore also guidance in Compendium Method TO–17 relate to the efficiency of the passive sam- (http://www.epa.gov/ttnamti1/ pling process. The best direct measure of airtox.html#compendium) (Reference 1), which passive sampling efficiency is the stability of describes active (pumped) sampling of VOCs the uptake rate. Quantitative passive sam- from ambient air onto tubes packed with pling is compromised when the sorbent no thermally stable adsorbents. longer acts as a perfect sink—i.e., when the 1.5 Inorganic gases not suitable for anal- concentration of a target analyte imme- ysis by this method include oxides of carbon, diately above the sorbent sampling surface nitrogen and sulfur, ozone (O3), and other no longer approximates to zero. This causes diatomic permanent gases. Other pollutants a reduction in the uptake rate over time. If

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the uptake rate for a given analyte on a interest or otherwise interfere with the iden- given sorbent tube remains relatively con- tification or quantitation of target analytes. stant —i.e., if the uptake rate determined for 4.1.1 Sorbent decomposition artifacts are 48 hours is similar to that determined for 7 VOCs that form when sorbents degenerate, or 14 days—the user can be confident that e.g., when exposed to reactive species during passive sampling is occurring at a constant sampling. For example, benzaldehyde, phe- rate. As a general rule of thumb, such ideal nol, and acetophenone artifacts are reported passive sampling conditions typically exist to be formed via oxidation of the polymeric for analyte:sorbent combinations where the sorbent Tenax® when sampling high con- breakthrough volume exceeds 100 L (Ref- centration (100–500 ppb) ozone atmospheres erence 4). (Reference 5). 3.3 Continuing calibration verification sam- 4.1.2 Preparation and storage artifacts are ple (CCV). Single level calibration samples VOCs that were not completely cleaned from run periodically to confirm that the analyt- the sorbent tube during conditioning or that ical system continues to generate sample re- are an inherent feature of that sorbent at a sults within acceptable agreement to the given temperature. current calibration curve. 4.2 Humidity. Moisture captured during 3.4 Focusing trap is a cooled, secondary sampling can interfere with VOC analysis. sorbent trap integrated into the analytical Passive sampling using tubes packed with thermal desorber. It typically has a smaller hydrophobic sorbents, like those described in i.d. and lower thermal mass than the origi- this method, minimizes water retention. nal sample tube allowing it to effectively However, if water interference is found to be refocus desorbed analytes and then heat rap- an issue under extreme conditions, one or idly to ensure efficient transfer/injection more of the water management steps de- into the capillary GC analytical column. scribed in Section 2.4 can be applied. 3.5 High Resolution Capillary Column Chro- 4.3 Contamination from Sample Handling. matography uses fused silica capillary col- The type of analytical thermal desorption μ umns with an inner diameter of 320 m or equipment selected should exclude the possi- less and with a stationary phase film thick- bility of outer tube surface contamination μ ness of 5 m or less. entering the sample flow path (see Section 3.6 h is time in hours. 6.6). If the available system does not meet 3.7 i.d. is inner diameter. this requirement, sampling tubes and caps 3.8 min is time in minutes. must be handled only while wearing clean, 3.9 Method Detection Limit is the lowest white cotton or powder free nitrile gloves to level of analyte that can be detected in the prevent contamination with body oils, hand sample matrix with 99% confidence. lotions, perfumes, etc. 3.10 MS–SCAN is the mode of operation of a GC quadrupole mass spectrometer detector 5.0 SAFETY that measures all ions over a given mass range over a given period of time. 5.1 This method does not address all of 3.11 MS–SIM is the mode of operation of a the safety concerns associated with its use. GC quadrupole mass spectrometer detector It is the responsibility of the user of this that measures only a single ion or a selected standard to establish appropriate field and number of discrete ions for each analyte. laboratory safety and health practices prior 3.12 o.d. is outer diameter. to use. 3.13 ppbv is parts per billion by volume. 5.2 Laboratory analysts must exercise ex- 3.14 Thermal desorption is the use of heat treme care in working with high-pressure and a flow of inert (carrier) gas to extract gas cylinders. volatiles from a solid matrix. No solvent is 5.3 Due to the high temperatures in- required. volved, operators must use caution when 3.15 Total ion chromatogram is the chro- conditioning and analyzing tubes. matogram produced from a mass spectrometer detector collecting full spectral infor- 6.0 EQUIPMENT AND SUPPLIES mation. 6.1 Tube Dimensions and Materials. The 3.16 Two-stage thermal desorption is the sampling tubes for this method are 3.5-inches process of thermally desorbing analytes from (89 mm) long, 1⁄4 inch (6.4 mm) o.d., and 5 mm a sorbent tube, reconcentrating them on a i.d. passive sampling tubes (see Figure 6.1). focusing trap (see Section 3.4), which is then The tubes are made of inert-coated stainless itself rapidly heated to ‘‘inject’’ the con- steel with the central section (up to 60 mm) centrated compounds into the GC analyzer. packed with sorbent, typically supported be- 3.17 VOC is volatile organic compound. tween two 100 mesh stainless steel gauze. The tubes have a cross sectional area of 19.6 4.0 ANALYTICAL INTERFERENCES square mm (5 mm i.d.). When used for passive 4.1 Interference from Sorbent Artifacts. Arti- sampling, these tubes have an internal diffu- facts may include target analytes as well as sion (air) gap (DG) of 1.5 cm between the sor- other VOC that co-elute bent retaining gauze at the sampling end of chromatographically with the compounds of the tube, and the gauze in the diffusion cap.

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6.2 TUBE CONDITIONING APPARATUS 6.4 BLANK AND SAMPLED TUBE STORAGE APPARATUS 6.2.1 Freshly packed or newly purchased tubes must be conditioned as described in 6.4.1 Long-term storage caps. Seal clean, Section 9 using an appropriate dedicated blank and sampled sorbent tubes using inert, tube conditioning unit or the thermal long-term tube storage caps comprising non- desorber. Note that the analytical TD sys- greased, 2-piece, 0.25-inch, metal SwageLok®- tem should be used for tube conditioning if it type screw caps fitted with combined poly- supports a dedicated tube conditioning mode tetrafluoroethylene ferrules. in which effluent from contaminated tubes is 6.4.2 Storage and transportation con- directed to vent without passing through tainers. Use clean glass jars, metal cans or key parts of the sample flow path such as the rigid, non-emitting polymer boxes. focusing trap. NOTE: You may add a small packet of new activated charcoal or charcoal/silica gel to 6.2.2 Dedicated tube conditioning units the shipping container for storage and trans- must be leak-tight to prevent air ingress, portation of batches of conditioned sorbent allow precise and reproducible temperature tubes prior to use. Coolers without ice packs ± ° selection ( 5 C), offer a temperature range make suitable shipping boxes for containers at least as great as that of the thermal of tubes because the coolers help to insulate desorber, and support inert gas flows in the the samples from extreme temperatures (e.g., range up to 100 mL/min. if left in a parked vehicle). NOTE: For safety and to avoid laboratory contamination, effluent gases from freshly 6.5 UNHEATED GC INJECTION UNIT FOR packed or highly contaminated tubes should LOADING STANDARDS ONTO BLANK TUBES be passed through a charcoal filter during A suitable device has a simple push fit or the conditioning process to prevent desorbed finger-tightening connector for attaching VOCs from polluting the laboratory atmos- the sampling end of blank sorbent tubes phere. without damaging the tube. It also has a means of controlling carrier gas flow 6.3 TUBE LABELING through the injector and attached sorbent 6.3.1 Label the sample tubes with a unique tube at 50–100 mL/min and includes a low permanent identification number and an in- emission septum cap that allows the intro- dication of the sampling end of the tube. La- duction of gas or liquid standards via appro- beling options include etching and TD-com- priate syringes. Reproducible and quan- patible electronic (radio frequency identi- titative transfer of higher boiling compounds fication (RFID)) tube labels. in liquid standards is facilitated if the injec- 6.3.2 To avoid contamination, do not tion unit allows the tip of the syringe to just make ink markings of any kind on clean sor- touch the sorbent retaining gauze inside the bent tubes or apply adhesive labels. tube. NOTE: TD-compatible electronic (RFID) 6.6 THERMAL DESORPTION APPARATUS tube labels are available commercially and are compatible with some brands of thermal The manual or automated thermal desorber. If used, these may be programmed desorption system must heat sorbent tubes with relevant tube and sample information, while a controlled flow of inert (carrier) gas which can be read and automatically tran- passes through the tube and out of the sam- scribed into the sequence report by the TD pling end. The apparatus must also incor- system (see Section 8.6 of Method 325A). porate a focusing trap to quantitatively

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refocus compounds desorbed from the tube. thicknesses of stationary phase have been Secondary desorption of the focusing trap used successfully for non-polar and mod- should be fast/efficient enough to transfer erately polar compounds. However, given the the compounds into the high resolution cap- diversity of potential target lists, GC column illary GC column without band broadening choice is left to the operator, subject to the and without any need for further pre- or on- performance criteria of this method. column focusing. Typical TD focusing traps comprise small sorbent traps (Reference 16) 6.10 MASS SPECTROMETER that are electrically-cooled using multistage Linear quadrupole, magnetic sector, ion Peltier cells (References 17, 18). The direc- trap or time-of-flight mass spectrometers tion of gas flow during trap desorption may be used provided they meet specified should be the reverse of that used for focus- performance criteria. The mass detector ing to extend the compatible analyte vola- must be capable of collecting data from 35 to tility range. Closed cycle coolers offer an- 300 atomic mass units (amu) every 1 second other cryogen-free trap cooling option. Other or less, utilizing 70 volts (nominal) electron TD system requirements and operational energy in the electron ionization mode, and stages are described in Section 11 and in Fig- producing a mass spectrum that meets all ures 17–2 through 17–4. the instrument performance acceptance cri- 6.7 THERMAL DESORBER—GC INTERFACE teria in Section 9 when 50 hg or less of p- bromofluorobenzene is analyzed. 6.7.1 The interface between the thermal desorber and the GC must be heated uni- 7.0 REAGENTS AND STANDARDS formly and the connection between the transfer line insert and the capillary GC ana- 7.1 SORBENT SELECTION lytical column itself must be leak tight. 7.1.1 Use commercially packed tubes 6.7.2 A portion of capillary column can al- meeting the requirements of this method or ternatively be threaded through the heated prepare tubes in the laboratory using sieved transfer line/TD interface and connected di- sorbents of particle size in the range 20 to 80 rectly to the thermal desorber. mesh that meet the retention and quality NOTE: Use of a metal syringe-type needle control requirements of this method. or unheated length of fused silica pushed 7.1.2 This passive air monitoring method through the septum of a conventional GC in- can be used without the evaluation specified jector is not permitted as a means of inter- in Addendum A if the type of tubes described facing the thermal desorber to the chro- in Section 6.1 are packed with 4–6 cm (typi- matograph. Such connections result in cold cally 400–650 mg) of the sorbents listed in spots, cause band broadening and are prone Table 12.1 and used for the respective target to leaks. analytes. NOTE: Although CarbopackTM X is the opti- 6.8 GC/MS ANALYTICAL COMPONENTS mum sorbent choice for passive sampling of 6.8.1 The GC system must be capable of 1,3-butadiene, recovery of compounds with temperature programming and operation of a vapor pressure lower than benzene may be high resolution capillary column. Depending difficult to achieve without exceeding sor- on the choice of column (e.g., film thickness) bent maximum temperature limitations (see and the volatility of the target compounds, Table 8.1). See ISO 16017–2:2003(E) or ASTM it may be necessary to cool the GC oven to D6196–03 (Reapproved 2009) (both incor- subambient temperatures (e.g., ¥50 °C) at porated by reference—see § 63.14) for more de- the start of the run to allow resolution of tails on sorbent choice for air monitoring very volatile organic compounds. using passive sampling tubes. 6.8.2 All carrier gas lines supplying the 7.1.3 If standard passive sampling tubes GC must be constructed from clean stainless are packed with other sorbents or used for steel or copper tubing. Non-polytetrafluoro- analytes other than those tabulated in Sec- ethylene thread sealants. Flow controllers, tion 12.0, method performance and relevant cylinder regulators, or other pneumatic com- uptake rates should be verified according to ponents fitted with rubber components are Addendum A to this method or by following not suitable. the techniques described in one of the following national/international standard 6.9 CHROMATOGRAPHIC COLUMNS methods: ISO 16017–2:2003(E), ASTM D6196–03 High-resolution, fused silica or equivalent (Reapproved 2009), or BS EN 14662–4:2005 (all capillary columns that provide adequate sep- incorporated by reference—see § 63.14)—or re- aration of sample components to permit ported in the peer-reviewed open literature. identification and quantitation of target A summary table and the supporting evalua- compounds must be used. tion data demonstrating the selected sorbent NOTE: 100-percent methyl silicone or 5-per- meets the requirements in Addendum A to cent phenyl, 95-percent methyl silicone fused this method must be submitted to the regu- silica capillary columns of 0.25- to 0.32-mm latory authority as part of a request to use i.d. of varying lengths and with varying an alternative sorbent.

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7.1.4 Passive (diffusive) sampling and 7.2.3 Follow manufacturer’s guidelines thermal desorption methods that have been concerning storage conditions and recertifi- evaluated at relatively high atmospheric cation of the concentrated gas phase stand- concentrations (i.e., mid-ppb to ppm) and ard. Gas standards must be recertified a min- published for use in workplace air and indus- imum of once every 12 months. trial/mobile source emissions testing (Ref- erences 9–20) may be applied to this proce- 7.3 LIQUID STANDARDS dure. However, the validity of any shorter Target analytes can also be introduced to term uptake rates must be verified and ad- the sampling end of sorbent tubes in the justed if necessary for the longer monitoring form of liquid calibration standards. periods required by this method by following 7.3.1 The concentration of liquid stand- procedures described in Addendum A to this ards must be such that an injection of 0.5–2 method or those presented in national/inter- μl of the solution introduces the same mass national standard methods: ISO 16017– of target analyte that is expected to be col- 2:2003(E), ASTM D6196–03 (Reapproved 2009), lected during the passive air sampling pe- or BS EN 14662–4:2005 (all incorporated by riod. reference-see § 63.14). 7.3.2 Solvent Selection. The solvent se- 7.1.5 Suitable sorbents for passive sam- lected for the liquid standard must be pure pling must have breakthrough volumes of at (contaminants <10 percent of minimum least 20 L (preferably >100 L) for the com- analyte levels) and must not interfere pounds of interest and must quantitatively chromatographically with the compounds of release the analytes during desorption with- interest. out exceeding maximum temperatures for 7.3.3 If liquid standards are sourced com- the sorbent or instrumentation. mercially, follow manufacturer’s guidelines 7.1.6 Repack/replace the sorbent tubes or concerning storage conditions and shelf life demonstrate tube performance following the of unopened and opened liquid stock stand- requirements in Addendum A to this method ards. at least every 2 years or every 50 uses, which- NOTE: Commercial VOC standards are typi- ever occurs first. cally supplied in volatile or non-interfering 7.2 GAS PHASE STANDARDS solvents such as methanol. 7.3.4 Working standards must be stored at 7.2.1 Static or dynamic standard 6 °C or less and used or discarded within two atmospheres may be used to prepare calibra- weeks of preparation. tion tubes and/or to validate passive sampling uptake rates and can be generated from 7.4 GAS PHASE INTERNAL STANDARDS pure chemicals or by diluting concentrated 7.4.1 Gas-phase deuterated or fluorinated gas standards. The standard atmosphere organic compounds may be used as internal must be stable at ambient pressure and accu- standards for MS-based systems. rate to ±10 percent of the target gas concentration. It must be possible to maintain 7.4.2 Typical compounds include standard atmosphere concentrations at the deuterated toluene, perfluorobenzene and same or lower levels than the target com- perfluorotoluene. pound concentration objectives of the test. 7.4.3 Use multiple internal standards to Test atmospheres used for validation of up- cover the volatility range of the target take rates must also contain at least 35 per- analytes. cent relative humidity. 7.4.4 Gas-phase standards must be ob- NOTE: Accurate, low-(ppb-) level gas-phase tained in pressurized cylinders and con- VOC standards are difficult to generate from taining vendor certified gas concentrations ± pure materials and may be unstable depend- accurate to 5 percent. The concentration ing on analyte polarity and volatility. Par- should be such that the mass of internal allel monitoring of vapor concentrations standard components introduced is similar with alternative methods, such as pumped to those of the target analytes collected dur- sorbent tubes or sensitive/selective on-line ing field monitoring. detectors, may be necessary to minimize un- 7.5 PRELOADED STANDARD TUBES certainty. For these reasons, standard atmospheres are rarely used for routine cali- Certified, preloaded standard tubes, accu- bration. rate within ±5 percent for each analyte at 7.2.2 Concentrated, pressurized gas phase the microgram level and ±10 percent at the standards. Accurate (±5 percent or better), nanogram level, are available commercially concentrated gas phase standards supplied in and may be used for auditing and quality pressurized cylinders may also be used for control purposes. (See Section 9.5 for audit calibration. The concentration of the stand- accuracy evaluation criteria.) Certified pre- ard should be such that a 0.5–5.0 mL volume loaded tubes may also be used for routine contains approximately the same mass of calibration. analytes as will be collected from a typical NOTE: Proficiency testing schemes are also air sample. available for TD/GC/MS analysis of sorbent

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tubes preloaded with common analytes such 8.0 SORBENT TUBE HANDLING (BEFORE AND as benzene, toluene, and xylene. AFTER SAMPLING)

7.6 CARRIER GASES 8.1 SAMPLE TUBE CONDITIONING Use inert, 99.999-percent or higher purity 8.1.1 Sampling tubes must be conditioned helium as carrier gas. Oxygen and organic using the apparatus described in Section 6.2. filters must be installed in the carrier gas 8.1.2 New tubes should be conditioned for 2 lines supplying the analytical system ac- hours to supplement the vendor’s conditioning procedure. Recommended tempera- cording to the manufacturer’s instructions. tures for tube conditioning are given in Keep records of filter and oxygen scrubber Table 8.1. replacement. 8.1.3 After conditioning, the blank must be verified on each new sorbent tube and on 10 percent of each batch of reconditioned tubes. See Section 9.0 for acceptance criteria.

TABLE 8.1—EXAMPLE SORBENT TUBE CONDITIONING PARAMETERS

Maximum Conditioning Sampling sorbent temperature temperature Carrier gas ( °C) ( °C) flow rate

Carbotrap® C ...... >400 350 100 mL/min CarbopackTM C Anasorb® GCB2 CarbographTM 1 TD Carbotrap® CarbopackTM B Anasorb® GCB1 Tenax® TA CarbopackTM X ...... 350 330 100 mL/min

8.2 CAPPING, STORAGE AND SHIPMENT OF 10.9.4. (at least one per analysis sequence or CONDITIONED TUBES every 24 hours), and duplicate samples as specified in Section 9.4 (at least one dupli- 8.2.1 Conditioned tubes must be sealed cate sample is required for every 10 sampling using long-term storage caps (see Section locations during each monitoring period). 6.4) pushed fully down onto both ends of the PS sorbent tube, tightened by hand and then 8.4 SAMPLE COLLECTION tighten an additional quarter turn using an appropriate tool. 8.4.1 Allow the tubes to equilibrate with 8.2.2 The capped tubes must be kept in ap- ambient temperature (approximately 30 min- propriate containers for storage and trans- utes to 1 hour) at the monitoring location portation (see Section 6.4.2). Containers of before removing them from their storage/ sorbent tubes may be stored and shipped at shipping container for sample collection. ambient temperature and must be kept in a 8.4.2 Tubes must be used for sampling clean environment. within 30 days of conditioning (Reference 4). 8.2.3 You must keep batches of capped 8.4.3 During field monitoring, the long- tubes in their shipping boxes or wrap them term storage cap at the sampling end of the in uncoated aluminum foil before placing tube is replaced with a diffusion cap and the them in their storage container, especially whole assembly is arranged vertically, with before air freight, because the packaging the sampling end pointing downward, under helps hold caps in position if the tubes get a protective hood or shield—See Section 6.1 very cold. of Method 325A for more details.

8.3 CALCULATING THE NUMBER OF TUBES 8.5 SAMPLE STORAGE REQUIRED FOR A MONITORING EXERCISE 8.5.1 After sampling, tubes must be imme- 8.3.1 Follow guidance given in Method diately resealed with long-term storage caps 325A to determine the number of tubes re- and placed back inside the type of storage quired for site monitoring. container described in Section 6.4.2. 8.3.2 The following additional samples 8.5.2 Exposed tubes may not be placed in will also be required: Laboratory blanks as the same container as clean tubes. They specified in Section 9.1.2 (one per analytical should not be taken back out of the consequence minimum), field blanks as specified tainer until ready for analysis and after they in Section 9.3.2 (two per sampling period have had time to equilibrate with ambient minimum), CCV tubes as specified in Section temperature in the laboratory.

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8.5.3 Sampled tubes must be inspected be- 9.2.3 If unacceptable levels of VOCs are fore analysis to identify problems such as observed in the tube blanks, then the proc- loose or missing caps, damaged tubes, tubes esses of tube conditioning and checking the that appear to be leaking sorbent or con- blanks must be repeated. tainer contamination. Any and all such problems must be documented together with the 9.3 FIELD BLANKS unique identification number of the tube or 9.3.1 Field blank tubes must be prepared tubes concerned. Affected tubes must not be from tubes that are identical to those used analyzed but must be set aside. for field sampling—i.e., they should be from 8.5.4 Intact tubes must be analyzed within the same batch, have a similar history, and 30 days of the end of sample collection (with- be conditioned at the same time. in one week for limonene, carene, bis- 9.3.2 Field blanks must be shipped to the chloromethyl ether, labile sulfur or nitro- monitoring site with the sampling tubes and gen-containing compounds, and other reac- must be stored at the sampling location tive VOCs). throughout the monitoring exercise. The NOTE: Ensure ambient temperatures stay field blanks must be installed under a pro- below 23 °C during transportation and stor- tective hood/cover at the sampling location, age. Refrigeration is not normally required but the long-term storage caps must remain unless the samples contain reactive com- in place throughout the monitoring period pounds or cannot be analyzed within 30 days. (see Method 325A). The field blanks are then If refrigeration is used, the atmosphere in- shipped back to the laboratory in the same side the refrigerator must be clean and free container as the sampled tubes. Collect at of organic solvents. least two field blank samples per sampling period to ensure sample integrity associated 9.0 QUALITY CONTROL with shipment, collection, and storage. 9.1 LABORATORY BLANK 9.3.3 Field blanks must contain no greater than one-third of the measured target The analytical system must be dem- analyte or compliance limit for field samples onstrated to be contaminant free by per- (see Table 17.1). If either field blank fails, forming a blank analysis at the beginning of flag all data that do not meet this criterion each analytical sequence to demonstrate with a note that the associated results are that the secondary trap and TD/GC/MS ana- estimated and likely to be biased high due to lytical equipment are free of any significant field blank background. interferents. 9.1.1 Laboratory blank tubes must be pre- 9.4 DUPLICATE SAMPLES pared from tubes that are identical to those Duplicate (co-located) samples collected used for field sampling. must be analyzed and reported as part of 9.1.2 Analysis of at least one laboratory method quality control. They are used to blank is required per analytical sequence. evaluate sampling and analysis precision. The laboratory blank must be stored in the Relevant performance criteria are given in laboratory under clean, controlled ambient Section 9.9. temperature conditions. 9.1.3 Laboratory blank/artifact levels 9.5 METHOD PERFORMANCE CRITERIA must meet the requirements of Section 9.2.2 (see also Table 17.1). If the laboratory blank Unless otherwise noted, monitoring meth- does not meet requirements, stop and per- od performance specifications must be dem- form corrective actions and then re-analyze onstrated for the target compounds using laboratory blank to ensure it meets require- the procedures described in Addendum A to ments. this method and the statistical approach presented in Method 301. 9.2 TUBE CONDITIONING 9.6 METHOD DETECTION LIMIT 9.2.1 Conditioned tubes must be demonstrated to be free of contaminants and in- Determine the method detection limit terference by running 10 percent of the blank under the analytical conditions selected (see tubes selected at random from each condi- Section 11.3) using the procedure in Section tioned batch under standard sample analysis 15 of Method 301. The method detection limit conditions (see Section 8.1). is defined for each system by making seven 9.2.2 Confirm that artifacts and back- replicate measurements of a concentration ground contamination are ≤ 0.2 ppbv or less of the compound of interest within a factor than three times the detection limit of the of five of the detection limit. Compute the procedure or less than 10 percent of the tar- standard deviation for the seven replicate get compound(s) mass that would be col- concentrations, and multiply this value by lected if airborne concentrations were at the three. The results should demonstrate that regulated limit value, whichever is larger. the method is able to detect analytes such as Only tubes that meet these criteria can be benzene at concentrations as low as 50 ppt or used for field monitoring, field or laboratory 1/3rd (preferably 1/10th) of the lowest con- blanks, or for system calibration. centration of interest, whichever is larger.

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NOTE: Determining the detection limit alytical bias must be demonstrated during may be an iterative process as described in 40 initial setup of this method and as part of CFR part 136, Appendix B. the CCV carried out with every sequence of 10 samples or less (see Section 9.14). Calibra- 9.7 ANALYTICAL BIAS tion standard tubes (see Section 10.0) may be Analytical bias must be demonstrated to used for this purpose. be within ±30 percent using Equation 9.1. An-

Eq. 9.1 9.8 ANALYTICAL PRECISION Where: Demonstrate an analytical precision with- Spiked Value = A known mass of VOCs added in ±20 percent using Equation 9.2. Analytical to the tube. precision must be demonstrated during ini- Measured Value = Mass determined from tial setup of this method and at least once analysis of the tube. per year. Calibration standard tubes may be used (see Section 10.0) and data from CCV may also be applied for this purpose.

Eq. 9.2 9.9 FIELD REPLICATE PRECISION Where: Use Equation 9.3 to determine and report A1 = A measurement value taken from one replicate precision for duplicate field sam- spiked tube. ples (see Section 9.4). The level of agreement A2 = A measurement value taken from a sec- between duplicate field samples is a measure ond spiked tube. of the precision achievable for the entire A = The average of A1 and A2. sampling and analysis procedure. Flag data sets for which the duplicate samples do not agree within 30 percent.

Eq. 9.3 9.10 DESORPTION EFFICIENCY AND COMPOUND Where: RECOVERY F1 = A measurement value (mass) taken The efficiency of the thermal desorption from one of the two field replicate tubes method must be determined. used in sampling. 9.10.1 Quantitative (>95 percent) com- F2 = A measurement value (mass) taken pound recovery must be demonstrated by re- from the second of two field replicate peat analyses on a same standard tube. tubes used in sampling. 9.10.2 Compound recovery through the TD F = The average of F1 and F2. system can also be demonstrated by comparing the calibration check sample response factor obtained from direct GC injection of liquid standards with that obtained from thermal desorption analysis response factor

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using the same column under identical con- 9.14 CCV AT THE END OF A SEQUENCE ditions. Run another CCV after running each se- 9.10.3 If the relative response factors ob- quence of samples. The initial CCV for a sub- tained for one or more target compounds in- sequent set of samples may be used as the troduced to the column via thermal final CCV for a previous analytical sequence, desorption fail to meet the criteria in Sec- provided the same analytical method is used tion 9.10.1, you must adjust the TD param- and the subsequent set of samples is ana- eters to meet the criteria and repeat the ex- lyzed immediately (within 4 hours) after the periment. Once the thermal desorption con- last CCV. ditions have been optimized, you must repeat this test each time the analytical sys- 9.15 ADDITIONAL VERIFICATION tem is recalibrated to demonstrate contin- Use a calibration check standard from a ued method performance. second, separate source to verify the original calibration at least once every three months. 9.11 AUDIT SAMPLES Certified reference standard samples must 9.16 INTEGRATION METHOD be used to audit this procedure (if available). Document the procedure used for integra- Accuracy within 30 percent must be dem- tion of analytical data including field sam- onstrated for relevant ambient air con- ples, calibration standards and blanks. centrations (0.5 to 25 ppb). 9.17 QC RECORDS 9.12 MASS SPECTROMETER TUNING CRITERIA Maintain all QC reports/records for each Tune the mass spectrometer (if used) ac- TD/GC/MS analytical system used for appli- cording to manufacturer’s specifications. cation of this method. Routine quality con- Verify the instrument performance by ana- trol requirements for this method are listed lyzing a 50 hg injection of below and summarized in Table 17.1. bromofluorobenzene. Prior to the beginning of each analytical sequence or every 24 hours 10.0 CALIBRATION AND STANDARDIZATION during continuous GC/MS operation for this 10.1 Calibrate the analytical system using method demonstrate that the standards covering the range of analyte bromofluorobenzene tuning performance cri- masses expected from field samples. teria in Table 9.1 have been met. 10.2 Analytical results for field samples must fall within the calibrated range of the TABLE 9.1—GC/MS TUNING CRITERIA 1 analytical system to be valid. 10.3 Calibration standard preparation Target Rel. to mass Lower limit % Upper limit % must be fully traceable to primary standards mass of mass and/or volume, and/or be confirmed using an independent certified reference 50 ...... 95 8 40 method. 75 ...... 95 30 66 95 ...... 95 100 100 10.3.1 Preparation of calibration standard 96 ...... 95 5 9 tubes from standard atmospheres. 173 ...... 174 0 2 10.3.1.1 Subject to the requirements in 174 ...... 95 50 120 Section 7.2.1, low-level standard atmospheres 175 ...... 174 4 9 may be introduced to clean, conditioned sor- 176 ...... 174 93 101 bent tubes in order to produce calibration 177 ...... 176 5 9 standards. 10.3.1.2 The standard atmosphere gener- 1 All ion abundances must be normalized to m/z 95, the ator or system must be capable of producing nominal base peak, even though the ion abundance of m/z 174 may be up to 120 percent that of m/z 95. sufficient flow at a constant rate to allow the required analyte mass to be introduced 9.13 ROUTINE CCV AT THE START OF A within a reasonable time frame and without SEQUENCE affecting the concentration of the standard atmosphere itself. 9.13 Run CCV before each sequence of 10.3.1.3 The sampling manifold may be analyses and after every tenth sample to en- heated to minimize risk of condensation but sure that the previous multi-level calibra- the temperature of the gas delivered to the tion (see section 10.0) is still valid. sorbent tubes may not exceed 100 °F. 9.13.1 The sample concentration used for 10.3.1.4 The flow rates passed through the the CCV should be near the mid-point of the tube should be in the order of 50–100 mL/min multi-level calibration range. and the volume of standard atmosphere sam- 9.13.2 Quantitation software must be up- pled from the manifold or chamber must not dated with response factors determined from exceed the breakthrough volume of the sor- the CCV standard. The percent deviation be- bent at the given temperature. tween the initial calibration and the CCV for 10.4 Preparation of calibration standard all compounds must be within 30 percent. tubes from concentrated gas standards.

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10.4.1 If a suitable concentrated gas stand- ference between the before spiking volume ard (see Section 7.2.2) can be obtained, follow and the after spiking volume. A bias occurs the manufacturer’s recommendations relat- with this method when sample is drawn con- ing to suitable storage conditions and prod- tinuously up into the syringe to the specified uct lifetime. volume and the calibration solution in the 10.4.2 Introduce precise 0.5 to 500.0 mL syringe tip is ignored. aliquots of the standard to the sampling end 10.6 Preparation of calibration standard of conditioned sorbent tubes in a 50–100 mL/ tubes from multiple standards. min flow of pure carrier gas. 10.6.1 If it is not possible to prepare one NOTE: This can be achieved by connecting standard containing all the compounds of in- the sampling end of the tube to an unheated terest (e.g., because of chemical reactivity or GC injector (see Section 6.6) and introducing the breadth of the volatility range), standard the aliquot of gas using a suitable gas sy- tubes can be prepared from multiple gas or ringe. Gas sample valves could alternatively liquid standards. be used to meter the standard gas volume. 10.6.2 Follow the procedures described in 10.4.3 Each sorbent tube should be left Sections 10.4 and 10.5, respectively, for intro- connected to the flow of gas for 2 minutes ducing each gas and/or liquid standard to the after standard introduction. As soon as each tube and load those containing the highest spiked tube is removed from the injection boiling compounds of interest first and the unit, seal it with long-term storage caps and lightest species last. place it in an appropriate tube storage/trans- 10.7 Additional requirements for prepara- portation container if it is not to be ana- tion of calibration tubes. lyzed within 24 hours. 10.7.1 Storage of Calibration Standard 10.5 Preparation of calibration standard Tubes tubes from liquid standards. 10.7.1.1 Seal tubes with long-term storage 10.5.1 Suitable standards are described in caps immediately after they have been dis- Section 7.3. connected from the standard loading mani- 10.5.2 Introduce precise 0.5 to 2 μl aliquots fold or injection apparatus. of liquid standards to the sampling end of 10.7.1.2 Calibration standard tubes may be sorbent tubes in a flow (50–100 mL/min) of stored for no longer than 30 days and should carrier gas using a precision syringe and an be refrigerated if there is any risk of chem- unheated injector (Section 6.5). The flow of ical interaction or degradation. Audit stand- gas should be sufficient to completely vapor- ards (see section 9.11) are exempt from this ize the liquid standard. criteria and may be stored for the shelf-life NOTE: If the analytes of interest are higher specified on their certificates. boiling than n-decane, reproducible analyte 10.8 Keep records for calibration standard transfer to the sorbent bed is optimized by tubes to include the following: allowing the tip of the syringe to gently 10.8.1 The stock number of any commer- touch the sorbent retaining gauze at the cial liquid or gas standards used. sampling end of the tube. 10.8.2 A chromatogram of the most recent 10.5.3 Each sorbent tube is left connected blank for each tube used as a calibration to the flow of gas for 5 minutes after liquid standard together with the associated ana- standard introduction. lytical conditions and date of cleaning. 10.5.3.1 As soon as each spiked tube is re- 10.8.3 Date of standard loading. moved from the injection unit, seal it with 10.8.4 List of standard components, ap- long-term storage caps and place it in an approximate masses and associated confidence propriate tube storage container if it is not levels. to be analyzed within 24 hours. 10.8.5 Example analysis of an identical NOTE: In cases where it is possible to selec- standard with associated analytical condi- tively purge the solvent from the tube while tions. all target analytes are quantitatively re- 10.8.6 A brief description of the method tained, a larger 2 μL injection may be made used for standard preparation. for optimum accuracy. However, if the sol- 10.8.7 The standard’s expiration date. vent cannot be selectively purged and will be 10.9 TD/GC/MS using standard tubes to present during analysis, the injection vol- calibrate system response. ume should be as small as possible (e.g., 0.5 10.9.1 Verify that the TD/GC/MS analyt- μL) to minimize solvent interference. ical system meets the instrument perform- NOTE: This standard preparation technique ance criteria given in Section 9.1. requires the entire liquid plug including the 10.9.2 The prepared calibration standard tip volume be brought into the syringe bar- tubes must be analyzed using the analytical rel. The volume in the barrel is recorded, the conditions applied to field samples (see Sec- syringe is inserted into the septum of the tion 11.0) and must be selected to ensure spiking apparatus. The liquid is then quickly quantitative transfer and adequate injected. Any remaining liquid in the syringe chromatographic resolution of target com- tip is brought back into the syringe barrel. pounds, surrogates, and internal standards in The volume in the barrel is recorded and the order to enable reliable identification and amount spiked onto the tube is the dif- quantitation of compounds of interest. The

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analytical conditions should also be suffi- same concentration as the daily CCV stand- ciently stringent to prevent buildup of high- ard (e.g., the mass collected when sampling er boiling, non-target contaminants that air at typical concentrations). may be collected on the tubes during field 10.9.5 Calibration frequency. Each GC/MS monitoring. system must be recalibrated with a full 5- 10.9.3 Calibration range. Each TD/GC/MS point calibration curve following corrective system must be calibrated at five concentra- action (e.g., ion source cleaning or repair, tions that span the monitoring range of in- column replacement) or if the instrument terest before being used for sample analysis. fails the daily calibration acceptance cri- This initial multi-level calibration deter- teria. mines instrument sensitivity under the ana- 10.9.5.1 CCV checks must be carried out lytical conditions selected and the linearity on a regular routine basis as described in of GC/MS response for the target compounds. Section 9.14. One of the calibration points must be within 10.9.5.2 Quantitation ions for the target a factor of five of the detection limit for the compounds are shown in Table 10.1. Use the compounds of interest. primary ion unless interferences are present, 10.9.4 One of the calibration points from in which case you should use a secondary the initial calibration curve must be at the ion.

TABLE 10.1—CLEAN AIR ACT VOLATILE ORGANIC COMPOUNDS FOR PASSIVE SORBENT SAMPLING

Vapor Characteristic ion(s) BP b Compound CAS No. ( °C) pressure MW (mmHg) a Primary Secondary

1,1-Dichloroethene ...... 75–35–4 32 500 96.9 61 96 3-Chloropropene ...... 107–05–1 44.5 340 76.5 76 41, 39, 78 1,1,2-Trichloro-1,2,2- trifluoroethane-1,1- Dichloroethane ...... 75–34–3 57.0 230 99 63 65, 83, 85, 98, 100 1,2-Dichloroethane ...... 107–06–2 83.5 61.5 99 62 98 1,1,1-Trichloroethane ...... 71–55–6 74.1 100 133.4 97 99, 61 Benzene ...... 71–43–2 80.1 76.0 78 78 Carbon tetrachloride ...... 56–23–5 76.7 90.0 153.8 117 119 1,2-Dichloropropane ...... 78–87–5 97.0 42.0 113 63 112 Trichloroethene ...... 79–01–6 87.0 20.0 131.4 95 97, 130, 132 1,1,2-Trichloroethane ...... 79–00–5 114 19.0 133.4 83 97, 85 Toluene ...... 108–88–3 111 22.0 92 92 91 Tetrachloroethene ...... 127–18–4 121 14.0 165.8 164 129, 131, 166 Chlorobenzene ...... 108–90–7 132 8.8 112.6 112 77, 114 Ethylbenzene ...... 100–41–4 136 7.0 106 91 106 m,p-Xylene ...... 108–38–3, 138 6.5 106.2 106 91 106–42–3 Styrene ...... 100–42–5 145 6.6 104 104 78 o-Xylene ...... 95–47–6 144 5.0 106.2 106 91 p-Dichlorobenzene ...... 106–46–7 173 0.60 147 146 111, 148 a Pressure in millimeters of mercury. b Molecular weight.

11.0 ANALYTICAL PROCEDURE 11.2 PRE-DESORPTION SYSTEM CHECKS AND PROCEDURES 11.1 PREPARATION FOR SAMPLE ANALYSIS 11.2.1 Ensure all sample tubes and field 11.1.1 Each sequence of analyses must be blanks are at ambient temperature before re- ordered as follows: moving them from the storage container. 11.1.1.1 CCV. 11.2.2 If using an automated TD/GC/MS 11.1.1.2 A laboratory blank. analyzer, remove the long-term storage caps 11.1.1.3 Field blank. from the tubes, replace them with appro- 11.1.1.4 Sample(s). priate analytical caps, and load them into 11.1.1.5 Field blank. the system in the sequence described in Sec- 11.1.1.6 CCV after 10 field samples. tion 11.1. Alternatively, if using a manual 11.1.1.7 CCV at the end of the sample system, uncap and analyze each tube, one at batch. a time, in the sequence described in Section 11.1. 11.2.3 The following thermal desorption system integrity checks and procedures are required before each tube is analyzed.

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NOTE: Commercial thermal desorbers 11.3 ANALYTICAL PROCEDURE should implement these steps automatically. 11.2.3.1 Tube leak test: Each tube must be 11.3.1 STEPS REQUIRED FOR THERMAL DESORPTION leak tested as soon as it is loaded into the carrier gas flow path before analysis to en- 11.3.1.1 Ensure that the pressure and pu- sure data integrity. rity of purge and carrier gases supplying the 11.2.3.2 Conduct the leak test at the GC TD/GC/MS system, meet manufacturer speci- carrier gas pressure, without heat or gas fications and the requirements of this meth- flow applied. Tubes that fail the leak test od. should not be analyzed, but should be re- 11.3.1.2 Ensure also that the analytical sealed and stored intact. On automated sys- method selected meets the QC requirements of this method (Section 9) and that all the tems, the instrument should continue to analytical parameters are at set point. leak test and analyze subsequent tubes after 11.3.1.3 Conduct predesorption system a given tube has failed. Automated systems checks (see Section 11.2). must also store and record which tubes in a 11.3.1.4 Desorb the sorbent tube under sequence have failed the leak test. Informa- conditions demonstrated to achieve >95 per- tion on failed tubes should be downloaded cent recovery of target compounds (see Sec- with the batch of sequence information from tion 9.5.2). the analytical system. NOTE: Typical tube desorption conditions 11.2.3.3 Leak test the sample flow path. range from 280–350 °C for 5–15 minutes with a Leak check the sample flow path of the ther- carrier gas flow of 30–100 mL/min passing mal desorber before each analysis without through the tube from the non-sampling end heat or gas flow applied to the sample tube. such that analytes are flushed out of the Stop the automatic sequence of tube tube from the sampling end. Desorbed VOCs desorption and GC analysis if any leak is de- are concentrated (refocused) on a secondary, tected in the main sample flow path. This cooled sorbent trap integrated into the ana- process may be carried out as a separate step lytical equipment (see Figure 17.4). The fo- or as part of Section 11.2.3.2. cusing trap is typically maintained at a temperature between ¥30 and +30 °C during fo- 11.2.4 OPTIONAL DRY PURGE cusing. Selection of hydrophobic sorbents for focusing and setting a trapping temperature 11.2.4.1 Tubes may be dry purged with a of +25 to 27 °C aid analysis of humid samples flow of pure dry gas passing into the tube because these settings allow selective elimi- from the sampling end, to remove water nation of any residual water from the sys- vapor and other very volatile interferents if tem, prior to GC/MS analysis. required. NOTE: The transfer of analytes from the tube to the focusing trap during primary 11.2.5 INTERNAL STANDARD (IS) ADDITION (tube) desorption can be carried out splitless or under controlled split conditions (see Fig- 11.2.5.1 Use the internal standard addition ure 17.4) depending on the masses of target function of the automated thermal desorber compounds sampled and the requirements of (if available) to introduce a precise aliquot the system—sensitivity, required calibration of the internal standard to the sampling end range, column overload limitations, etc. In- of each tube after the leak test and shortly strument controlled sample splits must be before primary (tube) desorption). demonstrated by showing the reproducibility NOTE: This step can be combined with dry using calibration standards. Field and lab- purging the tube (Section 11.2.4) if required. oratory blank samples must be analyzed at 11.2.5.2 If the analyzer does not have a fa- the same split as the lowest calibration cility for automatic IS addition, gas or liq- standard. During secondary (trap) desorption uid internal standard can be manually intro- the focusing trap is heated rapidly (typically duced to the sampling end of tubes in a flow at rates >40 °C/s) with inert (carrier) gas of carrier gas using the types of procedure flowing through the trap (3–100 mL/min) in described in Sections 10.3 and 10.4, respec- the reverse direction to that used during fo- tively. cusing. 11.3.1.5 The split conditions selected for 11.2.6 Pre-purge. Each tube should be optimum field sample analysis must also be purged to vent with carrier gas flowing in demonstrated on representative standards. the desorption direction (i.e., flowing into NOTE: Typical trap desorption tempera- the tube from the non-sampling end) to re- tures are in the range 250–360 °C, with a move oxygen before heat is applied. This is ‘‘hold’’ time of 1–3 minutes at the highest to prevent analyte and sorbent oxidation and temperature. Trap desorption automatically to prevent deterioration of key analyzer triggers the start of GC analysis. The trap components such as the GC column and mass desorption can also be carried out under spectrometer (if applicable). A series of sche- splitless conditions (i.e., with everything matics illustrating these steps is presented desorbed from the trap being transferred to in Figures 17.2 and 17.3. the analytical column and GC detector) or,

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more commonly, under controlled split con- 11.3.2.5 Whenever the thermal ditions (see Figure 17.4). The selected split desorption—GC/MS analytical method is ratio depends on the masses of target com- changed or major equipment maintenance is pounds sampled and the requirements of the performed, you must conduct a new five- system—sensitivity, required calibration level calibration (see section 10.0). System range, column overload limitations, etc. If a calibration remains valid as long as results split is selected during both primary (trap) from subsequent CCV are within 30 percent desorption and secondary (trap) desorption, of the most recent 5-point calibration (see the overall split ratio is the product of the section 9.13). Include relevant CCV data in two. Such ‘double’ split capability gives op- the supporting information in the data re- timum flexibility for accommodating con- port for each set of samples. centrated samples as well as trace-level sam- 11.3.2.6 Document, flag and explain all ples on the TD/GC/MS analytical system. sample results that exceed the calibration High resolution capillary columns and most range. Report flags and provide documenta- GC/MS detectors tend to work best with ap- tion in the analytical results for the affected proximately 20–200 ng per compound per tube sample(s). to avoid saturation. The overall split ratio 12.0 DATA ANALYSIS, CALCULATIONS, AND must be adjusted such that, when it is ap- REPORTING plied to the sample mass that is expected to be collected during field monitoring, the 12.1 RECORDKEEPING PROCEDURES FOR amount reaching the column will be attenu- SORBENT TUBES ated to fall within this range. As a rule of 12.1.1 Label sample tubes with a unique ∼ thumb this means that 20 ng samples will identification number as described in Sec- ∼ require splitless or very low split analysis, 2 tion 6.3. μ g samples will require a split ratio in the 12.1.2 Keep records of the tube numbers ∼ μ order of 50:1 and 200 g samples will require and sorbent lots used for each sampling pe- a double split method with an overall split riod. ratio in the order of 2,000:1. 12.1.3 Keep records of sorbent tube pack- 11.3.1.6 Analyzed tubes must be resealed ing if tubes are manually prepared in the with long-term storage caps immediately laboratory and not supplied commercially. after analysis (manual systems) or after These records must include the masses and/ completion of a sequence (automated sys- or bed lengths of sorbent(s) contained in tems). This prevents contamination, mini- each tube, the maximum allowable tempera- mizing the extent of tube reconditioning re- ture for that tube and the date each tube was quired before subsequent reuse. packed. If a tube is repacked at any stage, record the date of tube repacking and any 11.3.2 GC/MS ANALYTICAL PROCEDURE other relevant information required in Sec- tion 12.1. 11.3.2.1 Heat/cool the GC oven to its start- 12.1.4 Keep records of the conditioning ing set point. and blanking of tubes. These records must 11.3.2.2 If using a GC/MS system, it can be include, but are not limited to, the unique operated in either MS-Scan or MS–SIM mode identification number and measured back- (depending on required sensitivity levels and ground resulting from the tube conditioning. the type of mass spectrometer selected). As 12.1.5 Record the location, dates, tube soon as trap desorption and transfer of identification and times associated with analytes into the GC column triggers the each sample collection. Record this informa- start of the GC/MS analysis, collect mass tion on a Chain of Custody form that is sent spectral data over a range of masses from 35 to the analytical laboratory. to 300 amu. Collect at least 10 data points per 12.1.6 Field sampling personnel must com- eluting chromatographic peak in order to plete and send a Chain of Custody to the adequately integrate and quantify target analysis laboratory (see Section 8.6.4 of compounds. Method 325A for what information to include 11.3.2.3 Use secondary ion quantitation and Section 17.0 of this method for an exam- only when there are sample matrix inter- ple form). Duplicate copies of the Chain of ferences with the primary ion. If secondary Custody must be included with the sample ion quantitation is performed, flag the data report and stored with the field test data ar- and document the reasons for the alternative chive. quantitation procedure. 12.1.7 Field sampling personnel must also 11.3.2.4 Data reduction is performed by keep records of the unit vector wind direc- the instruments post processing program tion, sigma theta, temperature and baro- that is automatically accessed after data ac- metric pressure averages for the sampling quisition is completed at the end of the GC period. See Section 8.3.4 of Method 325A. run. The concentration of each target com- 12.1.8 Laboratory personnel must record pound is calculated using the previously es- the sample receipt date, and analysis date. tablished response factors for the CCV ana- 12.1.9 Laboratory personnel must main- lyzed in Section 11.1.1.6. tain records of the analytical method and

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sample results in electronic or hardcopy in 12.2 CALCULATIONS sufficient detail to reconstruct the calibra- 12.2.1 Complete the calculations in this tion, sample, and quality control results section to determine compliance with cali- from each sampling period. bration quality control criteria (see also Table 17.1). 12.2.1.1 Response factor (RF). Calculate the RF using Equation 12.1:

Where: Ms = Mass of the analyte. M = Mass of the internal standard. As = Peak area for the characteristic ion of is the analyte. 12.2.1.2 Standard deviation of the response Ais = Peak area for the characteristic ion of factors (SDRF). Calculate the SDRF using the internal standard. Equation 12.2:

Where: n = Number of calibration standards.

RFi = RF for each of the calibration com- 12.2.1.3 Percent deviation (%DEV). Cal- pounds. culate the %DEV using Equation 12.3: RF = Mean RF for each compound from the initial calibration.

Where: 12.2.1.4 Relative percent difference (RPD).

SDRF = Standard deviation. Calculate the RPD using Equation 12.4: RF = Mean RF for each compound from the initial calibration.

Where: tions determined at the sampling site tem- R1, R2 = Values that are being compared (i.e., perature and atmospheric pressure to stand- response factors in CCV). ard conditions (25 °C and 760 mm mercury) using Equation 12.5. 12.2.2 Determine the equivalent concentrations of compounds in atmospheres as follows. Correct target compound concentra-

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Where: into sorbent tubes of the dimensions specified in section 6.1, are listed in Table 12.1. mmeas = The mass of the compound as measured in the sorbent tube (μg). Adjust analytical conditions to keep expected sampled masses within range (see sec- t = The exposure time (minutes). tions 11.3.1.3 to 11.3.1.5). Best possible method t = The average temperature during the col- ss detection limits are typically in the order of lection period at the sampling site (K). 0.1 ppb for 1,3-butadiene and 0.05 ppb for vola- UNTP = The method defined diffusive uptake tile aromatics such as benzene for 14-day rate (sampling rate) (mL/min). monitoring. However, actual detection lim- NOTE: Diffusive uptake rates (UNTP) for its will depend upon the analytical condi- common VOCs, using carbon sorbents packed tions selected.

TABLE 12.1—VALIDATED SORBENTS AND UPTAKE RATES (ML/MIN) FOR SELECTED CLEAN AIR ACT COMPOUNDS

TM TM TM Compound Carbopack Carbograph 1 Carbopack Xa TD B

1,1-Dichloroethene ...... 0.57 ±0.14 not available ...... not available. 3-Chloropropene ...... 0.51 ±0.3 not available ...... not available. 1,1-Dichloroethane ...... 0.57 ±0.1 not available ...... not available. 1,2-Dichloroethane ...... 0.57 ±0.08 not available ...... not available. 1,1,1-Trichloroethane ...... 0.51 ±0.1 not available ...... not available. Benzene ...... 0.67 ±0.06 0.63 ±0.07b ...... 0.63 ±0.07b. Carbon tetrachloride ...... 0.51 ±0.06 not available ...... not available. 1,2-Dichloropropane ...... 0.52 ±0.1 not available ...... not available. Trichloroethene ...... 0.5 ±0.05 not available ...... not available. 1,1,2-Trichloroethane ...... 0.49 ±0.13 not available ...... not available. Toluene ...... 0.52 ±0.14 0.56 ±0.06c ...... 0.56 ±0.06c. Tetrachloroethene ...... 0.48 ±0.05 not available ...... not available. Chlorobenzene ...... 0.51 ±0.06 not available ...... not available. Ethylbenzene ...... 0.46 ±0.07 not available...... 0.50c. m,p-Xylene ...... 0.46 ±0.09 0.47 ±0.04c ...... 0.47 ±0.04c. Styrene ...... 0.5 ±0.14 not available ...... not available. o-Xylene ...... 0.46 ±0.12 0.47 ±0.04c ...... 0.47 ±0.04c. p-Dichlorobenzene ...... 0.45 ±0.05 not available ...... not available. a Reference 3, McClenny, J. Environ. Monit. 7:248–256. Based on 24-hour duration. b Reference 24, BS EN 14662–4:2005 (incorporated by reference—see § 63.14). Based on 14-day duration. c Reference 25, ISO 16017–2:2003(E) (incorporated by reference—see § 63.14). Based on 14-day duration.

13.0 METHOD PERFORMANCE 13.2 Diffusive sorbent tubes compatible with passive sampling and thermal The performance of this procedure for VOC desorption methods have been evaluated at not listed in Table 12.1 is determined using relatively high atmospheric concentrations the procedure in Addendum A of this Method (i.e., mid-ppb to ppm) and published for use or by one of the following national/inter- in workplace air and industrial/mobile national standard methods: ISO 16017– source emissions (References 15–16, 21–22). 2:2003(E), ASTM D6196–03 (Reapproved 2009), 13.3 Best possible detection limits and or BS EN 14662–4:2005 (all incorporated by maximum quantifiable concentrations of air reference—see § 63.14). pollutants range from sub-part-per-trillion 13.1 The valid range for measurement of (sub-ppt) for halogenated species such as VOC is approximately 0.5 μg/m3 to 5 mg/m3 in CCl4 and the freons using an electron cap- air, collected over a 14-day sampling period. ture detector (ECD), SIM Mode GC/MS, triple The upper limit of the useful range depends quad MS or GC/TOF MS to sub-ppb for vola- on the split ratio selected (Section 11.3.1) and tile hydrocarbons collected over 72 hours fol- the dynamic range of the analytical system. lowed by analysis using GC with quadrupole The lower limit of the useful range depends MS operated in the full SCAN mode. on the noise from the analytical instrument 13.3.1 Actual detection limits for atmos- detector and on the blank level of target pheric monitoring vary depending on several compounds or interfering compounds on the key factors. These factors are: sorbent tube (see Section 13.3). • Minimum artifact levels.

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• GC detector selection. 8. Gibitch, J., Ogle, L., and Radenheimer, P., • Time of exposure for passive sorbent ‘‘Analysis of Ozone Precursor Compounds tubes. in Houston, Texas Using Automated Con- • Selected analytical conditions, particu- tinuous GCs,’’ in Proceedings of the Air larly column resolution and split ratio. and Waste Management Association Con- ference: Measurement of Toxic and Re- 14.0 POLLUTION PREVENTION lated Air Pollutants, Air and Waste Man- agement Association, Pittsburgh, PA, This method involves the use of ambient May 1995. concentrations of gaseous compounds that 9. Vandendriessche, S., and Griepink, B., post little or no danger of pollution to the ‘‘The Certification of Benzene, Toluene environment. and m-Xylene Sorbed on Tenax® TA in Tubes,’’ CRM–112 CEC, BCR, EUR12308 15.0 WASTE MANAGEMENT EN, 1989. Dispose of expired calibration solutions as 10. MDHS 2 (Acrylonitrile in Air), ‘‘Labora- hazardous materials. Exercise standard lab- tory Method Using Porous Polymer Ad- oratory environmental practices to minimize sorption Tubes, and Thermal Desorption the use and disposal of laboratory solvents. with Gas Chromatographic Analysis,’’ Methods for the Determination of Haz- 16.0 REFERENCES ardous Substances (MDHS), UK Health 1. Winberry, W. T. Jr., et al., Determination and Safety Executive, Sheffield, UK. 11. MDHS 22 (Benzene in Air), ‘‘Laboratory of Volatile Organic Compounds in Ambi- Method Using Porous Polymer Adsorbent ent Air Using Active Sampling onto Sor- Tubes, Thermal Desorption and Gas bent Tubes: Method TO–17r, Second Edi- Chromatography,’’ Method for the Deter- tion, U.S. Environmental Protection mination of Hazardous Substances Agency, Research Triangle Park, NC (MDHS), UK Health and Safety Execu- 27711, January 1999. http://www.epa.gov/ tive, Sheffield, UK. ttnamti1/airtox.html#compendium 12. MDHS 23 (Glycol Ether and Glycol Ace- 2. Ciccioli, P., Brancaleoni, E., Cecinato, A., tate Vapors in Air), ‘‘Laboratory Method Sparapini, R., and Frattoni, M., ‘‘Identi- Using Tenax® Sorbent Tubes, Thermal fication and Determination of Biogenic Desorption and Gas Chromatography,’’ and Anthropogenic VOCs in Forest Areas Method for the Determination of Haz- of Northern and Southern Europe and a ardous Substances (MDHS), UK Health Remote Site of the Himalaya Region by and Safety Executive, Sheffield, UK. High-resolution GC–MS,’’ J. of Chrom., 13. MDHS 40 (Toluene in air), ‘‘Laboratory 643, pp 55–69, 1993. Method Using Pumped Porous Polymer 3. McClenny, W.A., K.D. Oliver, H.H. Adsorbent Tubes, Thermal Desorption Jacumin, Jr., E.H. Daughtrey, Jr., D.A. and Gas Chromatography,’’ Method for Whitaker. 2005. 24 h diffusive sampling of the Determination of Hazardous Sub- toxic VOCs in air onto CarbopackTM X stances (MDHS), UK Health and Safety solid adsorbent followed by thermal Executive, Sheffield, UK. desorption/GC/MS analysis—laboratory 14. MDHS 60 (Mixed Hydrocarbons (C to C) in studies. J. Environ. Monit. 7:248–256. Air), ‘‘Laboratory Method Using Pumped 4. Markes International (www.markes.com/ Porous Polymer 3 10 and Carbon Sorbent publications): Thermal desorption Tech- Tubes, Thermal Desorption and Gas nical Support Note 2: Prediction of up- Chromatography,’’ Method for the Deter- take rates for diffusive tubes. mination of Hazardous Substances 5. Ciccioli, P., Brancaleoni, E., Cecinato, A., (MDHS), UK Health and Safety Execu- DiPalo, C., Brachetti, A., and Liberti, A., tive, Sheffield, UK. ‘‘GC Evaluation of the Organic Compo- 15. Price, J. A., and Saunders, K. J., ‘‘Deter- nents Present in the Atmosphere at mination of Airborne Methyl tert-Butyl Trace Levels with the Aid of Ether in Gasoline Atmospheres,’’ Ana- CarbopackTM B for Preconcentration of lyst, Vol. 109, pp. 829–834, July 1984. the Sample,’’ J. of Chrom., 351, pp 433– 16. Coker, D. T., van den Hoed, N., Saunders, 449, 1986. K. J., and Tindle, P. E., ‘‘A Monitoring 6. Broadway, G. M., and Trewern, T., ‘‘Design Method for Gasoline Vapour Giving De- Considerations for the Optimization of a tailed Composition,’’ Ann. Occup, Hyg., Packed Thermal Desorption Cold Trap Vol 33, No. 11, pp 15–26, 1989. for Capillary Gas Chromatography,’’ 17. DFG, ‘‘Analytische Methoden zur prufing Proc. 13th Int’l Symposium on Capil. gesundheitsschadlicher Arbeistsstoffe,’’ Chrom., Baltimore, MD, pp 310–320, 1991. Deutsche Forschungsgemeinschaft, 7. Broadway, G. M., ‘‘An Automated System Verlag Chemie, Weinheim FRG, 1985. for use Without Liquid Cryogen for the 18. NNI, ‘‘Methods in NVN Series Determination of VOC’s in Ambient (Luchtkwaliteit; Werkplekatmasfeer),’’ Air,’’ Proc. 14th Int’l. Symposium on Nederlands Normailsatie—Institut, Delft, Capil. Chrom., Baltimore, MD, 1992. The Netherlands, 1986–88.

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19. ‘‘Sampling by Solid Adsorption Tech- lect Gases or Vapors with Solid Sorbent niques,’’ Standards Association of Aus- Diffusive Samplers. tralia Organic Vapours, Australian 23. Martin, http://www.hsl.gov.uk/media/1619/ Standard 2976, 1987. issue14.pdf. 20. Woolfenden, E. A., ‘‘Monitoring VOCs in 24. BS EN 14662–4:2005, Ambient air quality— Air Using Pumped Sampling onto Sor- Standard method for the measurement of bent Tubes Followed by Thermal benzene concentrations—Part 4: Diffu- Desorption-capillary GC Analysis: Sum- sive sampling followed by thermal mary of Reported Data and Practical Guidelines for Successful Application,’’ desorption and gas chromatography. J. Air & Waste Manage. Assoc., Vol. 47, 25. ISO 16017–2:2003(E): Indoor, ambient and 1997, pp. 20–36. workplace air—Sampling and analysis of 21. Validation Guidelines for Air Sampling volatile organic compounds by sorbent Methods Utilizing Chromatographic tube/thermal desorption/capillary gas Analysis, OSHA T–005, Version 3.0, May chromatography—Part 2: Diffusive sam- 2010, http://www.osha.gov/dts/sltc/methods/ pling. chromguide/chromguide.pdf. 22. ASTM D4597–10, Standard Practice for 17.0 TABLES, DIAGRAMS, FLOWCHARTS AND Sampling Workplace Atmospheres to col- VALIDATION DATA≤

TABLE 17.1—SUMMARY OF GC/MS ANALYSIS QUALITY CONTROL PROCEDURES

Parameter Frequency Acceptance criteria Corrective action

Bromofluorobenzene Instru- Daily a prior to sample anal- Evaluation criteria presented (1) Retune and or ment Tune Performance ysis. in Section 9.5 and Table (2) Perform Maintenance. Check. 9.2. Five point calibration brack- Following any major change, (1) Percent Deviation (%DEV) (1) Repeat calibration sample eting the expected sample repair or maintenance or if of response factors ±30%. analysis. concentration. daily CCV does not meet (2) Relative Retention Times (2) Repeat linearity check. method requirements. Re- (RRTs) for target peaks (3) Prepare new calibration calibration not to exceed ±0.06 units from mean RRT. standards as necessary three months. and repeat analysis. Calibration Verification (CCV Following the calibration The response factor ±30% (1) Repeat calibration check. Second source calibration curve. DEV from calibration curve (2) Repeat calibration curve. verification check). average response factor. Laboratory Blank Analysis ...... Daily a following bromofluoro (1) ≤0.2 ppbv per analyte or (1) Repeat analysis with new benzene and calibration ≤3 times the LOD, which- blank tube. check; prior to sample anal- ever is greater. (2) Check system for leaks, ysis. (2) Internal Standard (IS) area contamination. response ±40% and IS Re- (3) Analyze additional blank. tention Time (RT) ±0.33 min. of most recent calibration check. Blank Sorbent Tube Certifi- One tube analyzed for each <0.2 ppbv per VOC targeted Re-clean all tubes in batch cation. batch of tubes cleaned or compound or 3 times the and reanalyze. 10 percent of tubes which- LOD, whichever is greater. ever is greater. Samples—Internal Standards .. All samples ...... IS area response ±40% and Flag Data for possible invali- IS RT ±0.33 min. of most dation. recent calibration validation. Field Blanks ...... Two per sampling period ...... No greater than one-third of Flag Data for possible invali- the measured target dation due to high blank analyte or compliance limit. bias. a Every 24 hours.

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ADDENDUM A to Method 325B—Method A.1 SCOPE AND APPLICATION 325 Performance Evaluation A.1.1 To be measured by Methods 325A and 325B, each new target volatile organic compound (VOC) or sorbent that is not listed

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in Table 12.1 must be evaluated by exposing A.3.2 ECD is electron capture detector. the selected sorbent tube to a known con- A.3.3 FID is flame ionization detector. centration of the target compound(s) in an A.3.4 LED is light-emitting diode. exposure chamber following the procedure in A.3.5 MFC is mass flow controller. this Addendum or by following the proce- A.3.6 MFM is mass flow meter. dures in the national/international standard A.3.7 min is minute. methods: ISO 16017–2:2003(E), ASTM D6196–03 A.3.8 ppbv is parts per billion by volume. (Reapproved 2009), or BS EN 14662–4:2005 (all A.3.9 ppmv is parts per million by volume. incorporated by reference—see § 63.14), or re- A.3.10 PSD is passive sampling device. ported in peer-reviewed open literature. A.3.11 psig is pounds per square inch A.1.2 You must determine the uptake rate gauge. and the relative standard deviation com- A.3.12 RH is relative humidity. pared to the theoretical concentration of A.3.13 VOC is volatile organic compound. volatile material in the exposure chamber for each of the tests required in this method. A.4 INTERFERENCES If data that meet the requirement of this Ad- dendum are available in the peer reviewed A.4.1 VOC contaminants in water can con- open literature for VOCs of interest collected tribute interference or bias results high. Use on your passive sorbent tube configuration, only distilled, organic-free water for dilution then such data may be submitted in lieu of gas humidification. the testing required in this Addendum. A.4.2 Solvents and other VOC-containing A.1.3 You must expose sorbent tubes in a liquids can contaminate the exposure cham- test chamber to parts per trillion by volume ber. Store and use solvents and other VOC- (pptv) and low parts per billion by volume containing liquids in the exhaust hood when (ppbv) concentrations of VOCs in humid exposure experiments are in progress to pre- atmospheres to determine the sorbent tube vent the possibility of contamination of uptake rate and to confirm compound cap- VOCs into the chamber through the cham- ture and recovery. ber’s exhaust vent. NOTE: Whenever possible, passive sorbent A.2 SUMMARY OF METHOD evaluation should be performed in a VOC free laboratory. NOTE: The technique described here is one A.4.3 PSDs should be handled by per- approach for determining uptake rates for sonnel wearing only clean, white cotton or new sorbent/sorbate pairs. It is equally valid powder free nitrile gloves to prevent con- to follow the techniques described in any one tamination of the PSDs with oils from the of the following national/international hands. standards methods: ISO 16017–2:2003(E), A.4.4 This performance evaluation proce- ASTM D6196–03 (Reapproved 2009), or BS EN dure is applicable to only volatile materials 14662–4:2005 (all incorporated by reference— that can be measured accurately with direct see § 63.14). interface gas chromatography or whole gas A.2.1 Known concentrations of VOC are sample collection, concentration and anal- metered into an exposure chamber con- ysis. Alternative methods to confirm the taining sorbent tubes filled with media se- concentration of volatile materials in expo- lected to capture the volatile organic com- sure chambers are subject to Administrator pounds of interest (see Figure A.1 and A.2 for approval. an example of the exposure chamber and sorbent tube retaining rack). VOC are diluted A.5 SAFETY with humid air and the chamber is allowed to equilibrate for 6 hours. Clean passive sam- A.5.1 This procedure does not address all pling devices are placed into the chamber of the safety concerns associated with its and exposed for a measured period of time. use. It is the responsibility of the user of this The passive uptake rate of the passive sam- standard to establish appropriate field and pling devices is determined using the stand- laboratory safety and health practices and ard and dilution gas flow rates. Chamber determine the applicability of regulatory concentrations are confirmed with whole gas limitations prior to use. sample collection and analysis or direct A.5.2 Laboratory analysts must exercise interface volatile organic compound meas- appropriate care in working with high-pres- urement methods. sure gas cylinders. A.2.2 An exposure chamber and known gas concentrations must be used to challenge A.6 EQUIPMENT AND SUPPLIES and evaluate the collection and recovery of A.6.1 You must use an exposure chamber target compounds from the sorbent and tube of sufficient size to simultaneously expose a selected to perform passive measurements of minimum of eight sorbent tubes. VOC in atmospheres. A.6.2 Your exposure chamber must not contain VOC that interfere with the com- A.3 DEFINITIONS pound under evaluation. Chambers made of A.3.1 cc is cubic centimeter. glass and/or stainless steel have been used

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successfully for measurement of known con- and error before performing method evalua- centration of selected VOC compounds. tion tests. A.6.3 The following equipment and sup- A.8.2 Prepare and condition sorbent tubes plies are needed: following the procedures in Method 325B Sec- • Clean, white cotton or nitrile gloves; tion 7.0. • Conditioned passive sampling device A.8.3 You must verify that the exposure tubes and diffusion caps; and chamber does not leak. • NIST traceable high resolution digital A.8.4 You must complete two evaluation gas mass flow meters (MFMs) or flow controllers (MFCs). tests using a minimum of eight passive sampling tubes in each test with less than 5-per- A.7 REAGENTS AND STANDARDS cent depletion of test analyte by the samplers. A.7.1 You must generate an exposure gas that contains between 35 and 75 percent rel- A.8.4.1 Perform at least one evaluation at ative humidity and a concentration of target two to five times the estimated analytical compound(s) within 2 to 5 times the con- detection limit or less. centration to be measured in the field. A.8.4.2 Perform second evaluation at a A.7.2 Target gas concentrations must be concentration equivalent to the middle of generated with certified gas standards and the analysis calibration range. diluted with humid clean air. Dilution to A.8.5 You must evaluate the samplers in reach the desired concentration must be the test chamber operating between 35 per- done with zero grade air or better. cent and 75 percent RH, and at 25 ±5 °C. A.7.3 The following reagents and stand- Allow the exposure chamber to equilibrate ards are needed: for 6 hours before starting an evaluation. • Distilled water for the humidification; A.8.6 The flow rate through the chamber • VOC standards mixtures in high-pressure must be ≤0.5 meter per second face velocity cylinder certified by the supplier (NOTE: The across the sampler face. accuracy of the certified standards has a direct bearing on the accuracy of the measure- A.8.7 Place clean, ready to use sorbent ment results. Typical vendor accuracy is ±5 tubes into the exposure chamber for pre- percent accuracy but some VOC may only be determined amounts of time to evaluate col- available at lower accuracy (e.g., acrolein at lection and recovery from the tubes. The ex- 10 percent)); and posure time depends on the concentration of • Purified dilution air containing less than volatile test material in the chamber and the 0.2 ppbv of the target VOC. detection limit required for the sorbent tube sampling application. Exposure time should A.8 SAMPLE COLLECTION, PRESERVATION AND match sample collection time. The sorbent STORAGE tube exposure chamber time may not be less A.8.1 You must use certified gas stand- than 24 hours and should not be longer than ards diluted with humid air. Generate hu- 2 weeks. midified air by adding distilled organic free A.8.7.1 To start the exposure, place the water to purified or zero grade air. Humidi- clean PSDs equipped with diffusion caps on fication may be accomplished by quan- the tube inlet into a retaining rack. titative addition of water to the air dilution A.8.7.2 Place the entire retaining rack in- gas stream in a heated chamber or by pass- side the exposure chamber with the diffusive ing purified air through a humidifying bub- sampling end of the tubes facing into the bler. You must control the relative humidity chamber flow. Seal the chamber and record in the test gas throughout the period of pas- the exposure start time, chamber RH, cham- sive sampler exposure. ber temperature, PSD types and numbers, NOTE: The RH in the exposure chamber is orientation of PSDs, and volatile material directly proportional to the fraction of the mixture composition (see Figure A.2). purified air that passes through the water in the bubbler before entering the exposure A.8.7.3 Diluted, humidified target gas chamber. Achieving uniform humidification must be continuously fed into the exposure in the proper range is a trial-and-error proc- chamber during cartridge exposure. Measure ess with a humidifying bubbler. You may the flow rate of target compound standard need to heat the bubbler to achieve sufficient gas and dilution air to an accuracy of 5 per- humidity. An equilibration period of ap- cent. proximately 15 minutes is required following A.8.7.4 Record the time, temperature, and each adjustment of the air flow through the RH at the beginning, middle, and end of the humidifier. Several adjustments or equili- exposure time. bration cycles may be required to achieve A.8.7.5 At the end of the exposure time, the desired RH level. remove the PSDs from the exposure cham- NOTE: You will need to determine both the ber. Record the exposure end time, chamber dilution rate and the humidification rate for RH, and temperature. your design of the exposure chamber by trial

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A.9 QUALITY CONTROL A.10 CALIBRATION AND STANDARDIZATION A.9.1 Monitor and record the exposure A.10.1 Follow the procedures described in chamber temperature and RH during PSD Method 325B Section 10.0 for calibration. exposures. A.10.2 Verify chamber concentration by A.9.2 Measure the flow rates of standards direct injection into a gas chromatograph and purified humified air immediately fol- calibrated for the target compound(s) or by lowing PSD exposures. collection of an integrated SUMMA canister followed by analysis using a

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preconcentration gas chromatographic A.12 RECORDKEEPING PROCEDURES FOR method such as EPA Compendium Method SORBENT TUBE EVALUATION TO–15, Determination of VOCs in Air Col- lected in Specially-Prepared Canisters and Keep records for the sorbent tube evalua- Analyzed By GC/MS. tion to include at a minimum the following A.10.2.1 To use direct injection gas chro- information: matography to verify the exposure chamber A.12.1 Sorbent tube description and speci- concentration, follow the procedures in fications. Method 18 of 40 CFR part 60, Appendix A–6. A.12.2 Sorbent material description and The method ASTM D6420–99 (Reapproved specifications. 2010) (incorporated by reference—see § 63.14) A.12.3 Volatile analytes used in the sam- is an acceptable alternative to EPA Method pler test. 18 of 40 CFR part 60). A.12.4 Chamber conditions including flow NOTE: Direct injection gas chromatography rate, temperature, and relative humidity. may not be sufficiently sensitive for all compounds. Therefore, the whole gas A.12.5 Relative standard deviation of the preconcentration sample and analysis meth- sampler results at the conditions tested. od may be required to measure at low con- A.12.6 95 percent confidence limit on the centrations. sampler overall accuracy. A.10.2.2 To verify exposure chamber con- A.12.7 The relative accuracy of the sor- centrations using SUMMA canisters, prepare bent tube results compared to the direct clean canister(s) and measure the concentra- chamber measurement by direct gas chroma- tion of VOC collected in an integrated tography or SUMMA canister analysis. SUMMA canister over the period used for the evaluation (minimum 24 hours). Analyze the A.13 METHOD PERFORMANCE TO–15 canister sample following EPA Com- pendium Method TO–15. A.13.1 Sorbent tube performance is ac- A.10.2.3 Compare the theoretical con- ceptable if the relative accuracy of the pas- centration of volatile material added to the sive sorbent sampler agrees with the active test chamber to the measured concentration measurement method by ±10 percent at the to confirm the chamber operation. Theo- 95 percent confidence limit and the uptake retical concentration must agree with the ratio is equal to greater than 0.5 mL/min (1 measured concentration within 30 percent. ng/ppm-min). NOTE: For example, there is a maximum A.11 ANALYSIS PROCEDURE deviation comparing Perkin-Elmer passive Analyze the sorbent tubes following the type sorbent tubes packed with CarbopackTM procedures described in Section 11.0 of Meth- X of 1.3 to 10 percent compared to active od 325B. sampling using the following uptake rates.

1,3-butadiene Estimated Benzene Estimated uptake rate detection limit uptake rates detection limit mL/min (2 week) mL/min (2 week)

CarbopackTM X (2 week) ...... 0.61 ±0.11 a 0.1 ppbv 0.67 a 0.05 ppbv a McClenny, W.A., K.D. Oliver, H.H. Jacumin, Jr., E.H. Daughtrey, Jr., D.A. Whitaker. 2005. 24 h diffusive sampling of toxic VOCs in air onto CarbopackTM X solid adsorbent followed by thermal desorption/GC/MS analysis—laboratory studies. J. Environ. Monit. 7:248–256.

A13.2 Data Analysis and Calculations for A.13.2.1 Calculate the theoretical con- Method Evaluation centration of VOC standards using Equation A.1.

Where: FRt = The flow rate of all target compounds from separate if multiple cylinders are Cf = The final concentration of standard in the exposure chamber (ppbv). used (mL/min). FRa = The flow rate of dilution air plus mois- FRi = The flow rate of the target compound I (mL/min). ture (mL/min).

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Cs = The concentration of target compound A.13.2.3 Determine the uptake rate of the in the standard cylinder (parts per mil- target gas being evaluated using Equation lion by volume). A.2.

Where: A.13.2.4 Estimate the variance (relative standard deviation (RSD)) of the inter-sam- MX = The mass of analyte measured on the sampling tube (hg). pler results at each condition tested using Ce = The theoretical exposure chamber con- Equation A.3. RSD for the sampler is esti- centration (hg/mL). mated by pooling the variance estimates Tt = The exposure time (minutes). from each test run.

Where: n = The number of measurements of the analyte. Xi = The measured mass of analyte found on sorbent tube i. A.13.2.4 Determine the percent relative standard deviation of the inter-sampler re- Xi = The mean value of all Xi. sults using Equation A.4.

A.13.2.5 Determine the 95 percent con- sorbent combination. For the minimum test fidence interval for the sampler results using requirement of eight samplers tested at two Equation A.5. The confidence interval is de- concentrations, the number of tests is 16 and termined based on the number of test runs the degrees of freedom are 15. performed to evaluate the sorbent tube and

Where: A.13.2.6 Determine the relative accuracy of the sorbent tube combination compared to D95% = 95 percent confidence interval. %RSD = percent relative standard deviation. the active sampling results using Equation A.6. t0.95 = The Students t statistic for f degrees of freedom at 95 percent confidence. f = The number of degrees of freedom. n = Number of samples.

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Where: METHOD 326—METHOD FOR DETERMINATION OF RA = Relative accuracy. ISOCYANATES IN STATIONARY SOURCE EMIS- SIONS Xi = The mean value of all Xi. Xi = The average concentration of analyte 1.0 Scope and Application measured by the active measurement method. This method is applicable to the collection and analysis of isocyanate compounds from D = 95 percent confidence interval. 95% the emissions associated with manufacturing A.14 POLLUTION PREVENTION processes. This method is not inclusive with respect to specifications (e.g., equipment and This method involves the use of ambient supplies) and sampling procedures essential concentrations of gaseous compounds that to its performance. Some material is incor- post little or no pollution to the environ- porated by reference from other EPA meth- ment. ods. Therefore, to obtain reliable results, persons using this method should have a A.15 WASTE MANAGEMENT thorough knowledge of at least Method 1, Method 2, Method 3, and Method 5 found in Expired calibration solutions should be dis- Appendices A–1, A–2, and A–3 in Part 60 of posed of as hazardous materials. this title. 1.1 Analytes. This method is designed to A.16 REFERENCES determine the mass emission of isocyanates 1. ISO TC 146/SC 02 N 361 Workplace being emitted from manufacturing processes. atmospheres—Protocol for evaluating the The following is a table (Table 1–1) of the performance of diffusive samplers. isocyanates and the manufacturing process at which the method has been evaluated:

TABLE 326–1—ANALYTES

Compound’s name CAS No. Detection limit Manufacturing process (ng/m3) a

2,4-Toluene Diisocyanate (TDI) ...... 584–84–9 106 Flexible Foam Production. 1,6-Hexamethylene Diisocyanate (HDI) ...... 822–06–0 396 Paint Spray Booth. Methylene Diphenyl Diisocyanate (MDI) ...... 101–68–8 112 Pressed Board Production. Methyl Isocyanate (MI) ...... 624–83–0 228 Not used in production. a Estimated detection limits are based on a sample volume of 1 m3 and a 10-ml sample extraction volume.

1.2 Applicability. Method 326 is a method a multicomponent sampling train. The pri- designed for determining compliance with mary components of the train include a National Emission Standards for Hazardous heated probe, three impingers containing Air Pollutants (NESHAP). Method 326 may derivatizing reagent in toluene, an empty also be specified by New Source Performance impinger, an impinger containing charcoal, Standards (NSPS), State Implementation and an impinger containing silica gel. Plans (SIPs), and operating permits that re- 2.2 The liquid impinger contents are require measurement of isocyanates in sta- covered, concentrated to dryness under vacu- tionary source emissions, to determine com- um, brought to volume with acetonitrile pliance with an applicable emission standard (ACN) and analyzed with a high pressure liq- or limit. uid chromatograph (HPLC). 1.3 Data Quality Objectives (DQO). The principal objective is to ensure the accuracy 3.0 Definitions [Reserved] of the data at the actual emissions levels and in the actual emissions matrix encountered. 4.0 Interferences To meet this objective, method performance 4.1 The greatest potential for interference tests are required and NIST-traceable cali- comes from an impurity in the derivatizing bration standards must be used. reagent, 1-(2-pyridyl)piperazine (1,2-PP). This compound may interfere with the resolution 2.0 Summary of Method of MI from the peak attributed to unreacted 2.1 Gaseous and/or aerosol isocyanates are 1,2-PP. withdrawn from an emission source at an 4.2 Other interferences that could result isokinetic sampling rate and are collected in in positive or negative bias are (1) alcohols

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that could compete with the 1,2-PP for reac- never exceeds the temperature where Teflon tion with an isocyanate and (2) other com- is estimated to become unstable [approxi- pounds that may co-elute with one or more mately 210 °C (410 °F)]. of the derivatized isocyanates. 6.1.3 Pitot Tube, Differential Pressure 4.3 Method interferences may be caused Gauge, Filter Heating System, Metering Sys- by contaminants in solvents, reagents, glass- tem, Barometer, Gas Density Determination ware, and other sample processing hardware. Equipment. Same as Method 5, sections All these materials must be routinely shown 6.1.1.3, 6.1.1.4, 6.1.1.6, 6.1.1.9, 6.1.2, and 6.1.3. to be free from interferences under condi- 6.1.4 Impinger Train. Glass impingers are tions of the analysis by preparing and ana- connected in series with leak-free ground- lyzing laboratory method (or reagent) glass joints following immediately after the blanks. heated probe. The first impinger shall be of 4.3.1 Glassware must be cleaned thor- the Greenburg-Smith design with the stand- oughly before using. The glassware should be ard tip. The remaining five impingers shall washed with laboratory detergent in hot be of the modified Greenburg-Smith design, water followed by rinsing with tap water and modified by replacing the tip with a 1.3-cm distilled water. The glassware may be dried (1⁄2-in.) I.D. glass tube extending about 1.3 cm by baking in a glassware oven at 400 °C for at (1⁄2 in.) from the bottom of the outer cyl- least one hour. After the glassware has inder. A water-jacketed condenser is placed cooled, it should be rinsed three times with between the outlet of the first impinger and methylene chloride and three times with the inlet to the second impinger to reduce acetonitrile. Volumetric glassware should the evaporation of toluene from the first im- not be heated to 400 °C. Instead, after wash- pinger. ing and rinsing, volumetric glassware may 6.1.5 Moisture Measurement. For the pur- be rinsed with acetonitrile followed by meth- pose of calculating volumetric flow rate and ylene chloride and allowed to dry in air. isokinetic sampling, you must also collect 4.3.2 The use of high purity reagents and either Method 4 in Appendix A–3 to this part solvents helps to reduce interference prob- or other moisture measurement methods ap- lems in sample analysis. proved by the Administrator concurrent with each Method 326 test run. 5.0 Safety 6.2 Sample Recovery 6.2.1 Probe and Nozzle Brushes; Polytetra- 5.1 Organizations performing this method fluoroethylene (PTFE) bristle brushes with are responsible for maintaining a current stainless steel wire or PTFE handles are re- awareness file of Occupational Safety and quired. The probe brush shall have exten- Health Administration (OSHA) regulations sions constructed of stainless steel, PTFE, or regarding safe handling of the chemicals inert material at least as long as the probe. specified in this method. A reference file of The brushes shall be properly sized and material safety data sheets should also be shaped to brush out the probe liner and the made available to all personnel involved in probe nozzle. performing the method. Additional ref- 6.2.2 Wash Bottles. Three. PTFE or glass erences to laboratory safety are available. wash bottles are recommended; polyethylene wash bottles must not be used because or- 6.0 Equipment and Supplies ganic contaminants may be extracted by ex- 6.1 Sample Collection. A schematic of the posure to organic solvents used for sample sampling train used in this method is shown recovery. in Figure 207–1. This sampling train configu- 6.2.3 Glass Sample Storage Containers. ration is adapted from Method 5 procedures, Chemically resistant, borosilicate amber and, as such, most of the required equipment glass bottles, 500-mL or 1,000-mL. Bottles is identical to that used in Method 5 deter- should be tinted to prevent the action of minations. The only new component required light on the sample. Screw-cap liners shall is a condenser. be either PTFE or constructed to be leak- 6.1.1 Probe Nozzle. Borosilicate or quartz free and resistant to chemical attack by or- glass; constructed and calibrated according ganic recovery solvents. Narrow-mouth glass to Method 5, sections 6.1.1.1 and 10.1, and bottles have been found to leak less fre- coupled to the probe liner using a Teflon quently. union; a stainless steel nut is recommended 6.2.4 Graduated Cylinder. To measure im- for this union. When the stack temperature pinger contents to the nearest 1 ml or 1 g. exceeds 210 °C (410 °F), a one-piece glass noz- Graduated cylinders shall have subdivisions zle/liner assembly must be used. not >2 mL. 6.1.2 Probe Liner. Same as Method 5, sec- 6.2.5 Plastic Storage Containers. Screw- tion 6.1.1.2, except metal liners shall not be cap polypropylene or polyethylene con- used. Water-cooling of the stainless steel tainers to store silica gel and charcoal. sheath is recommended at temperatures ex- 6.2.6 Funnel and Rubber Policeman. To ceeding 500 °C (932 °F). Teflon may be used in aid in transfer of silica gel or charcoal to limited applications where the minimum container (not necessary if silica gel is stack temperature exceeds 120 °C (250 °F) but weighed in field).

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6.2.7 Funnels. Glass, to aid in sample re- erated area away from light, and used within covery. ten days of preparation. 6.3 Sample Preparation and Analysis. 7.2 Sample Recovery Reagents. The following items are required for sam- 7.2.1 Toluene. HPLC grade is required for ple analysis. sample recovery and cleanup (see NOTE to 6.3.1 Rotary Evaporator. Buchii Model 7.2.2 below). EL–130 or equivalent. 7.2.2 Acetonitrile. HPLC grade is required 6.3.2 1000 ml Round Bottom Flask for use for sample recovery and cleanup. NOTE: Or- with a rotary evaporator. ganic solvents stored in metal containers 6.3.3 Separatory Funnel. 500-ml or larger, may have a high residue blank and should with PTFE stopcock. not be used. Sometimes suppliers transfer 6.3.4 Glass Funnel. Short-stemmed or solvents from metal to glass bottles; thus equivalent. blanks shall be run before field use and only 6.3.5 Vials. 15-ml capacity with PTFE solvents with a low blank value should be lined caps. used. 6.3.6 Class A Volumetric Flasks. 10-ml for 7.3 Analysis Reagents. Reagent grade bringing samples to volume after concentra- chemicals should be used in all tests. All re- tion. agents shall conform to the specifications of 6.3.7 Filter Paper. Qualitative grade or the Committee on Analytical Reagents of equivalent. the American Chemical Society, where such 6.3.8 Buchner Funnel. Porcelain with 100 specifications are available. 7.3.1 Toluene, C H CH . HPLC Grade or mm ID or equivalent. 6 5 3 equivalent. 6.3.9 Erlenmeyer Flask. 500-ml with side 7.3.2 Acetonitrile, CH CN (ACN). HPLC arm and vacuum source. 3 Grade or equivalent. 6.3.10 HPLC with at least a binary pump- 7.3.3 Methylene Chloride, CH Cl . HPLC ing system capable of a programmed gra- 2 2 Grade or equivalent. dient. 7.3.4 Hexane, C6H14. HPLC Grade or equiv- 6.3.11 Column Systems Column systems alent. used to measure isocyanates must be capable 7.3.5 Water, H2O. HPLC Grade or equiva- of achieving separation of the target com- lent. pounds from the nearest eluting compound 7.3.6 Ammonium Acetate, CH CO NH . or interferents with no more than 10 percent 3 2 4 7.3.7 Acetic Acid (glacial), CH3CO2H. peak overlap. 7.3.8 1-(2-Pyridyl)piperazine, (1,2-PP), 6.3.12 Detector. UV detector at 254 nm. A ≥99.5% or equivalent. fluorescence detector (FD) with an exci- 7.3.9 Absorption Solution. Prepare a solu- tation of 240 nm and an emission at 370 nm tion of 1-(2-pyridyl)piperazine in toluene at a may be also used to allow the detection of concentration of 40 mg/300 ml. This solution low concentrations of isocyanates in sam- is used for method blanks and method ples. spikes. 6.3.13 Data system for measuring peak 7.3.10 Ammonium Acetate Buffer Solution areas and retention times. (AAB). Prepare a solution of ammonium acetate in water at a concentration of 0.1 M by 7.0 Reagents and Standards transferring 7.705 g of ammonium acetate to 7.1 Sample Collection Reagents. a 1,000 ml volumetric flask and diluting to 7.1.1 Charcoal. Activated, 6–16 mesh. Used volume with HPLC Grade water. Adjust pH to absorb toluene vapors and prevent them to 6.2 with glacial acetic acid. from entering the metering device. Use once with each train and discard. 8.0 Sample Collection, Storage and Transport 7.1.2 Silica Gel and Crushed Ice. Same as NOTE: Because of the complexity of this Method 5, sections 7.1.2 and 7.1.4 respectively method, field personnel should be trained in 7.1.3 Impinger Solution. The impinger so- and experienced with the test procedures in lution is prepared by mixing a known order to obtain reliable results. amount of 1-(2-pyridyl) piperazine (purity 8.1 Sampling 99.5+%) in toluene (HPLC grade or equiva- 8.1.1 Preliminary Field Determinations. lent). The actual concentration of 1,2-PP Same as Method 5, section 8.2. should be approximately four times the 8.1.2 Preparation of Sampling Train. Fol- amount needed to ensure that the capacity low the general procedure given in Method 5, of the derivatizing solution is not exceeded. section 8.3.1, except for the following vari- This amount shall be calculated from the ations: Place 300 ml of the impinger absorb- stoichiometric relationship between 1,2-PP ing solution in the first impinger and 200 ml and the isocyanate of interest and prelimi- each in the second and third impingers. The nary information about the concentration of fourth impinger shall remain empty. The the isocyanate in the stack emissions. A con- fifth and sixth impingers shall have 400 g of centration of 130 μg/ml of 1,2-PP in toluene charcoal and 200–300 g of silica gel, respec- can be used as a reference point. This solu- tively. Alternatively, the charcoal and silica tion shall be prepared, stored in a refrig- gel may be combined in the fifth impinger.

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Set-up the train as in Figure 326–1. During tainer, seal the container, and mark the liq- assembly, do not use any silicone grease on uid level on the bottle. ground-glass joints. 8.2.2 Container No. 2, Impingers 3 and 4. NOTE: During preparation and assembly of Quantitatively transfer the liquid from each the sampling train, keep all openings where impinger into a glass container labeled with contamination can occur covered with PTFE the test run identification and ‘‘Container film or aluminum foil until just before as- No. 2.’’ Rinse each impinger and all con- sembly or until sampling is about to begin. necting glassware twice with toluene and 8.1.3 Leak-Check Procedures. Follow the twice again with acetonitrile and transfer leak-check procedures given in Method 5, the rinses into Container No. 2. After all sections 8.4.2 (Pretest Leak-Check), 8.4.3 components have been collected in the con- (Leak-Checks During the Sample Run), and tainer, seal the container, and mark the liq- 8.4.4 (Post-Test Leak-Check), with the excep- uid level on the bottle. tion that the pre-test leak-check is manda- NOTE: The contents of the fifth and sixth tory impinger (silica gel) can be discarded. 8.1.4 Sampling Train Operation. Follow 8.2.3 Container No. 3, Reagent Blank. the general procedures given in Method 5, Save a portion of both washing solutions section 8.5. Turn on the condenser coil cool- (toluene/acetonitrile) used for the cleanup as ant recirculating pump and monitor the gas a blank. Transfer 200 ml of each solution di- entry temperature. Ensure proper gas entry rectly from the wash bottle being used and temperature before proceeding and again be- combine in a glass sample container with the fore any sampling is initiated. It is impor- test identification and ‘‘Container No. 3.’’ tant that the gas entry temperature not ex- Seal the container, and mark the liquid level ceed 50 °C (122 °F), thus reducing the loss of on the bottle and add the proper label. toluene from the first impinger. For each 8.2.4 Field Train Proof Blanks. To dem- run, record the data required on a data sheet onstrate the cleanliness of sampling train such as the one shown in Method 5, Figure 5– glassware, you must prepare a full sampling 3. train to serve as a field train proof blank 8.2 Sample Recovery. Allow the probe to just as it would be prepared for sampling. At cool. When the probe can be handled safely, a minimum, one complete sampling train wipe off all external particulate matter near will be assembled in the field staging area, the tip of the probe nozzle and place a cap taken to the sampling area, and leak- over the tip to prevent losing or gaining par- checked. The probe of the blank train shall ticulate matter. Do not cap the probe tip be heated during and the train will be recov- tightly while the sampling train is cooling ered as if it were an actual test sample. No down because this will create a vacuum in gaseous sample will be passed through the the train. Before moving the sample train to sampling train. Field blanks are recovered in the cleanup site, remove the probe from the the same manner as described in sections sample train and cap the opening to the 8.2.1 and 8.2.2 and must be submitted with probe, being careful not to lose any conden- the field samples collected at each sampling sate that might be present. Cap the site. impingers and transfer the probe and the im- 8.2.5 Field Train Spike. To demonstrate pinger/condenser assembly to the cleanup the effectiveness of the sampling train, field area. This area should be clean and protected handling, and recovery procedures you must from the weather to reduce sample contami- prepare a full sampling train to serve as a nation or loss. Inspect the train prior to and field train spike just as it would be prepared during disassembly and record any abnormal for sampling. The field spike is performed in conditions. It is not necessary to measure the same manner as the field train proof the volume of the impingers for the purpose blank with the additional step of adding the of moisture determination as the method is Field Spike Solution to the first impinger not validated for moisture determination. after the initial leak check. The train will be Treat samples as follows: recovered as if it were an actual test sample. 8.2.1 Container No. 1, Probe and Impinger No gaseous sample will be passed through Numbers 1 and 2. Rinse and brush the probe/ the sampling train. Field train spikes are re- nozzle first with toluene twice and then covered in the same manner as described in twice again with acetonitrile and place the sections 8.2.1 and 8.2.2 and must be submitted wash into a glass container labeled with the with the samples collected for each test pro- test run identification and ‘‘Container No. gram. 1.’’ When using these solvents ensure that 8.3 Sample Transport Procedures. Con- proper ventilation is available. Quan- tainers must remain in an upright position titatively transfer the liquid from the first at all times during shipment. Samples must two impingers and the condenser into Con- also be stored at <4 °C between the time of tainer No. 1. Rinse the impingers and all con- sampling and concentration. Each sample necting glassware twice with toluene and should be extracted and concentrated within then twice again with acetonitrile and trans- 30 days after collection and analyzed within fer the rinses into Container No. 1. After all 30 days after extraction. The extracted sam- components have been collected in the con- ple must be stored at 4 °C.

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8.4 Sample Custody. Proper procedures 9.2.1 Check for Breakthrough. Recover and documentation for sample chain of cus- and determine the isocyanate(s) concentra- tody are critical to ensuring data integrity. tion of the last two impingers separately The chain of custody procedures in ASTM from the first two impingers. D4840–99 (Reapproved 2018) e ‘‘Standard Guide 9.2.2 Field Train Proof Blank. Field for Sampling Chain-of-Custody Procedures’’ blanks must be submitted with the samples (incorporated by reference, see § 63.14) shall collected at each sampling site. be followed for all samples (including field 9.2.3 Reagent Blank and Field Train samples and blanks). Spike. At least one reagent blank and a field 9.0 Quality Control train spike must be submitted with the samples collected for each test program. 9.1 Sampling. Sampling Operations. The sampling quality control procedures and ac- 9.2.4 Determination of Method Detection ceptance criteria are listed in Table 326–2 Limit. Based on your instrument’s sensi- below; see also section 9.0 of Method 5. tivity and linearity, determine the calibra- 9.2 Analysis. The analytical quality con- tion concentrations or masses that make up trol procedures required for this method in- a representative low level calibration range. cludes the analysis of the field train proof The MDL must be determined at least annu- blank, field train spike, and reagent and ally for the analytical system using an MDL method blanks. Analytical quality control study such as that found in section 15.0 to procedures and acceptance criteria are listed Method 301 of appendix A to part 63 of this in Table 326–3 below. chapter.

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ust the dry gas meter and recalibrate.

as necessary. invalidating results. if necessary. the smallest volume. Completion: None, testing should be considered invalid. fication is met. specification is met. teria. brate. and repeat calibration, reanalyze samples until successful. range and dilute the sample so that it is within the calibration range. Appropriately flag any value below the calibration range. Prior to: Repair and repeat calibration. During/ Recalibrate; sensor may not be used until speci- Recalibrate; instrument may not be used until ONTROL ONTROL C C UALITY d blank ...... Locate source of contamination; reanalyze. UALITY Q Q ...... Invalidate the sample if greater than calibration cal batchcal ...... Verify integration, reintegrate. If necessary, recali- completion to sampling. test thereafter. test thereafter. SSURANCE AND Each TestEach ...... Adjust sample volumes using the factor that gives Prior to, during (optional) and at the Prior to initial use and before each Prior to initial use and before each batchanalytical Each ...... Incorporate additional calibration points to meet cri- Each test run ...... Invalidate test run. SSURANCE AND A A UALITY UALITY Q Q AMPLING NALYTICAL 326–2—S . c 326–3—A 5% Y 10% of true value ...... After each calibration ...... 10% of true value ...... Repeat secondary stand Daily and after every ten samples ...... Invalidate previous ten sample 10% of RPD ...... Each sample ...... Evaluate integrati 30% of true value ...... Each test program ...... Evaluate performance o 2% of average factor (individual) ...... Pre-test ...... Repeat calibration po ABLE ± ± ± ± ± ABLE ± 1% ...... Pre-test ...... Adj T ± T 1.5% of a reference sensor. 10 mm Hg of reading with a mercury barometer rate, whichever is less. with ± ± or NIST traceable barometer. pected range of analysis. total mass or >20% of the when measured results are 20% of the applicable standard. Alternatively, there is no breakthrough requirement when the measured results are 10% of the applicable standard. 0.00057 m3/min (0.020 cfm) or 4% of sampling 10% level of expected analyte ...... Each test program ...... Evaluate source of within 1.00 ≤ Within Within ≤ ). i ). c QA/QC criteria Acceptance criteria QA/QC criteria Frequency Acceptance criteria Consequence if not met Frequency Consequence if not met (individual correction factor—Y (average correction factor—Y verification. verification. Sampling Equipment Leak Checks ...... Dry Gas Meter Calibration—Pre-Test Dry Gas Meter Calibration—Pre-Test Calibration—Post-testMeter ....Gas Dry Average dry gas meter calibration factor agrees calibrationsensor Temperature ...... Absolute temperature measures by sensor within calibrationBarometer ...... Absolute pressure measured by instrument within Calibration—Method Blanks ...... PointsCalibration—Calibration ...... <5% level of expected analyte ...... At least six calibration point bracketing the ex- Each analytical metho Calibration—Linearity ...... Correlation coefficient >0.995 ...... Calibration—secondary standard Each analyti Calibration—continual calibration Sample Analysis ...... Within the valid calibration range ...... Each sample . Replicate Samples ...... Within Field Train Proof Blank ...... Field Train Spike ...... Within Breakthrough ...... Final two impingers Mass collected is >5% of the

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10.0 Calibration and Standardization isocyanates of interest from the individual isocyanate-urea derivative as prepared in NOTE: Maintain a laboratory log of all cali- sections 10.3.1 and 10.3.2. This is accom- brations. plished by dissolving 1 mg of each 10.1 Probe Nozzle, Pitot Tube Assembly, isocyanate-urea derivative in 10 ml of Aceto- Dry Gas Metering System, Probe Heater, nitrile. Calibration standards are prepared Temperature Sensors, Leak-Check of Meter- from this stock solution by making appro- ing System, and Barometer. Same as Method priate dilutions of aliquots of the stock into 5, sections 10.1, 10.2, 10.3, 10.4, 10.5, 8.4.1, and Acetonitrile. 10.6, respectively. 10.5 Preparation of Method Blanks. Pre- 10.2 High Performance Liquid Chro- pare a method blank for each test program matograph. Establish the retention times for (up to twenty samples) by transferring 300 the isocyanates of interest; retention times ml of the absorption solution to a 1,000-ml will depend on the chromatographic condi- round bottom flask and concentrate as out- tions. The retention times provided in Table lined in section 11.2. 10–1 are provided as a guide to relative reten- 10.6 Preparation of Field Spike Solution. tion times when using a C18, 250 mm x 4.6 Prepare a field spike solution for every test μ mm ID, 5 m particle size column, a 2 ml/min program in the same manner as calibration flow rate of a 1:9 to 6:4 Acetonitrile/Ammo- standards (see Section 10.4). The mass of the μ nium Acetate Buffer, a 50 l sample loop, and target isocyanate in the volume of the spike a UV detector set at 254 nm. solution for the field spike train shall be equivalent to that estimated to be captured TABLE 326–4—EXAMPLE RETENTION TIMES from the source concentration for each compound; alternatively, you may also prepare a Retention times solution that represents half the applicable Retention standard. Compound time 10.7 HPLC Calibrations. See Section 11.1. (minutes) 11.0 Analytical Procedure MI ...... 10.0 1,6-HDI ...... 19.9 11.1 Analytical Calibration. Perform a 2,4-TDI ...... 27.1 multipoint calibration of the instrument at MDI ...... 27.3 six or more upscale points over the desired quantitative range (multiple calibration 10.3 Preparation of Isocyanate Deriva- ranges shall be calibrated, if necessary). The tives. field samples analyzed must fall within at 10.3.1 HDI, TDI, MDI. Dissolve 500 mg of least one of the calibrated quantitative each isocyanate in individual 100 ml aliquots ranges and meet the performance criteria of methylene chloride (MeCl2), except MDI specified below. The lowest point in your which requires 250 ml of MeCl2. Transfer a 5- calibration curve must be at least 5, and ml aliquot of 1,2-PP (see section 7.3.8) to preferably 10, times the MDL. For each cali- each solution, stir and allow to stand over- bration curve, the value of the square of the night at room temperature. Transfer 150 ml linear correlation coefficient, i.e., r2, must be aliquots of hexane to each solution to pre- ≥0.995, and the analyzer response must be cipitate the isocyanate-urea derivative. within ±10 percent of the reference value at Using a Buchner funnel, vacuum filter the each upscale calibration point. Calibrations solid-isocyanate-urea derivative and rinse must be performed on each day of the anal- with 50 ml of hexane. Dissolve the precipi- ysis, before analyzing any of the samples. tate in a minimum aliquot of MeCl2. Repeat Following calibration, a secondary standard the hexane precipitation and filtration shall be analyzed. A continual calibration twice. After the third filtration, dry the verification (CCV) must also be performed crystals at 50 °C and transfer to bottles for prior to any sample and after every ten sam- storage. The crystals are stable for at least ples. The measured value of this independ- 21 months when stored at room temperature ently prepared standard must be within ±10 in a closed container. percent of the expected value. Report the re- 10.3.2 MI. Prepare a 200 μg/ml stock solu- sults for each calibration standard secondary tion of methyl isocyanate-urea, transfer 60 standard, and CCV as well as the conditions mg of 1,2-PP to a 100-ml volumetric flask of the HPLC. The reports should include at containing 50 ml of MeCl2. Carefully transfer least the peak area, height, and retention 20 mg of methyl isocyanate to the volu- time for each isocyanate compound meas- metric flask and shake for 2 minutes. Dilute ured as well as a chromatogram for each the solution to volume with MeCl2 and trans- standard. fer to a bottle for storage. Methyl isocyanate 11.2 Concentration of Samples. Transfer does not produce a solid derivative and each sample to a 1,000-ml round bottom standards must be prepared from this stock flask. Attach the flask to a rotary evapo- solution. rator and gently evaporate to dryness under 10.4 Preparation of calibration standards. vacuum in a 65 °C water bath. Rinse the Prepare a 100 μg/ml stock solution of the round bottom flask three times each with 2

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ml of acetonitrile and transfer the rinse to a CB = Concentration of a specific isocyanate 10-ml volumetric flask. Dilute the sample to compound in the replicate sample, μg/ml.

volume with acetonitrile and transfer to a CI = Concentration of a specific isocyanate 15-ml vial and seal with a PTFE lined lid. compound in the sample, μg/ml.

Store the vial ≤4 °C until analysis. Crec = Concentration recovered from spike 11.3 Analysis. Analyze replicative samples train, μg/ml. by HPLC, using the appropriate conditions CS = Concentration of isocyanate compound established in section 10.2. The width of the in the stack gas, μg/dscm

retention time window used to make identi- CT = Concentration of a specific isocyanate fications should be based upon measure- compound (Impingers 1–4), μg/dscm

ments of actual retention time variations of Cspike = Concentration spiked, μg/ml. standards over the course of a day. Three C4 = Concentration of a specific isocyanate times the standard deviation of a retention compound (Impingers 14), μg/dscm

time for a compound can be used to calculate FIm = Mass of Free Isocyanate a suggested window size; however, the expe- FTSrec = Field Train Spike Recovery rience of the analyst should weigh heavily in Im = Mass of the Isocyanate the interpretation of the chromatograms. If Imw = MW of the Isocyanate the peak area exceeds the linear range of the IUm = Mass of Isocyanate-urea derivative calibration curve, the sample must be di- IUmw = MW of the isocyanate-urea luted with acetonitrile and reanalyzed. Aver- M = Slope of the linear regression line, area age the replicate results for each run. For counts-ml/μg. each sample you must report the same infor- mI = Mass of isocyanate in the total sample mation required for analytical calibrations MW = Molecular weight (Section 11.1). For non-detect or values below RPD = Relative Percent Difference the detection limit of the method, you shall VF = Final volume of concentrated sample, report the value as ‘‘<’’ numerical detection typically 10 ml. limit. Vmstd = Volume of gas sample measured by the dry-gas meter, corrected to standard 12.0 Data Analysis and Calculations conditions, dscm (dscf). Nomenclature and calculations, same as in 12.2 Conversion from Isocyanate to the Method 5, section 6, with the following addi- Isocyanate-urea derivative. The equation for tions below. converting the amount of free isocyanate to 12.1 Nomenclature. the corresponding amount of isocyanate-urea AS = Response of the sample, area counts. derivative is as follows: b = Y-intercept of the linear regression line, 12.2 Conversion from Isocyanate to the area counts. Isocyanate-urea derivative. The equation for BR = Percent Breakthrough converting the amount of free isocyante to CA = Concentration of a specific isocyanate the corresponding amount of isocyante-urea compound in the initial sample, μg/ml. derivative is as follows:

The equation for converting the amount of IU derivative to the corresponding amount of FLm is as follows:

12.3 Calculate the correlation coefficient, 12.4 Calculate the concentration of slope, and intercepts for the calibration data isocyanate in the sample: using the least squares method for linear regression. Concentrations are expressed as the x-variable and response is expressed as the y- variable.

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12.5 Calculate the total amount collected tion (μg/ml) times the final volume of aceto- in the sample by multiplying the concentra- nitrile (10 ml).

12.6 Calculate the concentration of isocyanate (μg/dscm) in the stack gas.

12.7 Calculate Relative Percent Difference (RPD) for each replicative sample

12.8 Calculate Field Train Spike Recovery

12.9 Calculate Percent Breakthrough

Where: Section 9) for each associated analytical de- K = 35.314 ft3/m3 if Vm(std) is expressed in termination. The sampling and analytical English units. = 1.00 m3/m3 if Vm(std) is procedures must be challenged by the test expressed in metric units. compounds spiked at appropriate levels and carried through the procedures. 13.0 Method Performance Evaluation of sampling and analytical procedures for a selected series of compounds must meet the quality control criteria (See

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14.0 Pollution Prevention [Reserved] tem: Operator’s Manual, U.S. Environ- mental Protection Agency, EPA/600/8–85/ 15.0 Waste Management [Reserved] 003/1985). 16.0 Alternative Procedures [Reserved] 4. Shigehara, R.T., Adjustments in the EPA Nomograph for Different Pitot Tube Co- 17.0 References efficients and Dry Molecular Weights, 1. Martin, R.M., Construction Details of Stack Sampling News, 2:4–11 (October Isokinetic Source-Sampling Equipment, 1974). Research Triangle Park, NC, U.S. Envi- 5. U.S. Environmental Protection Agency, 40 ronmental Protection Agency, April 1971, CFR part 60, Appendices A–1, A–2, and A– PB–203 060/BE, APTD–0581, 35 pp. 3, Methods 1–5. 2. Rom, J.J., Maintenance, Calibration, and 6. Vollaro, R.F., A Survey of Commercially Operation of Isokinetic Source Sampling Available Instrumentation for the Meas- Equipment, Research Triangle Park, NC, urement of Low-Range Gas Velocities, U.S. Environmental Protection Agency, Research Triangle Park, NC, U.S. Envi- March 1972, PB–209 022/BE, APTD–0576, 39 ronmental Protection Agency, Emissions pp. Measurement Branch, November 1976 3. Schlickenrieder, L.M., Adams, J.W., and (unpublished paper). Thrun, K.E., Modified Method 5 Train and Source Assessment Sampling Sys- 18.0 Diagrams

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