40 CFR Ch. I (7–1–19 Edition) Pt. 61, App. B

Pt. 61, App. B 40 CFR Ch. I (7–1–19 Edition)

amendments which require the submission of 2. Controls such information may request a waiver of a. Describe the proposed type of control de- compliance from the Administrator of the vice to be added or modification to be made U.S. Environmental Protection Agency for to the process to reduce the emission of haz- the time period necessary to install appropriate control devices or make modifications ardous pollutants to an acceptable level. to achieve compliance. The Administrator (Use additional sheets if necessary.) may grant a waiver of compliance with the b. Describe the measures that will be taken standard for a period not exceeding two during the waiver period to assure that the years from the effective date of the haz- health of persons will be protected from im- ardous pollutant standards, if he finds that minent endangerment. (Use additional such period is necessary for the installation sheets if necessary.) of controls and that steps will be taken dur- 3. Increments of Progress—Specify the dates ing the period of the waiver to assure that by which the following increments of the health of persons will be protected from progress will be met. imminent endangerment. The report information provided in Section I Date by which contracts for emission control must accompany this application. Applica- systems or process modifications will be tions should be sent to the appropriate EPA awarded; or date by which orders will be regional office. issued for the purchase of the component parts to accomplish emission control or 1. Processes Involved—Indicate the process or processes emitting hazardous pollutants process modification. to which emission controls are to be applied.

B. Waiver of Emission Tests. A waiver of llllllllllllllllllllllll emission testing may be granted to owners llllllllllllllllllllllll or operators of sources subject to emission Date ———————————————————— testing if, in the judgment of the Adminis- Signature of the owner or operator ———— trator of the Environmental Protection Agency the emissions from the source com- (Sec. 114, of the Clean Air Act as amended (42 ply with the appropriate standard or if the U.S.C. 7414)) owners or operators of the source have re- quested a waiver of compliance or have been [40 FR 48303, Oct. 14, 1975, as amended at 43 granted a waiver of compliance. FR 8800, Mar. 3, 1978; 50 FR 46295, Sept. 9, 1985] This application should accompany the report information provided in Section I. APPENDIX B TO PART 61—TEST METHODS 1. Reason—State the reasons for requesting a waiver of emission testing. If the reason Method 101—Determination of particulate stated is that the emissions from the source and gaseous mercury emissions from chlor- are within the prescribed limits, documenta- alkali plants (air streams) tion of this condition must be attached.

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Method 101A—Determination of particulate Method 108B—Determination of arsenic con- and gaseous mercury emissions from sew- tent in ore samples from nonferrous smelt- age sludge incinerators ers Method 102—Determination of particulate Method 108C—Determination of arsenic con- and gaseous mercury emissions from chlor- tent in ore samples from nonferrous smelt- alkali plants (hydrogen streams) ers (molybdenum blue photometric proce- Method 103—Beryllium screening method dure) Method 104—Determination of beryllium Method 111—Determination of Polonium—210 emissions from stationary sources emissions from stationary sources Method 105—Determination of mercury in wastewater treatment plant sewage METHOD 101—DETERMINATION OF PARTICULATE sludges AND GASEOUS MERCURY EMISSIONS FROM Method 106—Determination of vinyl chloride CHLOR-ALKALI PLANTS (AIR STREAMS) emissions from stationary sources Method 107—Determination of vinyl chloride NOTE: This method does not include all of content of in-process wastewater samples, the specifications (e.g., equipment and sup- and vinyl chloride content of polyvinyl plies) and procedures (e.g., sampling and ana- chloride resin slurry, wet cake, and latex lytical) essential to its performance. Some samples material is incorporated by reference from Method 107A—Determination of vinyl chlo- methods in appendix A to 40 CFR part 60. ride content of solvents, resin-solvent solu- Therefore, to obtain reliable results, persons tion, polyvinyl chloride resin, resin slurry, using this method should have a thorough wet resin, and latex samples knowledge of at least the following addi- Method 108—Determination of particulate tional test methods: Method 1, Method 2, and gaseous arsenic emissions Method 3, and Method 5. Method 108A—Determination of arsenic con- 1.0 Scope and Application tent in ore samples from nonferrous smelters 1.1 Analytes.

Analyte CAS No. Sensitivity

Mercury (Hg)...... 7439–97–6 Dependent upon recorder and spectrophotometer.

1.2 Applicability. This method is applica- 4.2.1 ICl concentrations greater than 10¥4 ble for the determination of Hg emissions, molar inhibit the reduction of the Hg (II) ion including both particulate and gaseous Hg, in the aeration cell. from chlor-alkali plants and other sources 4.2.2 Condensation of water vapor on the (as specified in the regulations) where the optical cell windows causes a positive inter- carrier-gas stream in the duct or stack is ference. principally air. 5.0 Safety 1.3 Data Quality Objectives. Adherence to the requirements of this method will en- 5.1 Disclaimer. This method may involve hance the quality of the data obtained from hazardous materials, operations, and equip- air pollutant sampling methods. ment. This test method does not purport to address all of the safety problems associated 2.0 Summary of Method with its use. It is the responsibility of the user of this test method to establish appro- Particulate and gaseous Hg emissions are priate safety and health practices and deter- withdrawn isokinetically from the source mine the applicability of regulatory limita- and collected in acidic iodine monochloride tions prior to performing this test method. (ICl) solution. The Hg collected (in the mer- 5.2 Corrosive Reagents. The following re- curic form) is reduced to elemental Hg, agents are hazardous. Personal protective which is then aerated from the solution into equipment and safe procedures are useful in an optical cell and measured by atomic ab- preventing chemical splashes. If contact oc- sorption spectrophotometry. curs, immediately flush with copious amounts of water for at least 15 minutes. Re- 3.0 Definitions [Reserved] move clothing under shower and decontami- nate. Treat residual chemical burn as ther- 4.0 Interferences mal burn. 4.1 Sample Collection. Sulfur dioxide 5.2.1 Hydrochloric Acid (HCl). Highly

(SO2) reduces ICl and causes premature de- toxic and corrosive. Causes severe damage to pletion of the ICl solution. tissues. Vapors are highly irritating to eyes, 4.2 Sample Analysis. skin, nose, and lungs, causing severe damage. May cause bronchitis, pneumonia, or

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edema of lungs. Exposure to concentrations 6.3 Sample Preparation and Analysis. The of 0.13 to 0.2 percent can be lethal to humans following items are needed for sample prepa- in a few minutes. Provide ventilation to ration and analysis: limit exposure. Reacts with metals, pro- 6.3.1 Atomic Absorption Spectrophotom- ducing hydrogen gas. eter. Perkin-Elmer 303, or equivalent, con-

5.2.2 Nitric Acid (HNO3). Highly corrosive taining a hollow-cathode mercury lamp and to eyes, skin, nose, and lungs. Vapors cause the optical cell described in Section 6.3.2. bronchitis, pneumonia, or edema of lungs. 6.3.2 Optical Cell. Cylindrical shape with Reaction to inhalation may be delayed as quartz end windows and having the dimen- long as 30 hours and still be fatal. Provide sions shown in Figure 101–2. Wind the cell ventilation to limit exposure. Strong oxi- with approximately 2 meters (6 ft) of 24- dizer. Hazardous reaction may occur with or- gauge Nichrome wire, or equivalent, and ganic materials such as solvents. wrap with fiberglass insulation tape, or equivalent; do not let the wires touch each 5.2.3 Sulfuric Acid (H2SO4). Rapidly de- structive to body tissue. Will cause third de- other. gree burns. Eye damage may result in blind- 6.3.3 Aeration Cell. Constructed according ness. Inhalation may be fatal from spasm of to the specifications in Figure 101–3. Do not the larynx, usually within 30 minutes. 3 mg/ use a glass frit as a substitute for the blown m3 will cause lung damage. 1 mg/m3 for 8 glass bubbler tip shown in Figure 101–3. hours will cause lung damage or, in higher 6.3.4 Recorder. Matched to output of the concentrations, death. Provide ventilation to spectrophotometer described in Section 6.3.1. limit inhalation. Reacts violently with met- 6.3.5 Variable Transformer. To vary the als and organics. voltage on the optical cell from 0 to 40 volts. 6.3.6 Hood. For venting optical cell ex- 6.0 Equipment and Supplies. haust. 6.3.7 Flow Metering Valve. 6.1 Sample Collection. A schematic of the 6.3.8 Rate Meter. Rotameter, or equiva- sampling train used in performing this meth- lent, capable of measuring to within 2 per- od is shown in Figure 101–1; it is similar to cent a gas flow of 1.5 liters/min (0.053 cfm). the Method 5 sampling train. The following 6.3.9 Aeration Gas Cylinder. Nitrogen or items are required for sample collection: dry, Hg-free air, equipped with a single-stage 6.1.1 Probe Nozzle, Pitot Tube, Differen- regulator. tial Pressure Gauge, Metering System, Ba- 6.3.10 Tubing. For making connections. rometer, and Gas Density Determination Use glass tubing (ungreased ball and socket Equipment. Same as Method 5, Sections connections are recommended) for all tubing 6.1.1.1, 6.1.1.3, 6.1.1.4, 6.1.1.9, 6.1.2, and 6.1.3, re- connections between the solution cell and spectively. the optical cell; do not use Tygon tubing, 6.1.2 Probe Liner. Borosilicate or quartz other types of flexible tubing, or metal tub- glass tubing. A heating system capable of ing as substitutes. Teflon, steel, or copper maintaining a gas temperature of 120 ±14 °C tubing may be used between the nitrogen (248 ±25 °F) at the probe exit during sampling tank and flow metering valve (Section 6.3.7), may be used to prevent water condensation. and Tygon, gum, or rubber tubing between NOTE: Do not use metal probe liners. the flow metering valve and the aeration cell. 6.1.3 Impingers. Four Greenburg-Smith 6.3.11 Flow Rate Calibration Equipment. impingers connected in series with leak-free Bubble flow meter or wet-test meter for ground glass fittings or any similar leak-free measuring a gas flow rate of 1.5 ±0.1 liters/ noncontaminating fittings. For the first, min (0.053 ±0.0035 cfm). third, and fourth impingers, impingers that 6.3.12 Volumetric Flasks. Class A with are modified by replacing the tip with a 13- penny head standard taper stoppers; 100-, 250- mm ID (0.5-in.) glass tube extending to 13 , 500-, and 1000-ml. mm (0.5 in.) from the bottom of the flask 6.3.13 Volumetric Pipets. Class A; 1-, 2-, 3- may be used. , 4-, and 5-ml. 6.1.4 Acid Trap. Mine Safety Appliances 6.3.14 Graduated Cylinder. 50-ml. air line filter, Catalog number 81857, with 6.3.15 Magnetic Stirrer. General-purpose acid absorbing cartridge and suitable con- laboratory type. nections, or equivalent. 6.3.16 Magnetic Stirring Bar. Teflon-coat- 6.2 Sample Recovery. The following items ed. are needed for sample recovery: 6.3.17 Balance. Capable of weighing to ±0.5 6.2.1 Glass Sample Bottles. Leakless, with g. Teflon-lined caps, 1000- and 100-ml. 6.3.18 Alternative Analytical Apparatus. 6.2.2 Graduated Cylinder. 250-ml. Alternative systems are allowable as long as 6.2.3 Funnel and Rubber Policeman. To they meet the following criteria: aid in transfer of silica gel to container; not 6.3.18.1 A linear calibration curve is gen- necessary if silica gel is weighed in the field. erated and two consecutive samples of the 6.2.4 Funnel. Glass, to aid in sample re- same aliquot size and concentration agree covery. within 3 percent of their average.

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6.3.18.2 A minimum of 95 percent of the 7.2.1 Reagents. spike is recovered when an aliquot of a 7.2.1.1 Tin (II) Solution. Prepare fresh source sample is spiked with a known con- daily, and keep sealed when not being used. centration of Hg (II) compound. Completely dissolve 20 g of tin (II) chloride 6.3.18.3 The reducing agent should be (or 25 g of tin (II) sulfate) crystals (Baker added after the aeration cell is closed. Analyzed reagent grade or any other brand 6.3.18.4 The aeration bottle bubbler should that will give a clear solution) in 25 ml of not contain a frit. concentrated HCl. Dilute to 250 ml with 6.3.18.5 Any Tygon tubing used should be water. Do not substitute HNO3, H2SO4, or as short as possible and conditioned prior to other strong acids for the HCl. use until blanks and standards yield linear 7.2.1.2 Sulfuric Acid, 5 Percent (v/v). Di- and reproducible results. lute 25 ml of concentrated H2SO4 to 500 ml 6.3.18.6 If manual stirring is done before with water. aeration, it should be done with the aeration 7.2.2 Standards cell closed. 7.2.2.1 Hg Stock Solution, 1 mg Hg/ml. 6.3.18.7 A drying tube should not be used Prepare and store all Hg standard solutions unless it is conditioned as the Tygon tubing in borosilicate glass containers. Completely above. dissolve 0.1354 g of Hg (II) chloride in 75 ml 7.0 Reagents and Standards of water in a 100-ml glass volumetric flask. Add 10 ml of concentrated HNO3, and adjust Unless otherwise indicated, all reagents the volume to exactly 100 ml with water. Mix must conform to the specifications estab- thoroughly. This solution is stable for at lished by the Committee on Analytical Re- least one month. agents of the American Chemical Society; 7.2.2.2 Intermediate Hg Standard Solu- where such specifications are not available, tion, 10 μg Hg/ml. Prepare fresh weekly. use the best available grade. Pipet 5.0 ml of the Hg stock solution (Sec- 7.1 Sample Collection. The following re- tion 7.2.2.1) into a 500-ml glass volumetric agents are required for sample collection: flask, and add 20 ml of the 5 percent H2SO4 7.1.1 Water. Deionized distilled, to con- solution. Dilute to exactly 500 ml with form to ASTM D 1193–77 or 91 (incorporated water. Thoroughly mix the solution. by reference—see § 61.18), Type 1. If high con- 7.2.2.3 Working Hg Standard Solution, 200 centrations of organic matter are not ex- ng Hg/ml. Prepare fresh daily. Pipet 5.0 ml of pected to be present, the analyst may elimi- the intermediate Hg standard solution (Sec- nate the KMnO4 test for oxidizable organic tion 7.2.2.2) into a 250-ml volumetric glass matter. Use this water in all dilutions and flask. Add 10 ml of the 5 percent H2SO4 and solution preparations. 2 ml of the 0.1 M ICl absorbing solution 7.1.2 Nitric Acid, 50 Percent (v/v). Mix taken as a blank (Section 8.7.4.3), and dilute equal volumes of concentrated HNO3 and to 250 ml with water. Mix thoroughly. water, being careful to add the acid to the water slowly. 8.0 Sample Collection, Preservation, Transport, 7.1.3 Silica Gel. Indicating type, 6- to 16- and Storage mesh. If previously used, dry at 175 °C (350 °F) for 2 hours. The tester may use new silica Because of the complexity of this method, gel as received. testers should be trained and experienced 7.1.4 Potassium Iodide (KI) Solution, 25 with the test procedures to ensure reliable Percent. Dissolve 250 g of KI in water, and di- results. Since the amount of Hg that is col- lute to 1 liter. lected generally is small, the method must 7.1.5 Iodine Monochloride Stock Solution, be carefully applied to prevent contamina- 1.0 M. To 800 ml of 25 percent KI solution, tion or loss of sample. add 800 ml of concentrated HCl. Cool to room 8.1 Pretest Preparation. Follow the gen- temperature. With vigorous stirring, slowly eral procedure outlined in Method 5, Section add 135 g of potassium iodate (KIO3), and stir 8.1, except omit Sections 8.1.2 and 8.1.3. until all free iodine has dissolved. A clear or- 8.2 Preliminary Determinations. Follow ange-red solution occurs when all the KIO3 the general procedure outlined in Method 5, has been added. Cool to room temperature, Section 8.2, with the exception of the fol- and dilute to 1800 ml with water. Keep the lowing: solution in amber glass bottles to prevent 8.2.1 Select a nozzle size based on the degradation. range of velocity heads to assure that it is 7.1.6 Absorbing Solution, 0.1 M ICl. Dilute not necessary to change the nozzle size in 100 ml of the 1.0 M ICl stock solution to 1 order to maintain isokinetic sampling rates liter with water. Keep the solution in amber below 28 liters/min (1.0 cfm). glass bottles and in darkness to prevent deg- 8.2.2 Perform test runs such that samples radation. This reagent is stable for at least are obtained over a period or periods that ac- two months. curately determine the maximum emissions 7.2 Sample Preparation and Analysis. The that occur in a 24-hour period. In the case of following reagents and standards are re- cyclic operations, run sufficient tests for the quired for sample preparation and analysis: accurate determination of the emissions that

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occur over the duration of the cycle. A min- 8.7 Sample Recovery. Begin proper clean- imum sample time of 2 hours is rec- up procedure as soon as the probe is removed ommended. In some instances, high Hg or from the stack at the end of the sampling pe- high SO2 concentrations make it impossible riod. to sample for the desired minimum time. 8.7.1 Allow the probe to cool. When it can This is indicated by reddening (liberation of be safely handled, wipe off any external par- free iodine) in the first impinger. In these ticulate matter near the tip of the probe noz- cases, the sample run may be divided into zle, and place a cap over it. Do not cap off two or more subruns to ensure that the ab- the probe tip tightly while the sampling sorbing solution is not depleted. train is cooling. Capping would create a vac- 8.3 Preparation of Sampling Train. uum and draw liquid out from the impingers. 8.3.1 Clean all glassware (probe, 8.7.2 Before moving the sampling train to impingers, and connectors) by rinsing with the cleanup site, remove the probe from the train, wipe off the silicone grease, and cap 50 percent HNO3, tap water, 0.1 M ICl, tap water, and finally deionized distilled water. the open outlet of the probe. Be careful not Place 100 ml of 0.1 M ICl in each of the first to lose any condensate that might be three impingers. Take care to prevent the present. Wipe off the silicone grease from the absorbing solution from contacting any impinger. Use either ground-glass stoppers, plastic caps, or serum caps to close these greased surfaces. Place approximately 200 g openings. of preweighed silica gel in the fourth im- 8.7.3 Transfer the probe and impinger as- pinger. More silica gel may be used, but care sembly to a cleanup area that is clean, pro- should be taken to ensure that it is not en- tected from the wind, and free of Hg con- trained and carried out from the impinger tamination. The ambient air in laboratories during sampling. Place the silica gel con- located in the immediate vicinity of Hg- tainer in a clean place for later use in the using facilities is not normally free of Hg sample recovery. Alternatively, determine contamination. and record the weight of the silica gel plus 8.7.4 Inspect the train before and during impinger to the nearest 0.5 g. disassembly, and note any abnormal condi- 8.3.2 Install the selected nozzle using a tions. Treat the samples as follows. Viton A O-ring when stack temperatures are 8.7.4.1 Container No. 1 (Impingers and less than 260 °C (500 °F). Use a fiberglass Probe). string gasket if temperatures are higher. See 8.7.4.1.1 Using a graduated cylinder, meas- APTD–0576 (Reference 3 in Method 5) for de- ure the liquid in the first three impingers to tails. Other connecting systems using either within 1 ml. Record the volume of liquid 316 stainless steel or Teflon ferrules may be present (e.g., see Figure 5–6 of Method 5). used. Mark the probe with heat-resistant This information is needed to calculate the tape or by some other method to denote the moisture content of the effluent gas. (Use proper distance into the stack or duct for only glass storage bottles and graduated cyl- each sampling point. inders that have been precleaned as in Sec- 8.3.3 Assemble the train as shown in Fig- tion 8.3.1) Place the contents of the first ure 101–1, using (if necessary) a very light three impingers into a 1000-ml glass sample coat of silicone grease on all ground glass bottle. joints. Grease only the outer portion (see 8.7.4.1.2 Taking care that dust on the out- APTD–0576) to avoid the possibility of con- side of the probe or other exterior surfaces tamination by the silicone grease. does not get into the sample, quantitatively NOTE: An empty impinger may be inserted recover the Hg (and any condensate) from between the third impinger and the silica gel the probe nozzle, probe fitting, and probe to remove excess moisture from the sample liner as follows: Rinse these components stream. with two 50-ml portions of 0.1 M ICl. Next, rinse the probe nozzle, fitting and liner, and 8.3.4 After the sampling train has been as- each piece of connecting glassware between sembled, turn on and set the probe heating the probe liner and the back half of the third system, if applicable, at the desired oper- impinger with a maximum of 400 ml of water. ating temperature. Allow time for the tem- Add all washings to the 1000-ml glass sample peratures to stabilize. Place crushed ice bottle containing the liquid from the first around the impingers. three impingers. 8.4 Leak-Check Procedures. Follow the 8.7.4.1.3 After all washings have been col- leak-check procedures outlined in Method 5, lected in the sample container, tighten the Section 8.4. lid on the container to prevent leakage dur- 8.5 Sampling Train Operation. Follow the ing shipment to the laboratory. Mark the general procedure outlined in Method 5, Sec- height of the liquid to determine later tion 8.5. For each run, record the data re- whether leakage occurred during transport. quired on a data sheet such as the one shown Label the container to identify clearly its in Figure 101–4. contents. 8.6 Calculation of Percent Isokinetic. 8.7.4.2 Container No. 2 (Silica Gel). Same Same as Method 5, Section 8.6. as Method 5, Section 8.7.6.3.

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8.7.4.3 Container No. 3 (Absorbing Solu- 9.0 Quality Control tion Blank). Place 50 ml of the 0.1 M ICl absorbing solution in a 100-ml sample bottle. 9.1 Miscellaneous Quality Control Meas- Seal the container. Use this blank to prepare ures. the working Hg standard solution (Section 7.2.2.3).

Section Quality control measure Effect

8.4 10.2 ...... Sampling equipment leak-checks and calibra- Ensure accuracy and precision of sampling measurements. tion. 10.5, 10.6 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.3.3 ...... Check for matrix effects ...... Eliminate matrix effects.

9.2 Volume Metering System Checks. ible results, bring all solutions to room tem- Same as Method 5, Section 9.2. perature before use. 10.5.2 Set the spectrophotometer wave- 10.0 Calibration and Standardizations length at 253.7 nm, and make certain the op- NOTE: Maintain a laboratory log of all cali- tical cell is at the minimum temperature brations. that will prevent water condensation. Then 10.1 Before use, clean all glassware, both set the recorder scale as follows: Using a 50- new and used, as follows: brush with soap ml graduated cylinder, add 50 ml of water to the aeration cell bottle. Add three drops of and tap water, liberally rinse with tap water, Antifoam B to the bottle, and then pipet 5.0 soak for 1 hour in 50 percent HNO , and then 3 ml of the working Hg standard solution into rinse with deionized distilled water. the aeration cell. 10.2 Sampling Equipment. Calibrate the sampling equipment according to the proce- NOTE: Always add the Hg-containing solu- dures outlined in the following sections of tion to the aeration cell after the 50 ml of water. Method 5: Section 10.1 (Probe Nozzle), Sec- tion 10.2 (Pitot Tube Assembly), Section 10.3 10.5.3 Place a Teflon-coated stirring bar in (Metering System), Section 10.5 (Tempera- the bottle. Before attaching the bottle sec- ture Sensors), Section 10.6 (Barometer). tion to the bubbler section of the aeration 10.3 Aeration System Flow Rate Meter. cell, make certain that (1) the aeration cell Assemble the aeration system as shown in exit arm stopcock (Figure 101–3) is closed (so that Hg will not prematurely enter the opti- Figure 101–5. Set the outlet pressure on the cal cell when the reducing agent is being aeration gas cylinder regulator to a min- added) and (2) there is no flow through the imum pressure of 500 mm Hg (10 psi), and use bubbler. If conditions (1) and (2) are met, at- the flow metering valve and a bubble flow- tach the bottle section to the bubbler section meter or wet-test meter to obtain a flow rate of the aeration cell. Pipet 5 ml of tin (II) re- ± ± of 1.5 0.1 liters/min (0.053 0.0035 cfm) ducing solution into the aeration cell through the aeration cell. After the calibra- through the side arm, and immediately stop- tion of the aeration system flow rate meter per the side arm. Stir the solution for 15 sec- is complete, remove the bubble flowmeter onds, turn on the recorder, open the aeration from the system. cell exit arm stopcock, and immediately ini- 10.4 Optical Cell Heating System. Using a tiate aeration with continued stirring. De- 50-ml graduated cylinder, add 50 ml of water termine the maximum absorbance of the to the bottle section of the aeration cell, and standard, and set this value to read 90 per- attach the bottle section to the bubbler sec- cent of the recorder full scale. tion of the cell. Attach the aeration cell to 10.6 Calibration Curve. the optical cell and while aerating at 1.5 ±0.1 10.6.1 After setting the recorder scale, re- liters/min (0.053 ±0.0035 cfm), determine the peat the procedure in Section 10.5 using 0.0- minimum variable transformer setting nec- , 1.0-, 2.0-, 3.0-, 4.0-, and 5.0-ml aliquots of the essary to prevent condensation of moisture working standard solution (final amount of in the optical cell and in the connecting tub- Hg in the aeration cell is 0, 200, 400, 600, 800, ing. (This setting should not exceed 20 volts.) and 1000 ng, respectively). Repeat this proce- 10.5 Spectrophotometer and Recorder. dure on each aliquot size until two consecu- 10.5.1 The Hg response may be measured tive peaks agree within 3 percent of their av- by either peak height or peak area. erage value. NOTE: The temperature of the solution af- NOTE: To prevent Hg carryover from one fects the rate at which elemental Hg is re- sample to another, do not close the aeration leased from a solution and, consequently, it cell from the optical cell until the recorder affects the shape of the absorption curve pen has returned to the baseline.) (area) and the point of maximum absorbance 10.6.2 It should not be necessary to dis- (peak height). Therefore, to obtain reproduc- connect the aeration gas inlet line from the

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aeration cell when changing samples. After 11.3.1 Mercury Samples. Repeat the proce- separating the bottle and bubbler sections of dure used to establish the calibration curve the aeration cell, place the bubbler section with an appropriately sized aliquot (1 to 5 into a 600-ml beaker containing approxi- ml) of the diluted sample (from Section mately 400 ml of water. Rinse the bottle sec- 11.2.2) until two consecutive peak heights tion of the aeration cell with a stream of agree within 3 percent of their average value. water to remove all traces of the tin (II) re- The peak maximum of an aliquot (except the ducing agent. Also, to prevent the loss of Hg 5-ml aliquot) must be greater than 10 percent before aeration, remove all traces of the re- of the recorder full scale. If the peak max- ducing agent between samples by washing imum of a 1.0-ml aliquot is off scale on the with water. It will be necessary, however, to recorder, further dilute the original source wash the aeration cell parts with con- sample to bring the Hg concentration into centrated HCl if any of the following condi- the calibration range of the spectrophotom- tions occur: (1) A white film appears on any eter. inside surface of the aeration cell, (2) the 11.3.2 Run a blank and standard at least calibration curve changes suddenly, or (3) after every five samples to check the spec- the replicate samples do not yield reproduc- trophotometer calibration. The peak height ible results. of the blank must pass through a point no ± 10.6.3 Subtract the average peak height further from the origin than 2 percent of (or peak area) of the blank (0.0-ml aliquot)— the recorder full scale. The difference be- which must be less than 2 percent of recorder tween the measured concentration of the full scale—from the averaged peak heights of standard (the product of the corrected peak the 1.0-, 2.0-, 3.0-, 4.0-, and 5.0-ml aliquot height and the reciprocal of the least squares standards. If the blank absorbance is greater slope) and the actual concentration of the than 2 percent of full-scale, the probable standard must be less than 7 percent, or re- cause is Hg contamination of a reagent or calibration of the analyzer is required. 11.3.3 Check for Matrix Effects (optional). carry-over of Hg from a previous sample. Use the Method of Standard Additions as fol- Prepare the calibration curve by plotting the lows to check at least one sample from each corrected peak height of each standard solu- source for matrix effects on the Hg results. tion versus the corresponding final total Hg The Method of Standard Additions proce- weight in the aeration cell (in ng), and draw dures described on pages 9–4 and 9–5 of the the best fit straight line. This line should ei- section entitled ‘‘General Information’’ of ther pass through the origin or pass through the Perkin Elmer Corporation Atomic Ab- a point no further from the origin than ±2 sorption Spectrophotometry Manual, Num- percent of the recorder full scale. If the line ber 303–0152 (Reference 16 in Section 16.0) are does not pass through or very near to the or- recommended. If the results of the Method of igin, check for nonlinearity of the curve and Standard Additions procedure used on the for incorrectly prepared standards. single source sample do not agree to within ±5 percent of the value obtained by the rou- 11.0 Analytical Procedure tine atomic absorption analysis, then reana- 11.1 Sample Loss Check. Check the liquid lyze all samples from the source using the level in each container to see whether liquid Method of Standard Additions procedure. was lost during transport. If a noticeable 11.4 Container No. 2 (Silica Gel). Weigh amount of leakage occurred, either void the the spent silica gel (or silica gel plus im- sample or use methods subject to the ap- pinger) to the nearest 0.5 g using a balance. proval of the Administrator to account for (This step may be conducted in the field.) the losses. 12.0 Data Analysis and Calculations 11.2 Sample Preparation. Treat each sample as follows: Carry out calculations, retaining at least 11.2.1 Container No. 1 (Impingers and one extra decimal significant figure beyond Probe). Carefully transfer the contents of that of the acquired data. Round off figures Container No. 1 into a 1000-ml volumetric only after the final calculation. Other forms flask, and adjust the volume to exactly 1000 of the equations may be used as long as they ml with water. give equivalent results. 11.2.2 Dilutions. Pipet a 2-ml aliquot from 12.1 Average Dry Gas Meter Temperature the diluted sample from Section 11.2.1 into a and Average Orifice Pressure Drop, Dry Gas 250-ml volumetric flask. Add 10 ml of 5 per- Volume, Volume of Water Vapor Condensed, Moisture Content, and Isokinetic Variation. cent H2SO4, and adjust the volume to exactly 250 ml with water. This solution is stable for Same as Method 5, Sections 12.2 through 12.5 at least 72 hours. and 12.11, respectively. 12.2 Stack Gas Velocity. Using the data NOTE: The dilution factor will be 250/2 for from this test and Equation 2–9 of Method 2, this solution. calculate the average stack gas velocity vs. 11.3 Analysis. Calibrate the analytical 12.3 Total Mercury. equipment and develop a calibration curve as 12.3.1 For each source sample, correct the outlined in Sections 10.3 through 10.6. average maximum absorbance of the two

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consecutive samples whose peak heights final total weight of Hg in ng in the aeration agree within 3 percent of their average for cell for each source sample. the contribution of the solution blank (see 12.3.2 Correct for any dilutions made to Section 10.6.3). Use the calibration curve and bring the sample into the working range of these corrected averages to determine the the spectrophotometer. Then calculate the Hg in the original solution, mHg, as follows:

= ()() −3 mCHg []Hg() AC DFVSf ()10 / Eq. 101-1

Where: 10¥3 = Conversion factor, μg/ng. S = Aliquot volume added to aeration cell, CHg(AC) = Total ng of Hg in aliquot analyzed (reagent blank subtracted). ml. DF = Dilution factor for the Hg-containing 12.4 Mercury Emission Rate. Calculate solution (before adding to the aeration the daily Hg emission rate, R, using Equa- cell; e.g., DF = 250/2 if the source samples tion 101–2. For continuous operations, the op- were diluted as described in Section erating time is equal to 86,400 seconds per 11.2.2). day. For cyclic operations, use only the time Vf = Solution volume of original sample, 1000 per day each stack is in operation. The total ml for samples diluted as described in Hg emission rate from a source will be the Section 11.2.1. summation of results from all stacks.

× −6 KmHg V s A s()86, 400 10 R = Eq. 101-2 + () []VVTPm() std w () std ss/

Where: 13.1 Precision. The estimated intra-laboratory and inter-laboratory standard devi- K1 = 0.3858 °K/mm Hg for metric units. ations are 1.6 and 1.8 μg Hg/ml, respectively. K1 = 17.64 °R/in. Hg for English units. ¥6 13.2 Accuracy. The participating labora- K3 = 10 g/μg for metric units. tories that analyzed a 64.3 μg Hg/ml (in 0.1 M = 2.2046 ‘‘ × 10¥9 lb/μg for English units. ICl) standard obtained a mean of 63.7 μg Hg/ P = Absolute stack gas pressure, mm Hg (in. s ml. Hg). 13.3 Analytical Range. After initial dilu- t = Daily operating time, sec/day. tion, the range of this method is 0.5 to 120 μg T = Absolute average stack gas tempera- s Hg/ml. The upper limit can be extended by ture, °K (°R). further dilution of the sample. Vm(std) = Dry gas sample volume at standard conditions, scm (scf). 14.0 Pollution Prevention. [Reserved] Vw(std) = Volume of water vapor at standard conditions, scm (scf). 15.0 Waste Management. [Reserved] 12.5 Determination of Compliance. Each 16.0 Alternative Procedures performance test consists of three repetitions of the applicable test method. For the 16.1 Alternative Analyzer. Samples may purpose of determining compliance with an also be analyzed by cold vapor atomic fluo- applicable national emission standard, use rescence spectrometry. the average of the results of all repetitions. 17.0 References 13.0 Method Performance Same as Method 5, Section 17.0, References The following estimates are based on col- 1–3, 5, and 6, with the addition of the fol- laborative tests, wherein 13 laboratories per- lowing: formed duplicate analyses on two Hg-con- 1. Determining Dust Concentration in a taining samples from a chlor-alkali plant Gas Stream. ASME Performance Test Code and on one laboratory-prepared sample of No. 27. New York, NY. 1957. known Hg concentration. The sample concentrations ranged from 2 to 65 μg Hg/ml.

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2. DeVorkin, Howard, et al. Air Pollution of ASTM Standards, Part 23. ASTM Designa- Source Testing Manual. Air Pollution Con- tion D 2928–71. Philadelphia, PA 1971. trol District. Los Angeles, CA. November 10. Vennard, J.K. Elementary Fluid Me- 1963. chanics. John Wiley and Sons, Inc. New 3. Hatch, W.R., and W.I. Ott. Determina- York. 1947. tion of Sub-Microgram Quantities of Mer- 11. Mitchell, W.J. and M.R. Midgett. Im- cury by Atomic Absorption proved Procedure for Determining Mercury Spectrophotometry. Anal. Chem. 40:2085–87. Emissions from Mercury Cell Chlor-Alkali 1968. Plants. J. APCA. 26:674–677. July 1976. 4. Mark, L.S. Mechanical Engineers’ Hand- 12. Shigehara, R.T. Adjustments in the book. McGraw-Hill Book Co., Inc. New York, EPA Nomograph for Different Pitot Tube Co- NY. 1951. efficients and Dry Molecular Weights. Stack 5. Western Precipitation Division of Joy Sampling News. 2:4–11. October 1974. Manufacturing Co. Methods for Determina- 13. Vollaro, R.F. Recommended Procedure tion of Velocity, Volume, Dust and Mist Con- for Sample Traverses in Ducts Smaller than tent of Gases. Bulletin WP–50. Los Angeles, 12 Inches in Diameter. U.S. Environmental CA. 1968. Protection Agency, Emission Measurement 6. Perry, J.H. Chemical Engineers’ Hand- Branch. Research Triangle Park, NC. Novem- book. McGraw-Hill Book Co., Inc. New York, ber 1976. NY. 1960. 14. Klein, R. and C. Hach. Standard Addi- 7. Shigehara, R.T., W.F. Todd, and W.S. tions: Uses and Limitation in Smith. Significance of Errors in Stack Sam- Spectrophotometric Measurements. Amer. pling Measurements. Stack Sampling News. Lab. 9:21. 1977. 1(3):6–18. September 1973. 15. Perkin Elmer Corporation. Analytical 8. Smith, W.S., R.T. Shigehara, and W.F. Methods for Atomic Absorption Todd. A Method of Interpreting Stack Sam- Spectrophotometry. Norwalk, Connecticut. pling Data. Stack Sampling News. 1(2):8–17. September 1976. August 1973. 9. Standard Method for Sampling Stacks 18.0 Tables, Diagrams, Flowcharts, and for Particulate Matter. In: 1971 Annual Book Validation Data

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METHOD 101A—DETERMINATION OF PARTICU- in this part. Therefore, to obtain reliable re- LATE AND GASEOUS MERCURY EMISSIONS sults, persons using this method should also FROM SEWAGE SLUDGE INCINERATORS have a thorough knowledge of at least the following additional test methods: Methods NOTE: This method does not include all of 1, Method 2, Method 3, and Method 5 of part the specifications (e.g., equipment and sup- 60 (appendix A), and Method 101 part 61 (applies) and procedures (e.g., sampling and ana- pendix B). lytical) essential to its performance. Some material is incorporated by reference from 1.0 Scope and Application methods in appendix A to 40 CFR part 60 and 1.1 Analytes.

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Analyte CAS No. Sensitivity

Mercury (Hg) ...... 7439–97–6 Dependent upon spectrophotometer and recorder.

1.2 Applicability. This method is applica- bronchitis, pneumonia, or edema of lungs. ble for the determination of Hg emissions Reaction to inhalation may be delayed as from sewage sludge incinerators and other long as 30 hours and still be fatal. Provide sources as specified in an applicable subpart ventilation to limit exposure. Strong oxi- of the regulations. dizer. Hazardous reaction may occur with or- 1.3 Data Quality Objectives. Adherence to ganic materials such as solvents. the requirements of this method will en- 5.2.3 Sulfuric acid (H2SO4). Rapidly de- hance the quality of the data obtained from structive to body tissue. Will cause third de- air pollutant sampling methods. gree burns. Eye damage may result in blind- ness. Inhalation may be fatal from spasm of 2.0 Summary of Method the larynx, usually within 30 minutes. May 2.1 Particulate and gaseous Hg emissions cause lung tissue damage with edema. 3 mg/ are withdrawn isokinetically from the source m3 will cause lung damage in uninitiated. 1 and are collected in acidic potassium per- mg/m3 for 8 hours will cause lung damage or, in higher concentrations, death. Provide ven- manganate (KMnO4) solution. The Hg collected (in the mercuric form) is reduced to tilation to limit inhalation. Reacts violently elemental Hg, which is then aerated from the with metals and organics. solution into an optical cell and measured by 5.3 Chlorine Evolution. Hydrochloric acid atomic absorption spectrophotometry. reacts with KMnO4 to liberate chlorine gas. Although this is a minimal concern when 3.0 Definitions. [Reserved] small quantities of HCl (5–10 ml) are used in the impinger rinse, a potential safety hazard 4.0 Interferences may still exist. At sources that emit higher 4.1 Sample Collection. Excessive oxidiz- concentrations of oxidizable materials (e.g., able organic matter in the stack gas pre- power plants), more HCl may be required to maturely depletes the KMnO4 solution and remove the larger amounts of brown deposit thereby prevents further collection of Hg. formed in the impingers. In such cases, the 4.2 Analysis. Condensation of water vapor potential safety hazards due to sample con- on the optical cell windows causes a positive tainer pressurization are greater, because of interference. the larger volume of HCl rinse added to the recovered sample. These hazards are elimi- 5.0 Safety nated by storing and analyzing the HCl im- 5.1 Disclaimer. This method may involve pinger wash separately from the permanga- hazardous materials, operations, and equip- nate impinger sample. ment. This test method may not address all 6.0 Equipment and Supplies of the safety problems associated with its use. It is the responsibility of the user of this 6.1 Sample Collection and Sample Recov- test method to establish appropriate safety ery. Same as Method 101, Sections 6.1 and 6.2, and health practices and determine the ap- respectively, with the following exceptions: plicability of regulatory limitations prior to 6.1.1 Probe Liner. Same as in Method 101, performing this test method. Section 6.1.2, except that if a filter is used 5.2 Corrosive Reagents. The following re- ahead of the impingers, the probe heating agents are hazardous. Personal protective system must be used to minimize the con- equipment and safe procedures are useful in densation of gaseous Hg. preventing chemical splashes. If contact oc- 6.1.2 Filter Holder (Optional). Borosilicate curs, immediately flush with copious glass with a rigid stainless-steel wire-screen amounts of water for at least 15 minutes. Re- filter support (do not use glass frit supports) move clothing under shower and decontami- and a silicone rubber or Teflon gasket, de- nate. Treat residual chemical burns as ther- signed to provide a positive seal against mal burns. leakage from outside or around the filter. 5.2.1 Hydrochloric Acid (HCl). Highly The filter holder must be equipped with a fil- toxic. Vapors are highly irritating to eyes, ter heating system capable of maintaining a skin, nose, and lungs, causing severe dam- temperature around the filter holder of 120 age. May cause bronchitis, pneumonia, or ±14 °C (248 ±25 °F) during sampling to mini- edema of lungs. Exposure to concentrations mize both water and gaseous Hg condensa- of 0.13 to 0.2 percent can be lethal to humans tion. A filter may also be used in cases where in a few minutes. Provide ventilation to the stream contains large quantities of par- limit exposure. Reacts with metals, pro- ticulate matter. ducing hydrogen gas. 6.2 Sample Analysis. Same as Method 101, 5.2.2 Nitric Acid (HNO3). Highly corrosive Section 6.3, with the following additions and to eyes, skin, nose, and lungs. Vapors cause exceptions:

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6.2.1 Volumetric Pipets. Class A; 1-, 2-, 3- 40 g of KMnO4 in sufficient 10 percent H2SO4 , 4-, 5-, 10-, and 20-ml. to make 1 liter. Prepare and store in glass 6.2.2 Graduated Cylinder. 25-ml. bottles to prevent degradation. 6.2.3 Steam Bath. 7.1.7 Hydrochloric Acid, 8 N. Carefully add 6.2.4 Atomic Absorption Spectrophotom- and mix 67 ml of concentrated HCl to 33 ml eter or Equivalent. Any atomic absorption of water. unit with an open sample presentation area 7.2 Sample Analysis. The following re- in which to mount the optical cell is suit- agents and standards are required for sample able. Instrument settings recommended by analysis: the particular manufacturer should be fol- 7.2.1 Water. Same as in Section 7.1.1. lowed. Instruments designed specifically for 7.2.2 Tin (II) Solution. Prepare fresh the measurement of mercury using the cold- daily, and keep sealed when not being used. vapor technique are commercially available Completely dissolve 20 g of tin (II) chloride and may be substituted for the atomic ab- (or 25 g of tin (II) sulfate) crystals (Baker sorption spectrophotometer. Analyzed reagent grade or any other brand 6.2.5 Optical Cell. Alternatively, a heat that will give a clear solution) in 25 ml of lamp mounted above the cell or a moisture concentrated HCl. Dilute to 250 ml with trap installed upstream of the cell may be water. Do not substitute HNO3 H2SO4, or used. other strong acids for the HCl. 6.2.6 Aeration Cell. Alternatively, aer- 7.2.3 Sodium Chloride-Hydroxylamine So- ation cells available with commercial cold lution. Dissolve 12 g of sodium chloride and vapor instrumentation may be used. 12 g of hydroxylamine sulfate (or 12 g of hy- 6.2.7 Aeration Gas Cylinder. Nitrogen, droxylamine hydrochloride) in water and di- argon, or dry, Hg-free air, equipped with a lute to 100 ml. single-stage regulator. Alternatively, aer- 7.2.4 Hydrochloric Acid, 8 N. Same as Sec- ation may be provided by a peristaltic me- tion 7.1.7. tering pump. If a commercial cold vapor in- 7.2.5 Nitric Acid, 15 Percent (V/V). Care- strument is used, follow the manufacturer’s fully add 15 ml HNO to 85 ml of water. recommendations. 3 7.2.6 Antifoam B Silicon Emulsion. J.T. 7.0 Reagents and Standards Baker Company (or equivalent). 7.2.7 Mercury Stock Solution, 1 mg Hg/ml. Unless otherwise indicated, it is intended Prepare and store all Hg standard solutions that all reagents conform to the specifica- in borosilicate glass containers. Completely tions established by the Committee on Ana- dissolve 0.1354 g of Hg (II) chloride in 75 ml lytical Reagents of the American Chemical of water. Add 10 ml of concentrated HNO3, Society, where such specifications are avail- and adjust the volume to exactly 100 ml with able; otherwise, use the best available grade. water. Mix thoroughly. This solution is sta- 7.1 Sample Collection and Recovery. The ble for at least one month. following reagents are required for sample 7.2.8 Intermediate Hg Standard Solution, collection and recovery: 10 μg/ml. Prepare fresh weekly. Pipet 5.0 ml 7.1.1 Water. Deionized distilled, to con- of the Hg stock solution (Section 7.2.7) into form to ASTM D 1193–77 or 91 Type 1. If high a 500 ml volumetric flask, and add 20 ml of 15 concentrations of organic matter are not ex- percent HNO solution. Adjust the volume to pected to be present, the analyst may elimi- 3 exactly 500 ml with water. Thoroughly mix nate the KMnO test for oxidizable organic 4 the solution. matter. Use this water in all dilutions and solution preparations. 7.2.9 Working Hg Standard Solution, 200 7.1.2 Nitric Acid, 50 Percent (V/V). Mix ng Hg/ml. Prepare fresh daily. Pipet 5.0 ml from the ‘‘Intermediate Hg Standard Solu- equal volumes of concentrated HNO3 and water, being careful to add the acid to the tion’’ (Section 7.2.8) into a 250-ml volumetric water slowly. flask. Add 5 ml of 4 percent KMnO4 absorbing 7.1.3 Silica Gel. Indicating type, 6 to 16 solution and 5 ml of 15 percent HNO3. Adjust mesh. If previously used, dry at 175 °C (350 the volume to exactly 250 ml with water. Mix °F) for 2 hours. New silica gel may be used as thoroughly. received. 7.2.10 Potassium Permanganate, 5 Percent 7.1.4 Filter (Optional). Glass fiber filter, (W/V). Dissolve 5 g of KMnO4 in water and di- without organic binder, exhibiting at least lute to 100 ml. 99.95 percent efficiency on 0.3-μm dioctyl 7.2.11 Filter. Whatman No. 40, or equiva- phthalate smoke particles. The filter in lent. cases where the gas stream contains large 8.0 Sample Collection, Preservation, Transport, quantities of particulate matter, but blank and Storage filters should be analyzed for Hg content. 7.1.5 Sulfuric Acid, 10 Percent (V/V). Care- Same as Method 101, Section 8.0, with the fully add and mix 100 ml of concentrated exception of the following: H2SO4 to 900 ml of water. 8.1 Preliminary Determinations. Same as 7.1.6 Absorbing Solution, 4 Percent Method 101, Section 8.2, except that the lib- KMnO4 (W/V). Prepare fresh daily. Dissolve eration of free iodine in the first impinger 255

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due to high Hg or sulfur dioxide concentra- front half of the filter holder (if applicable), tions is not applicable. In this method, high and impingers as follows: Rinse these compo- oxidizable organic content may make it im- nents with a total of 400 ml (350 ml if an possible to sample for the desired minimum extra impinger was added as described in time. This problem is indicated by the com- Section 8.1) of fresh absorbing solution, care- plete bleaching of the purple color of the fully assuring removal of all loose particu- KMnO4 solution. In cases where an excess of late matter from the impingers; add all water condensation is encountered, collect washings to the 1000 ml glass sample bottle. two runs to make one sample, or add an To remove any residual brown deposits on extra impinger in front of the first impinger the glassware following the permanganate (also containing acidified KMnO4 solution). rinse, rinse with approximately 100 ml of 8.2 Preparation of Sampling Train. Same water, carefully assuring removal of all loose as Method 101, Section 8.3, with the excep- particulate matter from the impingers. Add tion of the following: this rinse to Container No. 1. 8.2.1 In this method, clean all the glass 8.4.2.1.3 If no visible deposits remain after components by rinsing with 50 percent HNO3, this water rinse, do not rinse with 8 N HCl. tap water, 8 N HCl, tap water, and finally If deposits do remain on the glassware after with deionized distilled water. Then place 50 the water rinse, wash impinger walls and ml of absorbing solution in the first im- stems with 25 ml of 8 N HCl, and place the pinger and 100 ml in each of the second and wash in a separate container labeled Con- third impingers. tainer No. 1A as follows: Place 200 ml of 8.2.2 If a filter is used, use a pair of tweez- water in a sample container labeled Con- ers to place the filter in the filter holder. Be tainer No. 1A. Wash the impinger walls and sure to center the filter, and place the gas- stem with the HCl by turning the impinger ket in the proper position to prevent the on its side and rotating it so that the HCl sample gas stream from bypassing the filter. contacts all inside surfaces. Pour the HCl Check the filter for tears after assembly is wash carefully with stirring into Container completed. Be sure also to set the filter heat- No. 1A. ing system at the desired operating tempera- 8.4.2.1.4 After all washings have been col- ture after the sampling train has been as- lected in the appropriate sample con- sembled. tainer(s), tighten the lid(s) on the con- 8.3 Sampling Train Operation. In addition tainer(s) to prevent leakage during shipment to the procedure outlined in Method 101, Sec- to the laboratory. Mark the height of the tion 8.5, maintain a temperature around the fluid level to allow subsequent determina- filter (if applicable) of 120 ±14 °C (248 ±25 °F). tion of whether leakage has occurred during 8.4 Sample Recovery. Same as Method 101, transport. Label each container to identify Section 8.7, with the exception of the fol- its contents clearly. lowing: 8.4.3 Container No. 2 (Silica Gel). Same as 8.4.1 Transfer the probe, impinger assem- Method 5, Section 8.7.6.3. bly, and (if applicable) filter assembly to the 8.4.4 Container No. 3 (Filter). If a filter cleanup area. was used, carefully remove it from the filter 8.4.2 Treat the sample as follows: holder, place it in a 100-ml glass sample bot- 8.4.2.1 Container No. 1 (Impinger, Probe, tle, and add 20 to 40 ml of absorbing solution. and Filter Holder) and, if applicable, Con- If it is necessary to fold the filter, be sure tainer No. 1A (HCl rinse). that the particulate cake is inside the fold. 8.4.2.1.1 Using a graduated cylinder, meas- Carefully transfer to the 100-ml sample bot- ure the liquid in the first three impingers to tle any particulate matter and filter fibers within 1 ml. Record the volume of liquid that adhere to the filter holder gasket by present (e.g., see Figure 5–6 of Method 5). using a dry Nylon bristle brush and a sharp- This information is needed to calculate the edged blade. Seal the container. Label the moisture content of the effluent gas. (Use container to identify its contents clearly. only graduated cylinder and glass storage Mark the height of the fluid level to allow bottles that have been precleaned as in Sec- subsequent determination of whether leak- tion 8.2.1.) Place the contents of the first age has occurred during transport. three impingers (four if an extra impinger 8.4.5 Container No. 4 (Filter Blank). If a was added as described in Section 8.1) into a filter was used, treat an unused filter from 1000-ml glass sample bottle labeled Container the same filter lot as that used for sampling No. 1. according to the procedures outlined in Sec- NOTE: If a filter is used, remove the filter tion 8.4.4. from its holder as outlined under Section 8.4.6 Container No. 5 (Absorbing Solution 8.4.3. Blank). Place 650 ml of 4 percent KMnO4 ab- 8.4.2.1.2 Taking care that dust on the out- sorbing solution in a 1000-ml sample bottle. side of the probe or other exterior surfaces Seal the container. does not get into the sample, quantitatively 8.4.7 Container No. 6 (HCl Rinse Blank). recover the Hg (and any condensate) from Place 200 ml of water in a 1000-ml sample the probe nozzle, probe fitting, probe liner, bottle, and add 25 ml of 8 N HCl carefully

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with stirring. Seal the container. Only one 9.0 Quality Control blank sample per 3 runs is required. 9.1 Miscellaneous Quality Control Meas- ures.

Section Quality control measure Effect

8.0, 10.0 ...... Sampling equipment leak-checks and calibra- Ensure accuracy and precision of sampling measurements. tion. 10.2 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.3.3 ...... Check for matrix effects ...... Eliminate matrix effects.

9.2 Volume Metering System Checks. the solution for 15 seconds, turn on the re- Same as Method 5, Section 9.2. corder, open the aeration cell exit arm stopcock, and immediately initiate aeration with 10.0 Calibration and Standardization continued stirring. Determine the maximum Same as Method 101, Section 10.0, with the absorbance of the standard, and set this following exceptions: value to read 90 percent of the recorder full 10.1 Optical Cell Heating System Calibra- scale. tion. Same as in Method 101, Section 10.4, except use a-25 ml graduated cylinder to add 25 11.0 Analytical Procedure ml of water to the bottle section of the aer- 11.1 Sample Loss Check. Check the liquid ation cell. level in each container to see if liquid was 10.2 Spectrophotometer and Recorder lost during transport. If a noticeable amount Calibration. of leakage occurred, either void the sample 10.2.1 The Hg response may be measured or use methods subject to the approval of the by either peak height or peak area. Administrator to account for the losses. NOTE: The temperature of the solution af- 11.2 Sample Preparation. Treat sample fects the rate at which elemental Hg is re- containers as follows: leased from a solution and, consequently, it 11.2.1 Containers No. 3 and No. 4 (Filter affects the shape of the absorption curve and Filter Blank). (area) and the point of maximum absorbance 11.2.1.1 If a filter is used, place the con- (peak height). To obtain reproducible re- tents, including the filter, of Containers No. sults, all solutions must be brought to room 3 and No. 4 in separate 250-ml beakers, and temperature before use. heat the beakers on a steam bath until most 10.2.2 Set the spectrophotometer wave of the liquid has evaporated. Do not heat to length at 253.7 nm, and make certain the op- dryness. Add 20 ml of concentrated HNO3 to tical cell is at the minimum temperature the beakers, cover them with a watch glass, that will prevent water condensation. Then and heat on a hot plate at 70 °C (160 °F) for set the recorder scale as follows: Using a 25- 2 hours. Remove from the hot plate. ml graduated cylinder, add 25 ml of water to 11.2.1.2 Filter the solution from digestion the aeration cell bottle. Add three drops of of the Container No. 3 contents through Antifoam B to the bottle, and then pipet 5.0 Whatman No. 40 filter paper, and save the fil- ml of the working Hg standard solution into trate for addition to the Container No. 1 fil- the aeration cell. trate as described in Section 11.2.2. Discard NOTE: Always add the Hg-containing solu- the filter paper. tion to the aeration cell after the 25 ml of 11.2.1.3 Filter the solution from digestion water. of the Container No. 4 contents through 10.2.3 Place a Teflon-coated stirring bar in Whatman No. 40 filter paper, and save the fil- the bottle. Add 5 ml of absorbing solution to trate for addition to Container No. 5 filtrate the aeration bottle, and mix well. Before at- as described in Section 11.2.3 below. Discard taching the bottle section to the bubbler sec- the filter paper. tion of the aeration cell, make certain that 11.2.2 Container No. 1 (Impingers, Probe, (1) the aeration cell exit arm stopcock (Fig- and Filter Holder) and, if applicable, No. 1A ure 101–3 of Method 101) is closed (so that Hg (HCl rinse). will not prematurely enter the optical cell 11.2.2.1 Filter the contents of Container when the reducing agent is being added) and No. 1 through Whatman No. 40 filter paper (2) there is no flow through the bubbler. If into a 1 liter volumetric flask to remove the conditions (1) and (2) are met, attach the brown manganese dioxide (MnO2) precipitate. bottle section to the bubbler section of the Save the filter for digestion of the brown aeration cell. Add sodium chloride-hydroxyl- MnO2 precipitate. Add the sample filtrate amine in 1 ml increments until the solution from Container No. 3 to the 1-liter volu- is colorless. Now add 5 ml of tin (II) solution metric flask, and dilute to volume with to the aeration bottle through the side arm, water. If the combined filtrates are greater and immediately stopper the side arm. Stir than 1000 ml, determine the volume to the

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nearest ml and make the appropriate correc- 12.0 Data Analysis and Calculations tions for blank subtractions. Mix thor- NOTE: Carry out calculations, retaining at oughly. Mark the filtrate as analysis Sample least one extra decimal significant figure be- No. A.1 and analyze for Hg within 48 hr of the yond that of the acquired data. Round off filtration step. Place the saved filter, which figures only after the final calculation. was used to remove the brown MnO2 precipi- Other forms of the equations may be used as tate, into an appropriate sized container. In long as they give equivalent results. a laboratory hood, add 25 ml of 8 N HCl to 12.1 Nomenclature. the filter and allow to digest for a minimum of 24 hours at room temperature. C(fltr)Hg = Total ng of Hg in aliquot of KMnO4 filtrate and HNO digestion of filter ana- 11.2.2.2 Filter the contents of Container 3 lyzed (aliquot of analysis Sample No. 1A through Whatman No. 40 filter paper into A.1). a 500-ml volumetric flask. Then filter the C(fltr blk)Hg = Total ng of Hg in aliquot of digestate of the brown MnO2 precipitate from KMnO4 blank and HNO3 digestion of Container No. 1 through Whatman No. 40 fil- blank filter analyzed (aliquot of analysis ter paper into the same 500-ml volumetric Sample No. A.1 blank). flask, and dilute to volume with water. Mark C(HC1 blk)Hg = Total ng of Hg analyzed in ali- this combined 500 ml dilute solution as anal- quot of the 500-ml analysis Sample No. ysis Sample No. A.2. Discard the filters. HCl A.2 blank. 11.2.3 Container No. 5 (Absorbing Solution C(HCl)Hg = Total ng of Hg analyzed in the ali- Blank) and No. 6 (HCl Rinse Blank). quot from the 500-ml analysis Sample No. 11.2.3.1 Treat Container No. 5 as Container HCl A.2. No. 1 (as described in Section 11.2.2), except DF = Dilution factor for the HCl-digested substitute the filter blank filtrate from Con- Hg-containing solution, Analysis Sample tainer No. 4 for the sample filtrate from Con- No. ‘‘HCl A.2.’’ tainer No. 3, and mark as Sample A.1 Blank. DFblk = Dilution factor for the HCl-digested 11.2.3.2 Treat Container No. 6 as Container Hg containing solution, Analysis Sample No. 1A, (as described in Section 11.2.2, except No. ‘‘HCl A.2 blank.’’ (Refer to sample No. ‘‘HCl A.2’’ dilution factor above.) substitute the filtrate from the digested m( ) = Total blank corrected μg of Hg in blank MnO precipitate for the filtrate from fltr Hg 2 KMnO filtrate and HNO digestion of fil- the digested sample MnO precipitate, and 4 3 2 ter sample. mark as Sample No. A.2 Blank. m(HCl)Hg = Total blank corrected μg of Hg in NOTE: When analyzing samples A.1 Blank HCl rinse and HCl digestate of filter sam- and HCl A.2 Blank, always begin with 10 ml ple. aliquots. This applies specifically to blank mHg = Total blank corrected Hg content in samples. each sample, μg. 11.3 Analysis. Calibrate the analytical S = Aliquot volume of sample added to aer- equipment and develop a calibration curve as ation cell, ml. S = Aliquot volume of blank added to aer- outlined in Section 10.0. blk ation cell, ml. 11.3.1 Mercury Samples. Then repeat the Vf(blk) = Solution volume of blank sample, procedure used to establish the calibration 1000 ml for samples diluted as described curve with appropriately sized aliquots (1 to in Section 11.2.2. 10 ml) of the samples (from Sections 11.2.2 Vf(fltr) = Solution volume of original sample, and 11.2.3) until two consecutive peak normally 1000 ml for samples diluted as heights agree within 3 percent of their aver- described in Section 11.2.2. age value. If the 10 ml sample is below the Vf(HCl) = Solution volume of original sample, detectable limit, use a larger aliquot (up to 500 ml for samples diluted as described in 20 ml), but decrease the volume of water Section 11.2.1. added to the aeration cell accordingly to pre- 10¥3 = Conversion factor, μg/ng. vent the solution volume from exceeding the 12.2 Average Dry Gas Meter Temperature capacity of the aeration bottle. If the peak and Average Orifice Pressure Drop, Dry Gas maximum of a 1.0 ml aliquot is off scale, fur- Volume, Volume of Water Vapor Condensed, ther dilute the original sample to bring the Moisture Content, Isokinetic Variation, and Hg concentration into the calibration range Stack Gas Velocity and Volumetric Flow of the spectrophotometer. If the Hg content Rate. Same as Method 5, Sections 12.2 of the absorbing solution and filter blank is through 12.5, 12.11, and 12.12, respectively. below the working range of the analytical 12.3 Total Mercury. method, use zero for the blank. 12.3.1 For each source sample, correct the 11.3.2 Run a blank and standard at least average maximum absorbance of the two after every five samples to check the spec- consecutive samples whose peak heights trophotometer calibration; recalibrate as agree within 3 percent of their average for necessary. the contribution of the blank. Use the cali- 11.3.3 Check for Matrix Effects (optional). bration curve and these corrected averages Same as Method 101, Section 11.3.3. to determine the final total weight of Hg in

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ng in the aeration cell for each source sam- 12.3.2 Correct for any dilutions made to ple. bring the sample into the working range of the spectrophotometer.

[]CDF() []CDF()blk = HCl Hg − HClblk Hg −3 m()HCl Hg Vf()HC1 ()10 Eq. 101A-1 S Sblk

NOTE: This dilution factor applies only to essary to bring the sample into the analyt- the intermediate dilution steps, since the ical instrument’s calibration range. original sample volume [(Vf)HCL] of ‘‘HCl A.2’’ NOTE: The maximum allowable blank sub- has been factored out in the equation along traction for the HCl is the lesser of the two with the sample aliquot (S). In Eq. 101A–1, following values: (1) the actual blank meas- the sample aliquot, S, is introduced directly ured value (analysis Sample No. HCl A.2 into the aeration cell for analysis according blank), or (2) 5% of the Hg content in the to the procedure outlined in Section 11.3.1. A combined HCl rinse and digested sample dilution factor is required only if it is nec- (analysis Sample No. HCl A.2).

[]CDFV() () []CDFV() blk () = fltr Hg f fltr − fltr blk Hg f blk m()fltr Hg Eq. 101A-2 S Sblk

NOTE: The maximum allowable blank sub- ured value (analysis Sample No. ‘‘A.1 traction for the HCl is the lesser of the two blank’’), or (2) 5% of the Hg content in the following values: (1) the actual blank meas- filtrate (analysis Sample No. ‘‘A.1’’).

=+ mHg m()HCl Hg m () fltr Hg Eq. 101A-3

12.3 Mercury Emission Rate. Same as analysis provided the following conditions Method 101, Section 12.3. are met: 12.4 Determination of Compliance. Same 16.1.1.1 Sample collection, sample prepa- as Method 101, Section 12.4. ration, and analytical preparation procedures are as defined in the method except as 13.0 Method Performance necessary for the ICP–AES application. 13.1 Precision. Based on eight paired-train 16.1.1.2 The quality control procedures are tests, the intra-laboratory standard devi- conducted as prescribed. ation was estimated to be 4.8 μg/ml in the 16.1.1.3 The limit of quantitation for the concentration range of 50 to 130 μg/m3. ICP–AES must be demonstrated and the 13.2 Bias. [Reserved] sample concentrations reported should be no 13.3 Range. After initial dilution, the less than two times the limit of quantita- range of this method is 20 to 800 ng Hg/ml. tion. The limit of quantitation is defined as The upper limit can be extended by further ten times the standard deviation of the dilution of the sample. blank value. The standard deviation of the 14.0 Pollution Prevention [Reserved] blank value is determined from the analysis of seven blanks. It has been reported that for 15.0 Waste Management [Reserved] mercury and those elements that form hy- drides, a continuous-flow generator coupled 16.0 Alternative Procedures to an ICP–AES offers detection limits com- 16.1 Alternative Analyzers. parable to cold vapor atomic absorption. 16.1.1 Inductively coupled plasma-atomic 16.1.2 Samples may also be analyzed by emission spectrometry (ICP–AES) may be cold vapor atomic fluorescence spectrom- used as an alternative to atomic absorption etry.

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17.0 References 18.0 Tables, Diagrams, Flowcharts, And Validation Data [Reserved] Same as Section 16.0 of Method 101, with the addition of the following: METHOD 102—DETERMINATION OF PARTICULATE 1. Mitchell, W.J., et al. Test Methods to De- AND GASEOUS MERCURY EMISSIONS FROM termine the Mercury Emissions from Sludge CHLOR-ALKALI PLANTS (HYDROGEN Incineration Plants. U.S. Environmental STREAMS) Protection Agency. Research Triangle Park, NOTE: This method does not include all of NC. Publication No. EPA–600/4–79–058. Sep- the specifications (e.g., equipment and sup- tember 1979. plies) and procedures (e.g., sampling and ana- 2. Wilshire, Frank W., et al. Reliability lytical) essential to its performance. Some Study of the U.S. EPA’s Method 101A—Deter- material is incorporated by reference from mination of Particulate and Gaseous Mer- other methods in this part and in appendix A cury Emissions. U.S. Environmental Protec- to 40 CFR part 60. Therefore, to obtain reli- tion Agency. Research Triangle Park, NC. able results, persons using this method Report No. 600/D–31/219 AREAL 367, NTIS Acc should have a thorough knowledge of at least No. PB91–233361. the following additional test methods: Meth- 3. Memorandum from William J. Mitchell od 1, Method 2, Method 3, Method 5, and to Roger T. Shigehara discussing the poten- Method 101. tial safety hazard in Section 7.2 of Method 1.0 Scope and Application 101A. February 28, 1990. 1.1 Analytes.

Analyte CAS No. Sensitivity

Mercury (Hg) ...... 7439–97–6 Dependent upon recorder and spectrophotometer.

1.2 Applicability. This method is applica- 5.2 Corrosive Reagents. Same as Method ble for the determination of Hg emissions, 101, Section 5.2. including both particulate and gaseous Hg, 5.3 Explosive Mixtures. The sampler must from chlor-alkali plants and other sources conduct the source test under conditions of (as specified in the regulations) where the utmost safety because hydrogen and air mix- carrier-gas stream in the duct or stack is tures are explosive. Since the sampling train principally hydrogen. essentially is leakless, attention to safe op- 1.3 Data Quality Objectives. Adherence to eration can be concentrated at the inlet and the requirements of this method will en- outlet. If a leak does occur, however, remove hance the quality of the data obtained from the meter box cover to avoid a possible ex- air pollutant sampling methods. plosive mixture. The following specific pre- cautions are recommended: 2.0 Summary of Method 5.3.1 Operate only the vacuum pump dur- 2.1 Particulate and gaseous Hg emissions ing the test. The other electrical equipment, are withdrawn isokinetically from the source e.g., heaters, fans, and timers, normally are and collected in acidic iodine monochloride not essential to the success of a hydrogen (ICl) solution. The Hg collected (in the mer- stream test. curic form) is reduced to elemental Hg, 5.3.2 Seal the sample port to minimize which is then aerated from the solution into leakage of hydrogen from the stack. an optical cell and measured by atomic ab- 5.3.3 Vent sampled hydrogen at least 3 m sorption spectrophotometry. (10 ft) away from the train. This can be accomplished by attaching a 13-mm (0.50-in.) 3.0 Definitions [Reserved] ID Tygon tube to the exhaust from the ori- 4.0 Interferences fice meter. Same as Method 101, Section 4.2. NOTE: A smaller ID tubing may cause the orifice meter calibration to be erroneous. 5.0 Safety Take care to ensure that the exhaust line is not bent or pinched. 5.1 Disclaimer. This method may involve hazardous materials, operations, and equip- 6.0 Equipment and Supplies ment. This test method may not address all of the safety problems associated with its Same as Method 101, Section 6.0, with the use. It is the responsibility of the user of this exception of the following: test method to establish appropriate safety 6.1 Probe Heating System. Do not use, un- and health practices and determine the ap- less otherwise specified. plicability of regulatory limitations prior to 6.2 Glass Fiber Filter. Do not use, unless performing this test method. otherwise specified.

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7.0 Reagents and Standards fice meter at flow conditions that simulate the conditions at the source is suggested. Same as Method 101, Section 7.0. Calibration should either be done with hy- 8.0 Sample Collection, Preservation, Transport, drogen or with some other gas having a simi- and Storage lar Reynolds Number so that there is simi- larity between the Reynolds Numbers during Same as Method 101, Section 8.0, with the calibration and during sampling. Alternative exception of the following: mercury-free thermometers may be used if 8.1 Setting of Isokinetic Rates. the thermometers are, at a minimum, equiv- 8.1.1 If a nomograph is used, take special alent in terms of performance or suitably ef- care in the calculation of the molecular fective for the specific temperature measure- weight of the stack gas and in the setting of ment application. the nomograph to maintain isokinetic condi- 8.1.1.2 The nomograph described in APTD– tions during sampling (Sections 8.1.1.1 0576 cannot be used to calculate the C factor through 8.1.1.3 below). because the nomograph is designed for use 8.1.1.1 Calibrate the meter box orifice. Use when the stack gas dry molecular weight is the techniques described in APTD–0576 (see 29 ±4. Instead, the following calculation Reference 9 in Section 17.0 of Method 5 of ap- should be made to determine the proper C pendix A to part 60). Calibration of the ori- factor:

2 ()1− B C= 0.@ 00154ΔHC2 T() PP / ws Eq. 102-1 psmm − + ()1Bws 18B ws

Where: be used. For sampling guidelines, see Ref- erence 14 in Section 17.0 of Method 101. Bws = Fraction by volume of water vapor in the stack gas. 9.0 Quality Control Cp = Pitot tube calibration coefficient, dimensionless. Same as Method 101, Section 9.0. M = Dry molecular weight of stack gas, lb/ d 10.0 Calibration and Standardizations lb-mole.

Ps = Absolute pressure of stack gas, in. Hg. Same as Method 101, Section 10.0. Pm = Absolute pressure of gas at the meter, in. Hg. 11.0 Analytical Procedure

Tm = Absolute temperature of gas at the ori- Same as Method 101, Section 11.0. fice, °R. 12.0 Data Analysis and Calculations DH@ = Meter box calibration factor obtained in Section 8.1.1.1, in. H2O. Same as Method 101, Section 12.0. 0.00154 = (in. H2O/°R). 13.0 Method Performance NOTE: This calculation is left in English units, and is not converted to metric units Same as Method 101, Section 13.0. because nomographs are based on English 13.1 Analytical Range. After initial dilu- units. tion, the range of this method is 0.5 to 120 μg 8.1.1.3 Set the calculated C factor on the Hg/ml. The upper limit can be extended by operating nomograph, and select the proper further dilution of the sample. nozzle diameter and K factor as specified in 14.0 Pollution Prevention. [Reserved] APTD–0576. If the C factor obtained in Sec- tion 8.1.1.2 exceeds the values specified on 15.0 Waste Management. [Reserved] the existing operating nomograph, expand the C scale logarithmically so that the val- 16.0 References ues can be properly located. Same as Method 101, Section 16.0. 8.1.2 If a calculator is used to set isokinetic rates, it is suggested that the 17.0 Tables, Diagrams, Flowcharts, and isokinetic equation presented in Reference 13 Validation Data. [Reserved] in Section 17.0 of Method 101 be consulted. 8.2 Sampling in Small (<12-in. Diameter) METHOD 103—BERYLLIUM SCREENING METHOD Stacks. When the stack diameter (or equiva- 1.0 Scope and Application lent diameter) is less than 12 inches, conventional pitot tube-probe assemblies should not 1.1 Analytes.

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Analyte CAS No. Sensitivity

Beryllium (Be) ...... 7440–41–7 Dependent upon analytical procedure used.

1.2 Applicability. This procedure details Whatman 41, or equivalent, be placed imme- guidelines and requirements for methods ac- diately against the back side of the Millipore ceptable for use in determining Be emissions filter as a guard against breakage of the in ducts or stacks at stationary sources. Millipore. Include the backup filter in the 1.3 Data Quality Objectives. Adherence to analysis. To be equivalent, other filters shall the requirements of this method will en- exhibit at least 99.95 percent efficiency (0.05 hance the quality of the data obtained from percent penetration) on 0.3 micron dioctyl air pollutant sampling methods. phthalate smoke particles, and be amenable to the Be analysis procedure. The filter effi- 2.0 Summary of Method ciency tests shall be conducted in accord- 2.1 Particulate Be emissions are with- ance with ASTM D 2986–71, 78, 95a (incor- drawn isokinetically from three points in a porated by reference—see § 61.18). Test data duct or stack and are collected on a filter. from the supplier’s quality control program The collected sample is analyzed for Be are sufficient for this purpose. using an appropriate technique. 6.1.4 Meter-Pump System. Any system that will maintain isokinetic sampling rate, 3.0 Definitions. [Reserved] determine sample volume, and is capable of a sampling rate of greater than 14 lpm (0.5 4.0 Interferences. [Reserved] cfm). 5.0 Safety 6.2 Measurement of Stack Conditions. The following equipment is used to measure 5.1 Disclaimer. This method may involve stack conditions: hazardous materials, operations, and equip- 6.2.1 Pitot Tube. Type S, or equivalent, ment. This test method may not address all with a constant coefficient (±5 percent) over of the safety problems associated with its the working range. use. It is the responsibility of the user of this 6.2.2 Inclined Manometer, or Equivalent. test method to establish appropriate safety To measure velocity head to ±10 percent of and health practices and determine the ap- the minimum value. plicability of regulatory limitations prior to 6.2.3 Temperature Measuring Device. To performing this test method. measure stack temperature to ±1.5 percent of 5.2 Hydrochloric Acid (HCl). Highly corro- the minimum absolute stack temperature. sive and toxic. Vapors are highly irritating 6.2.4 Pressure Measuring Device. To meas- to eyes, skin, nose, and lungs, causing severe ure stack pressure to ±2.5 mm Hg (0.1 in. Hg). damage. May cause bronchitis, pneumonia, 6.2.5 Barometer. To measure atmospheric or edema of lungs. Exposure to concentra- pressure to ±2.5 mm Hg (0.1 in. Hg). tions of 0.13 to 0.2 percent can be lethal to 6.2.6 Wet and Dry Bulb Thermometers, humans in a few minutes. Provide ventila- Drying Tubes, Condensers, or Equivalent. To tion to limit exposure. Reacts with metals, determine stack gas moisture content to ±1 producing hydrogen gas. Personal protective percent. equipment and safe procedures are useful in 6.3 Sample Recovery. preventing chemical splashes. If contact oc- 6.3.1 Probe Cleaning Equipment. Probe curs, immediately flush with copious brush or cleaning rod at least as long as amounts of water at least 15 minutes. Re- probe, or equivalent. Clean cotton balls, or move clothing under shower and decontami- equivalent, should be used with the rod. nate. Treat residual chemical burn as ther- 6.3.2 Leakless Glass Sample Bottles. To mal burn. contain sample. 6.4 Analysis. All equipment necessary to 6.0 Equipment and Supplies perform an atomic absorption, spectro- 6.1 Sample Collection. A schematic of the graphic, fluorometric, chromatographic, or required sampling train configuration is equivalent analysis. shown in Figure 103–1 in Section 17.0. The es- 7.0 Reagents and Standards sential components of the train are as follows: 7.1 Sample Recovery. 6.1.1 Nozzle. Stainless steel, or equivalent, 7.1.1 Water. Deionized distilled, to con- with sharp, tapered leading edge. form to ASTM D 1193–77, 91 (incorporated by 6.1.2 Probe. Sheathed borosilicate or reference—see § 61.18), Type 3. quartz glass tubing. 7.1.2 Acetone. Reagent grade. 6.1.3 Filter. Millipore AA, or equivalent, 7.1.3 Wash Acid, 50 Percent (V/V) Hydro- with appropriate filter holder that provides a chloric Acid (HCl). Mix equal volumes of con- positive seal against leakage from outside or centrated HCl and water, being careful to around the filter. It is suggested that a add the acid slowly to the water.

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7.2 Analysis. Reagents and standards as 8.3.2 Leak check the sampling train at the necessary for the selected analytical proce- sampling site. The leakage rate should not dure. be in excess of 1 percent of the desired sample rate. 8.0 Sample Collection, Preservation, Transport, 8.4 Sampling Train Operation. and Storage 8.4.1 For each run, measure the velocity Guidelines for source testing are detailed at the selected sampling point. Determine in the following sections. These guidelines the isokinetic sampling rate. Record the ve- are generally applicable; however, most sam- locity head and the required sampling rate. ple sites differ to some degree and temporary Place the nozzle at the sampling point with alterations such as stack extensions or ex- the tip pointing directly into the gas stream. pansions often are required to insure the Immediately start the pump and adjust the best possible sample site. Further, since Be flow to isokinetic conditions. At the conclu- is hazardous, care should be taken to mini- sion of the test, record the sampling rate. mize exposure. Finally, since the total quan- Again measure the velocity head at the sam- tity of Be to be collected is quite small, the pling point. The required isokinetic rate at test must be carefully conducted to prevent the end of the period should not have devi- contamination or loss of sample. ated more than 20 percent from that origi- 8.1 Selection of a Sampling Site and Num- nally calculated. Describe the reason for any ber of Sample Runs. Select a suitable sample deviation beyond 20 percent in the test re- site that is as close as practicable to the port. point of atmospheric emission. If possible, 8.4.2 Sample at a minimum rate of 14 li- stacks smaller than one foot in diameter ters/min (0.5 cfm). Obtain samples over such should not be sampled. a period or periods of time as are necessary 8.1.1 Ideal Sampling Site. The ideal sam- to determine the maximum emissions which pling site is at least eight stack or duct di- would occur in a 24-hour period. In the case ameters downstream and two diameters up- of cyclic operations, perform sufficient sam- stream from any flow disturbance such as a ple runs so as to allow determination or cal- bend, expansion or contraction. For rectan- culation of the emissions that occur over the gular cross sections, use Equation 103–1 in duration of the cycle. A minimum sampling Section 12.2 to determine an equivalent di- time of two hours per run is recommended. ameter, De. 8.5 Sample Recovery. 8.1.2 Alternate Sampling Site. Some sam- 8.5.1 It is recommended that all glassware pling situations may render the above sam- be precleaned as in Section 8.3. Sample re- pling site criteria impractical. In such cases, covery should also be performed in an area select an alternate site no less than two di- free of possible Be contamination. When the ameters downstream and one-half diameter sampling train is moved, exercise care to upstream from any point of flow disturbance. prevent breakage and contamination. Set Additional sample runs are recommended at aside a portion of the acetone used in the any sample site not meeting the criteria of sample recovery as a blank for analysis. The Section 8.1.1. total amount of acetone used should be 8.1.3 Number of Sample Runs Per Test. measured for accurate blank correction. Three sample runs constitute a test. Conduct Blanks can be eliminated if prior analysis each run at one of three different points. Se- shows negligible amounts. lect three points that proportionately divide the diameter, or are located at 25, 50, and 75 8.5.2 Remove the filter (and backup filter, percent of the diameter from the inside wall. if used) and any loose particulate matter For horizontal ducts, sample on a vertical from filter holder, and place in a container. line through the centroid. For rectangular 8.5.3 Clean the probe with acetone and a ducts, sample on a line through the centroid brush or long rod and cotton balls. Wash into and parallel to a side. If additional sample the container with the filter. Wash out the runs are performed per Section 8.1.2, propor- filter holder with acetone, and add to the tionately divide the duct to accommodate same container. the total number of runs. 9.0 Quality Control. [Reserved] 8.2 Measurement of Stack Conditions. Using the equipment described in Section 6.2, 10.0 Calibration and Standardization measure the stack gas pressure, moisture, and temperature to determine the molecular 10.1 Sampling Train. As a procedural weight of the stack gas. Sound engineering check, compare the sampling rate regulation estimates may be made in lieu of direct with a dry gas meter, spirometer, rotameter measurements. Describe the basis for such (calibrated for prevailing atmospheric condi- estimates in the test report. tions), or equivalent, attached to the nozzle 8.3 Preparation of Sampling Train. inlet of the complete sampling train. 8.3.1 Assemble the sampling train as 10.2 Analysis. Perform the analysis stand- shown in Figure 103–1. It is recommended ardization as suggested by the manufacturer that all glassware be precleaned by soaking of the instrument, or the procedures for the in wash acid for two hours. analytical method in use.

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11.0 Analytical Procedure R = Be emission rate, g/day. Make the necessary preparation of samples Vs(avg) = Average stack gas velocity, m/sec and analyze for Be. Any currently acceptable (ft/sec). 3 3 method (e.g., atomic absorption, spectro- Vtotal = Total volume of gas sampled, m (ft ). graphic, fluorometric, chromatographic) W = Width. may be used. Wt = Total weight of Be collected, mg. 10¥6 = Conversion factor, g/μg. 12.0 Data Analysis and Calculations 86,400 = Conversion factor, sec/day. 12.1 Nomenclature. 12.2 Calculate the equivalent diameter, 2 2 As(avg) = Stack area, m (ft ). De, for a rectangular cross section as fol- L = Length. lows:

2⋅⋅LW D = Eq. 103-1 e LW+

12.3 Calculate the Be emission rate, R, in day each stack is in operation. The total Be g/day for each stack using Equation 103–2. emission rate from a source is the summa- For cyclic operations, use only the time per tion of results from all stacks.

()−6 WVt s() avg As 86, 400() 10 R = Eq. 103-2 Vtotal

12.4 Test Report. Prepare a test report stack cross section, and stack dimensions that includes as a minimum: A detailed de- and distances from any point of disturbance. scription of the sampling train used, results of the procedural check described in Section 13.0 Method Performance. [Reserved] 10.1 with all data and calculations made, all 14.0 Pollution Prevention. [Reserved] pertinent data taken during the test, the basis for any estimates made, isokinetic 15.0 Waste Management. [Reserved] sampling calculations, and emission results. Include a description of the test site, with a 16.0 References. [Reserved] block diagram and brief description of the 17.0 Tables, Diagrams, Flow Charts, and process, location of the sample points in the Validation Data

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METHOD 104—DETERMINATION OF BERYLLIUM Therefore, to obtain reliable results, persons EMISSIONS FROM STATIONARY SOURCES using this method should have a thorough knowledge of at least the following addi- NOTE: This method does not include all of tional test methods: Method 1, Method 2, the specifications (e.g., equipment and sup- Method 3, and Method 5 in appendix A, part plies) and procedures (e.g., sampling and ana- 60. lytical) essential to its performance. Some material is incorporated by reference from 1.0 Scope and Application methods in appendix A to 40 CFR part 60. 1.1 Analytes.

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Analyte CAS No. Sensitivity

Beryllium (Be) ...... 7440–41–7 Dependent upon recorder and spectrophotometer.

1.2 Applicability. This method is applica- of 0.13 to 0.2 percent can be lethal to humans ble for the determination of Be emissions in in a few minutes. Provide ventilation to ducts or stacks at stationary sources. Unless limit exposure. Reacts with metals, pro- otherwise specified, this method is not in- ducing hydrogen gas. tended to apply to gas streams other than 5.2.2 Hydrogen Peroxide (H2O2). Irritating those emitted directly to the atmosphere to eyes, skin, nose, and lungs. without further processing. 5.2.3 Nitric Acid (HNO3). Highly corrosive 1.3 Data Quality Objectives. Adherences to eyes, skin, nose, and lungs. Vapors cause to the requirements of this method will en- bronchitis, pneumonia, or edema of lungs. hance the quality of the data obtained from Reaction to inhalation may be delayed as air pollutant sampling methods. long as 30 hours and still be fatal. Provide ventilation to limit exposure. Strong oxi- 2.0 Summary of Method dizer. Hazardous reaction may occur with or- 2.1 Particulate and gaseous Be emissions ganic materials such as solvents. are withdrawn isokinetically from the source 5.2.4 Sodium Hydroxide (NaOH). Causes and are collected on a glass fiber filter and in severe damage to eyes and skin. Inhalation water. The collected sample is digested in an causes irritation to nose, throat, and lungs. acid solution and is analyzed by atomic ab- Reacts exothermically with limited amounts sorption spectrophotometry. of water. 5.3 Beryllium is hazardous, and pre- 3.0 Definitions [Reserved] cautions should be taken to minimize exposure. 4.0 Interferences 6.0 Equipment and Supplies 4.1 Matrix Effects. Analysis for Be by flame atomic absorption spectrophotometry 6.1 Sample Collection. Same as Method 5, is sensitive to the chemical composition and Section 6.1, with the exception of the fol- to the physical properties (e.g., viscosity, pH) lowing: of the sample. Aluminum and silicon, in par- 6.1.1 Sampling Train. Same as Method 5, ticular, are known to interfere when present Section 6.1.1, with the exception of the fol- in appreciable quantities. The analytical lowing: procedure includes (optionally) the use of 6.1.2 Probe Liner. Borosilicate or quartz the Method of Standard Additions to check glass tubing. A heating system capable of for these matrix effects, and sample analysis maintaining a gas temperature of 120 ±14 °C using the Method of Standard Additions if (248 ±25 °F) at the probe exit during sampling significant matrix effects are found to be to prevent water condensation may be used. present (see Reference 2 in Section 17.0). NOTE: Do not use metal probe liners. 5.0 Safety 6.1.3 Filter Holder. Borosilicate glass, with a glass frit filter support and a silicone 5.1 Disclaimer. This method may involve rubber gasket. Other materials of construc- hazardous materials, operations, and equip- tion (e.g., stainless steel, Teflon, Viton) may ment. This test method may not address all be used, subject to the approval of the Ad- of the safety problems associated with its ministrator. The holder design shall provide use. It is the responsibility of the user of this a positive seal against leakage from the out- test method to establish appropriate safety side or around the filter. The holder shall be and health practices and determine the ap- attached immediately at the outlet of the plicability of regulatory limitations prior to probe. A heating system capable of main- performing this test method. taining the filter at a minimum temperature 5.2 Corrosive reagents. The following re- in the range of the stack temperature may agents are hazardous. Personal protective be used to prevent condensation from occur- equipment and safe procedures are useful in ring. preventing chemical splashes. If contact oc- 6.1.4 Impingers. Four Greenburg-Smith curs, immediately flush with copious impingers connected in series with leak-free amounts of water at least 15 minutes. Re- ground glass fittings or any similar leak-free move clothing under shower and decontami- noncontaminating fittings. For the first, nate. Treat residual chemical burn as ther- third, and fourth impingers, use impingers mal burn. that are modified by replacing the tip with a 5.2.1 Hydrochloric Acid (HCl). Highly 13 mm-ID (0.5 in.) glass tube extending to 13 toxic. Vapors are highly irritating to eyes, mm (0.5 in.) from the bottom of the flask skin, nose, and lungs, causing severe dam- may be used. age. May cause bronchitis, pneumonia, or 6.2 Sample Recovery. The following items edema of lungs. Exposure to concentrations are needed for sample recovery:

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6.2.1 Probe Cleaning Rod. At least as long stock beryllium standard solution to 100 ml as probe. with 25 percent HCl solution to give a con- 6.2.2 Glass Sample Bottles. Leakless, with centration of 1 mg/ml. Prepare this dilute Teflon-lined caps, 1000 ml. stock solution fresh daily. 6.2.3 Petri Dishes. For filter samples, glass or polyethylene, unless otherwise spec- 8.0 Sample Collection, Preservation, Transport, ified by the Administrator. and Storage 6.2.4 Graduated Cylinder. 250 ml. The amount of Be that is collected is gen- 6.2.5 Funnel and Rubber Policeman. To erally small, therefore, it is necessary to ex- aid in transfer of silica gel to container; not ercise particular care to prevent contamina- necessary if silica gel is weighed in the field. tion or loss of sample. 6.2.6 Funnel. Glass, to aid in sample re- 8.1 Pretest Preparation. Same as Method covery. 5, Section 8.1, except omit Section 8.1.3. 6.2.7 Plastic Jar. Approximately 300 ml. 8.2 Preliminary Determinations. Same as 6.3 Analysis. The following items are Method 5, Section 8.2, with the exception of needed for sample analysis: the following: 6.3.1 Atomic Absorption Spectrophotom- 8.2.1 Select a nozzle size based on the eter. Perkin-Elmer 303, or equivalent, with range of velocity heads to assure that it is nitrous oxide/acetylene burner. not necessary to change the nozzle size in 6.3.2 Hot Plate. order to maintain isokinetic sampling rates 6.3.3 Perchloric Acid Fume Hood. below 28 liters/min (1.0 cfm). 7.0 Reagents and Standards 8.2.2 Obtain samples over a period or periods of time that accurately determine the NOTE: Unless otherwise indicated, it is in- maximum emissions that occur in a 24-hour tended that all reagents conform to the spec- period. In the case of cyclic operations, per- ifications established by the Committee on form sufficient sample runs for the accurate Analytical Reagents of the American Chem- determination of the emissions that occur ical Society, where such specifications are over the duration of the cycle. A minimum available; otherwise, use the best available sample time of 2 hours per run is rec- grade. ommended. 7.1 Sample Collection. Same as Method 5, 8.3 Preparation of Sampling Train. Same Section 7.1, including deionized distilled as Method 5, Section 8.3, with the exception water conforming to ASTM D 1193–77 or 91 of the following: (incorporated by reference—see § 61.18), Type 8.3.1 Prior to assembly, clean all glass- 3. The Millipore AA filter is recommended. ware (probe, impingers, and connectors) by 7.2 Sample Recovery. Same as Method 5 first soaking in wash acid for 2 hours, fol- in appendix A, part 60, Section 7.2, with the lowed by rinsing with water. addition of the following: 8.3.2 Save a portion of the water for a 7.2.1 Wash Acid, 50 Percent (V/V) Hydro- blank analysis. chloric Acid (HCl). Mix equal volumes of con- 8.3.3 Procedures relating to the use of centrated HCl and water, being careful to metal probe liners are not applicable. add the acid slowly to the water. 8.3.4 Probe and filter heating systems are 7.3 Sample Preparation and Analysis. The needed only if water condensation is a prob- following reagents and standards and stand- lem. If this is the case, adjust the heaters to ards are needed for sample preparation and provide a temperature at or above the stack analysis: temperature. However, membrane filters 7.3.1 Water. Same as in Section 7.1. such as the Millipore AA are limited to 7.3.2. Perchloric Acid (HClO4). Con- about 107 °C (225 °F). If the stack gas is in ex- centrated (70 percent V/V). cess of about 93 °C (200 °F), consideration 7.3.3 Nitric Acid (HNO3). Concentrated. should be given to an alternate procedure 7.3.4 Beryllium Powder. Minimum purity such as moving the filter holder downstream 98 percent. of the first impinger to insure that the filter 7.3.5 Sulfuric Acid (H SO ) Solution, 12 N. 2 4 does not exceed its temperature limit. After Dilute 33 ml of concentrated H SO to 1 liter 2 4 the sampling train has been assembled, turn with water. on and set the probe heating system, if appli- 7.3.6 Hydrochloric Acid Solution, 25 Per- cable, at the desired operating temperature. cent HCl (V/V). Allow time for the temperatures to stabilize. 7.3.7 Stock Beryllium Standard Solution, Place crushed ice around the impingers. 10 μg Be/ml. Dissolve 10.0 mg of Be in 80 ml NOTE: An empty impinger may be inserted of 12 N H2SO4 in a 1000-ml volumetric flask. Dilute to volume with water. This solution is between the third impinger and the silica gel stable for at least one month. Equivalent to remove excess moisture from the sample strength Be stock solutions may be prepared stream. from Be salts such as BeCl2 and Be(NO3)2 (98 8.4 Leak Check Procedures, Sampling percent minimum purity). Train Operation, and Calculation of Percent 7.3.8 Working Beryllium Standard Solu- Isokinetic. Same as Method 5, Sections 8.4, tion, 1 μg Be/ml. Dilute a 10 ml aliquot of the 8.5, and 8.6, respectively.

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8.5 Sample Recovery. Same as Method 5, rinse solutions in the sample bottle with the Section 8.7, except treat the sample as fol- contents of the impingers. lows: Transfer the probe and impinger as- 8.5.3 Container No. 3. Same as Method 5, sembly to a cleanup area that is clean, pro- Section 8.7.6.3. tected from the wind, and free of Be con- 8.6 Blanks. tamination. Inspect the train before and dur- 8.6.1 Water Blank. Save a portion of the ing this assembly, and note any abnormal water as a blank. Take 200 ml directly from conditions. Treat the sample as follows: Dis- the wash bottle being used and place it in a connect the probe from the impinger train. plastic sample container labeled ‘‘H2O 8.5.1 Container No. 1. Same as Method 5, blank.’’ Section 8.7.6.1. 8.6.2 Filter. Save two filters from each lot 8.5.2 Container No. 2. Place the contents of filters used in sampling. Place these fil- (measured to 1 ml) of the first three ters in a container labeled ‘‘filter blank.’’ impingers into a glass sample bottle. Use the 8.7 Post-test Glassware Rinsing. If an ad- procedures outlined in Section 8.7.6.2 of ditional test is desired, the glassware can be Method 5, where applicable, to rinse the carefully double rinsed with water and reas- probe nozzle, probe fitting, probe liner, filter sembled. However, if the glassware is out of holder, and all glassware between the filter use more than 2 days, repeat the initial acid holder and the back half of the third im- wash procedure. pinger with water. Repeat this procedure with acetone. Place both water and acetone 9.0 QUALITY CONTROL

Section Quality control measure Effect

8.4, 10.1 ...... Sampling equipment leak checks and calibration Ensure accuracy and precision of sampling measurements. 10.2 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.5 ...... Check for matrix effects ...... Eliminate matrix effects.

10.0 Calibration and Standardization peak height of each standard solution versus the corresponding total Be weight in the NOTE: Maintain a laboratory log of all cali- standard (in μg). brations. 10.5 Spectrophotometer Calibration Qual- 10.1 Sampling Equipment. Same as Meth- ity Control. Calculate the least squares slope od 5, Section 10.0. of the calibration curve. The line must pass 10.2 Preparation of Standard Solutions. through the origin or through a point no fur- μ Pipet 1, 3, 5, 8, and 10 ml of the 1.0 g Be/ml ther from the origin than ±2 percent of the working standard solution into separate 100 recorder full scale. Multiply the corrected ml volumetric flasks, and dilute to the mark peak height by the reciprocal of the least with water. The total amounts of Be in these squares slope to determine the distance each μ standards are 1, 3, 5, 8, and 10 g, respec- calibration point lies from the theoretical tively. calibration line. The difference between the 10.3 Spectrophotometer and Recorder. calculated concentration values and the ac- The Be response may be measured by either tual concentrations (i.e., 1, 3, 5, 8, and 10 μg peak height or peak area. Analyze an aliquot Be) must be less than 7 percent for all stand- μ of the 10- g standard at 234.8 nm using a ni- ards. trous oxide/acetylene flame. Determine the maximum absorbance of the standard, and 11.0 Analytical Procedure set this value to read 90 percent of the recorder full scale. 11.1 Sample Loss Check. Prior to analysis, 10.4 Calibration Curve. check the liquid level in Container No. 2. 10.4.1 After setting the recorder scale, Note on the analytical data sheet whether analyze an appropriately sized aliquot of leakage occurred during transport. If a no- each standard and the BLANK (see Section ticeable amount of leakage occurred, either 11) until two consecutive peaks agree within void the sample or take steps, subject to the 3 percent of their average value. approval of the Administrator, to adjust the 10.4.3 Subtract the average peak height final results. (or peak area) of the blank—which must be 11.2 Glassware Cleaning. Before use, clean less than 2 percent of recorder full scale— all glassware according to the procedure of from the averaged peak heights of the stand- Section 8.3.1. ards. If the blank absorbance is greater than 11.3 Sample Preparation. The digestion of 2 percent of full-scale, the probable cause is Be samples is accomplished in part in con- Be contamination of a reagent or carry-over centrated HClO4. of Be from a previous sample. Prepare the NOTE: The sample must be heated to light calibration curve by plotting the corrected brown fumes after the initial HNO3 addition;

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otherwise, dangerous perchlorates may re- height and the reciprocal of the least squares sult from the subsequent HClO4 digestion. slope) and the actual concentration of the HClO4 should be used only under a hood. standard must be less than 7 percent, or re- 11.3.1 Container No. 1. Transfer the filter calibration of the analyzer is required. and any loose particulate matter from Con- 11.5.3 Check for Matrix Effects (optional). tainer No. 1 to a 150-ml beaker. Add 35 ml Use the Method of Standard Additions (see concentrated HNO3. To oxidize all organic Reference 2 in Section 17.0) to check at least matter, heat on a hotplate until light brown one sample from each source for matrix ef- fumes are evident. Cool to room tempera- fects on the Be results. If the results of the ture, and add 5 ml 12 N H2SO4 and 5 ml con- Method of Standard Additions procedure centrated HClO4. used on the single source sample do not 11.3.2 Container No. 2. Place a portion of agree to within 5 percent of the value ob- the water and acetone sample into a 150 ml tained by the routine atomic absorption beaker, and put on a hotplate. Add portions analysis, then reanalyze all samples from the of the remainder as evaporation proceeds and source using the Method of Standard Addi- evaporate to dryness. Cool the residue, and tions procedure. add 35 ml concentrated HNO3. To oxidize all 11.6 Container No. 2 (Silica Gel). Weigh organic matter, heat on a hotplate until the spent silica gel (or silica gel plus im- light brown fumes are evident. Cool to room pinger) to the nearest 0.5 g using a balance. temperature, and add 5 ml 12 N H2SO4 and 5 (This step may be conducted in the field.) ml concentrated HClO4. Then proceed with step 11.3.4. 12.0 Data Analysis and Calculations 11.3.3 Final Sample Preparation. Add the Carry out calculations, retaining at least sample from Section 11.3.2 to the 150-ml one extra decimal significant figure beyond beaker from Section 11.3.1. Replace on a that of the acquired data. Round off figures hotplate, and evaporate to dryness in a only after the final calculation. Other forms HClO4 hood. Cool the residue to room tem- of the equations may be used as long as they perature, add 10.0 ml of 25 percent V/V HCl, give equivalent results. and mix to dissolve the residue. 12.1 Nomenclature. 11.3.4 Filter and Water Blanks. Cut each K = 0.3858 °K/mm Hg for metric units. filter into strips, and treat each filter indi- 1 = 17.64 °R/in. Hg for English units. vidually as directed in Section 11.3.1. Treat K = 10¥6 g/μg for metric units. the 200-ml water blank as directed in Section 3 = 2.2046 × 10¥9 lb/μg for English units. 11.3.2. Combine and treat these blanks as di- m = Total weight of beryllium in the rected in Section 11.3.3. Be source sample. 11.4 Spectrophotometer Preparation. P = Absolute stack gas pressure, mm Hg (in. Turn on the power; set the wavelength, slit s Hg). width, and lamp current; and adjust the t = Daily operating time, sec/day. background corrector as instructed by the T = Absolute average stack gas tempera- manufacturer’s manual for the particular s ture, °K (°R). atomic absorption spectrophotometer. Ad- V ( ) = Dry gas sample volume at standard just the burner and flame characteristics as m std conditions, scm (scf). necessary. V ( ) = Volume of water vapor at standard 11.5 Analysis. Calibrate the analytical w std conditions, scm (scf). equipment and develop a calibration curve as outlined in Sections 10.4 and 10.5. 12.2 Average Dry Gas Meter Temperature 11.5.1 Beryllium Samples. Repeat the pro- and Average Orifice Pressure Drop, Dry Gas cedure used to establish the calibration Volume, Volume of Water Vapor Condensed, curve with an appropriately sized aliquot of Moisture Content, Isokinetic Variation, and each sample (from Section 11.3.3) until two Stack Gas Velocity and Volumetric Flow consecutive peak heights agree within 3 per- Rate. Same as Method 5, Sections 12.2 cent of their average value. The peak height through 12.5, 12.11, and 12.12, respectively. of each sample must be greater than 10 per- 12.3 Total Beryllium. For each source cent of the recorder full scale. If the peak sample, correct the average maximum ab- height of the sample is off scale on the re- sorbance of the two consecutive samples corder, further dilute the original source whose peak heights agree within 3 percent of sample to bring the Be concentration into their average for the contribution of the so- the calibration range of the spectrophotom- lution blank (see Sections 11.3.4 and 11.5.2). eter. Correcting for any dilutions if necessary, use 11.5.2 Run a blank and standard at least the calibration curve and these corrected after every five samples to check the spec- averages to determine the total weight of Be trophotometer calibration. The peak height in each source sample. of the blank must pass through a point no 12.4 Beryllium Emission Rate. Calculate further from the origin than ±2 percent of the daily Hg emission rate, R, using Equa- the recorder full scale. The difference be- tion 104–1. For continuous operations, the op- tween the measured concentration of the erating time is equal to 86,400 seconds per standard (the product of the corrected peak day. For cyclic operations, use only the time

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per day each stack is in operation. The total Hg emission rate from a source will be the summation of results from all stacks.

KKtm PvA R = 13 Be s s s Eq. 104-1 ⎛ ⎞ TV+ V s ⎝ m() std w() std ⎠

12.5 Determination of Compliance. Each may be used as an alternative to atomic ab- performance test consists of three sample sorption analysis. runs. For the purpose of determining compli- 16.3 Cold Vapor Atomic Fluorescence ance with an applicable national emission Spectrometry (CVAFS) Analysis. CVAFS standard, use the average of the results of all may be used as an alternative to atomic ab- sample runs. sorption analysis.

13.0 Method Performance. [Reserved] 17.0 References 14.0 Pollution Prevention. [Reserved] Same as References 1, 2, and 4–11 of Section 16.0 of Method 101 with the addition of the 15.0 Waste Management. [Reserved] following: 16.0 Alternative Procedures 1. Amos, M.D., and J.B. Willis. Use of High- Temperature Pre-Mixed Flames in Atomic 16.1 Inductively Coupled Plasma-Atomic Absorption Spectroscopy. Spectrochim. Emission Spectrometry (ICP–AES) Analysis. ICP–AES may be used as an alternative to Acta. 22:1325. 1966. atomic absorption analysis provided the fol- 2. Fleet, B., K.V. Liberty, and T. S. West. lowing conditions are met: A Study of Some Matrix Effects in the De- 16.1.1 Sample collection, sample prepara- termination of Beryllium by Atomic Absorp- tion, and analytical preparation procedures tion Spectroscopy in the Nitrous Oxide-Acet- are as defined in the method except as nec- ylene Flame. Talanta 17:203. 1970. essary for the ICP–AES application. 16.1.2 Quality Assurance/Quality Control 18.0 Tables, Diagrams, Flowcharts, And procedures, including audit material anal- Validation Data [Reserved] ysis, are conducted as prescribed in the method. The QA acceptance conditions must METHOD 105—DETERMINATION OF MERCURY IN be met. WASTEWATER TREATMENT PLANT SEWAGE 16.1.3 The limit of quantitation for the SLUDGES ICP–AES must be demonstrated and the NOTE: This method does not include all of sample concentrations reported should be no the specifications (e.g., equipment and sup- less than two times the limit of quantita- plies) and procedures (e.g., sampling and ana- tion. The limit of quantitation is defined as lytical) essential to its performance. Some ten times the standard deviation of the material is incorporated by reference from blank value. The standard deviation of the other methods in this part. Therefore, to ob- blank value is determined from the analysis tain reliable results, persons using this of seven blanks. It has been reported that for method should also have a thorough knowl- mercury and those elements that form hy- edge of at least the following additional test drides, a continuous-flow generator coupled methods: Method 101 and Method 101A. to an ICP–AES offers detection limits comparable to cold vapor atomic absorption. 1.0 Scope and Application 16.2 Inductively Coupled Plasma-Mass Spectrometry (ICP–MS) Analysis. ICP–MS 1.1 Analytes.

Analyte CAS No. Sensitivity

Mercury (Hg) ...... 7439–97–6 Dependent upon spectrophotometer and recorder.

1.2 Applicability. This method is applica- hance the quality of the data obtained from ble for the determination of total organic air pollutant sampling methods. and inorganic Hg content in sewage sludges. 1.3 Data Quality Objectives. Adherence to the requirements of this method will en-

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2.0 Summary of Method 6.1.3 Mixer. Mortar mixer, wheelbarrow- type, 57-liter (or equivalent) with electricity- 2.1 Time-composite sludge samples are driven motor. withdrawn from the conveyor belt subse- 6.1.4 Blender. Waring-type, 2-liter. quent to dewatering and before incineration 6.1.5 Scoop. To remove 100-ml and 20-ml or drying. A weighed portion of the sludge is samples of blended sludge. digested in aqua regia and is oxidized by po- 6.1.6 Erlenmeyer Flasks. Four, 125-ml. tassium permanganate (KMnO4). Mercury in 6.1.7 Beakers. Glass beakers in the fol- the digested sample is then measured by the lowing sizes: 50 ml (1), 200 ml (1), 400 ml (2). conventional spectrophotometric cold-vapor 6.2 Sample Preparation and Analysis. technique. Same as Method 101, Section 6.3, with the addition of the following: 3.0 Definitions [Reserved] 6.2.1 Hot Plate. 4.0 Interferences [Reserved] 6.2.2 Desiccator. 6.2.3 Filter Paper. S and S No. 588 (or 5.0 Safety equivalent). 6.2.4 Beakers. Glass beakers, 200 ml and 5.1 Disclaimer. This method may involve 400 ml (2 each). hazardous materials, operations, and equipment. This test method may not address all 7.0 Reagents and Standards of the safety problems associated with its NOTE: Unless otherwise indicated, it is in- use. It is the responsibility of the user of this tended that all reagents conform to the spec- test method to establish appropriate safety ifications established by the Committee on and health practices and determine the ap- Analytical Reagents of the American Chem- plicability of regulatory limitations prior to ical Society, where such specifications are performing this test method. available; otherwise, use the best available 5.2 Corrosive Reagents. The following re- grade. agents are hazardous. Personal protective 7.1 Sample Analysis. Same as Method equipment and safe procedures are useful in 101A, Section 7.2, with the following addi- preventing chemical splashes. If contact oc- tions and exceptions: curs, immediately flush with copious 7.1.1 Hydrochloric Acid. The concentrated amounts of water at least 15 minutes. Re- HCl specified in Method 101A, Section 7.2.4, is move clothing under shower and decontami- not required. nate. Treat residual chemical burn as ther- 7.1.2 Aqua Regia. Prepare immediately be- mal burn. fore use. Carefully add one volume of con- 5.2.1 Hydrochloric Acid (HCl). Highly centrated HNO3 to three volumes of con- toxic. Vapors are highly irritating to eyes, centrated HCl. skin, nose, and lungs, causing severe damage. May cause bronchitis, pneumonia, or 8.0 Sample Collection, Preservation, Storage, edema of lungs. Exposure to concentrations and Transport of 0.13 to 0.2 percent can be lethal to humans 8.1 Sludge Sampling. Withdraw equal vol- in a few minutes. Provide ventilation to ume increments of sludge [for a total of at limit exposure. Reacts with metals, pro- least 15 liters (16 quarts)] at intervals of 30 ducing hydrogen gas. min over an 8-hr period, and combine in a 5.2.2 Nitric Acid (HNO3). Highly corrosive rigid plastic container. to eyes, skin, nose, and lungs. Vapors cause 8.2 Sludge Mixing. Transfer the entire 15- bronchitis, pneumonia, or edema of lungs. liter sample to a mortar mixer. Mix the sam- Reaction to inhalation may be delayed as ple for a minimum of 30 min at 30 rpm. Take long as 30 hours and still be fatal. Provide six 100-ml portions of sludge, and combine in ventilation to limit exposure. Strong oxi- a 2-liter blender. Blend sludge for 5 min; add dizer. Hazardous reaction may occur with or- water as necessary to give a fluid consist- ganic materials such as solvents. ency. Immediately after stopping the blender, withdraw four 20-ml portions of blended 6.0 Equipment and Supplies sludge, and place them in separate, tared 125- ml Erlenmeyer flasks. Reweigh each flask to 6.1 Sample Collection and Mixing. The determine the exact amount of sludge added. following items are required for collection 8.3 Sample Holding Time. Samples shall and mixing of the sludge samples: be analyzed within the time specified in the 6.1.1 Container. Plastic, 50-liter. applicable subpart of the regulations. 6.1.2 Scoop. To remove 950-ml (1 quart.) sludge sample. 9.0 Quality Control

Section Quality control measure Effect

10.0 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.0 ...... Check for matrix effects ...... Eliminate matrix effects.

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10.0 Calibration and Standardization Cm = Concentration of Hg in the digested sample, μg/g. Same as Method 101A, Section 10.2. Fsb = Weight fraction of solids in the blended 11.0 Analytical Procedures sludge. Fsm = Weight fraction of solids in the col- 11.1 Solids Content of Blended Sludge. lected sludge after mixing. Dry one of the 20-ml blended samples from M = Hg content of the sewage sludge (on a Section 8.2 in an oven at 105 °C (221 °F) to dry basis), μg/g. constant weight. Cool in a desiccator, weigh m = Mass of Hg in the aliquot of digested and record the dry weight of the sample. sample analyzed, μg. 11.2 Aqua Regia Digestion of Blended n = number of digested samples (specified in Samples. Section 11.2 as three). 11.2.1 To each of the three remaining 20- ml samples from Section 8.2 add 25 ml of Va = Volume of digested sample analyzed, aqua regia, and digest the on a hot plate at ml. low heat (do not boil) for 30 min, or until Vs = Volume of digested sample, ml. samples are a pale yellow-brown color and Wb = Weight of empty sample beaker, g. are void of the dark brown color char- Wbs = Weight of sample beaker and sample, g. acteristic of organic matter. Remove from Wbd = Weight of sample beaker and sample hotplate and allow to cool. after drying, g. 11.2.2 Filter each digested sample sepa- Wf = Weight of empty sample flask, g. rately through an S and S No. 588 filter or Wfd = Weight of sample flask and sample equivalent, and rinse the filter contents with after drying, g. 50 ml of water. Transfer the filtrate and fil- Wfs = Weight of sample flask and sample, g. ter washing to a 100-ml volumetric flask, and 12.2 Mercury Content of Digested Sample carefully dilute to volume with water. (Wet Basis). 11.3 Solids Content of the Sludge Before 12.2.1 For each sample analyzed for Hg Blending. Remove two 100-ml portions of content, calculate the arithmetic mean max- mixed sludge from the mortar mixer and imum absorbance of the two consecutive place in separate, tared 400-ml beakers. Re- samples whose peak heights agree ±3 percent weigh each beaker to determine the exact of their average. Correct this average value amount of sludge added. Dry in oven at 105 for the contribution of the blank. Use the °C (221 °F) and cool in a desiccator to con- calibration curve and these corrected aver- stant weight. ages to determine the final Hg concentration 11.4 Analysis for Mercury. Analyze the in the solution cell for each sludge sample. three aqua regia-digested samples using the 12.2.2 Calculate the average Hg concentra- procedures outlined in Method 101A, Section tion of the digested samples by correcting 11.0. for any dilutions made to bring the sample into the working range of the spectro- 12.0 Data Analysis and Calculations photometer and for the weight of the sludge 12.1 Nomenclature. portion digested, using Equation 105–1.

n ⎡ ⎤ = mVs Cm ∑ ⎢ ⎥ Eq. 105-1 = ⎢VW()− W⎥ i 1 ⎣ afsf⎦i

12.3 Solids Content of Blended Sludge. De- termine the solids content of the blended sludge using Equation 105–2.

WW− F =−1fs fd Eq. 105-2 sb − WWfs f

12.4 Solids Content of Bulk Sample (be- 100 ml aliquot (Section 11.3), and average the fore blending but, after mixing in mortar results. mixer). Determine the solids content of each

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WW− F =−1bs bd Eq. 105-3 sm − WWbs b

12.5 Mercury Content of Bulk Sample ple, and calculate the Hg concentration of (Dry Basis). Average the results from the the composite sample on a dry basis. three samples from each 8-hr composite sam-

C M = m Eq. 105-4 Fsb

13.0 Method Performance Technique) (Provisional Method). U.S. Envi- ronmental Protection Agency. Cincinnati, 13.1 Range. The range of this method is 0.2 Ohio. April 1972. to 5 micrograms per gram; it may be extended by increasing or decreasing sample 6. Kopp, J.F., M.C. Longbottom, and L.B. size. Lobring. ‘‘Cold Vapor’’ Method for Deter- mining Mercury. Journal AWWA. 64(1):20–25. 14.0 Pollution Prevention. [Reserved] 1972. 7. Manual of Methods for Chemical Anal- 15.0 Waste Management. [Reserved] ysis of Water and Wastes. U.S. Environ- mental Protection Agency. Cincinnati, Ohio. 16.0 References Publication No. EPA–624/2–74–003. December 1. Bishop, J.N. Mercury in Sediments. On- 1974. pp. 118–138. tario Water Resources Commission. Toronto, 8. Mitchell, W.J., M.R. Midgett, J. Suggs, Ontario, Canada. 1971. R.J. Velton, and D. Albrink. Sampling and 2. Salma, M. Private Communication. EPA Homogenizing Sewage for Analysis. Environ- California/Nevada Basin Office. Alameda, mental Monitoring and Support Laboratory, California. Office of Research and Development, U.S. 3. Hatch, W.R. and W.L. Ott. Determina- Environmental Protection Agency. Research tion of Sub-Microgram Quantities of Mer- Triangle Park, N.C. March 1979. p. 7. cury by Atomic Absorption Spectrophotometry. Analytical Chemistry. 17.0 Tables, Diagrams, Flowcharts, and 40:2085. 1968. Validation Data. [Reserved] 4. Bradenberger, H., and H. Bader. The De- termination of Nanogram Levels of Mercury METHOD 106—DETERMINATION OF VINYL CHLO- in Solution by a Flameless Atomic Absorp- RIDE EMISSIONS FROM STATIONARY tion Technique. Atomic Absorption News- SOURCES letter. 6:101. 1967. 1.0 Scope and Application 5. Analytical Quality Control Laboratory (AQCL). Mercury in Sediment (Cold Vapor 1.1 Analytes.

Analyte CAS No. Sensitivity

Vinyl Chloride (CH2:CHCl) ...... 75–01–4 Dependent upon analytical equipment.

1.2 Applicability. This method is applica- 2.0 Summary of Method ble for the determination of vinyl chloride 2.1 An integrated bag sample of stack gas emissions from ethylene dichloride, vinyl containing vinyl chloride is subjected to GC chloride, and polyvinyl chloride manufac- analysis using a flame ionization detector turing processes. This method does not (FID). measure vinyl chloride contained in particulate matter. 3.0 Definitions. [Reserved] 1.3 Data Quality Objectives. Adherence to the requirements of this method will en- 4.0 Interferences hance the quality of the data obtained from 4.1 Resolution interferences of vinyl chlo- air pollutant sampling methods. ride may be encountered on some sources. Therefore, the chromatograph operator

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should select the column and operating pa- 6.1.11 Tubing Fittings and Connectors. rameters best suited to the particular anal- Teflon or stainless steel, to assemble sam- ysis requirements. The selection made is pling training. subject to approval of the Administrator. 6.2 Sample Recovery. Teflon tubing, 6.4- Approval is automatic, provided that con- mm outside diameter, to connect bag to GC firming data are produced through an ade- sample loop. Use a new unused piece for each quate supplemental analytical technique, series of bag samples that constitutes an and that the data are available for review by emission test, and discard upon conclusion of the Administrator. An example of this would analysis of those bags. be analysis with a different column or GC/ 6.3 Analysis. The following equipment is mass spectroscopy. required: 6.3.1 Gas Chromatograph. With FID 5.0 Safety potentiometric strip chart recorder and 1.0 to 5.0-ml heated sampling loop in automatic 5.1 Disclaimer. This method may involve sample valve. The chromatographic system hazardous materials, operations, and equip- shall be capable of producing a response to ment. This test method may not address all 0.1-ppmv vinyl chloride that is at least as of the safety problems associated with its great as the average noise level. (Response is use. It is the responsibility of the user of this measured from the average value of the base test method to establish appropriate safety line to the maximum of the wave form, while and health practices and determine the ap- standard operating conditions are in use.) plicability of regulatory limitations prior to 6.3.2 Chromatographic Columns. Columns performing this test method. as listed below. Other columns may be used 5.2 Toxic Analyte. Care must be exercised provided that the precision and accuracy of to prevent exposure of sampling personnel to the analysis of vinyl chloride standards are vinyl chloride, which is a carcinogen. not impaired and that information is available for review confirming that there is ade- 6.0 Equipment and Supplies quate resolution of vinyl chloride peak. 6.1 Sample Collection (see Figure 106–1). (Adequate resolution is defined as an area The sampling train consists of the following overlap of not more than 10 percent of the components: vinyl chloride peak by an interferent peak. 6.1.1 Probe. Stainless steel, borosilicate Calculation of area overlap is explained in glass, Teflon tubing (as stack temperature Procedure 1 of appendix C to this part: ‘‘De- permits), or equivalent, equipped with a termination of Adequate Chromatographic glass wool plug to remove particulate mat- Peak Resolution.’’) ter. 6.3.2.1 Column A. Stainless steel, 2.0 m by 6.1.2 Sample Lines. Teflon, 6.4-mm outside 3.2 mm, containing 80/100-mesh Chromasorb diameter, of sufficient length to connect 102. probe to bag. Use a new unused piece for 6.3.2.2 Column B. Stainless steel, 2.0 m by each series of bag samples that constitutes 3.2 mm, containing 20 percent GE SF–96 on an emission test, and discard upon comple- 60/ip-mesh Chromasorb P AW; or stainless tion of the test. steel, 1.0 m by 3.2 mm containing 80/100-mesh 6.1.3 Quick Connects. Stainless steel, Porapak T. Column B is required as a sec- male (2) and female (2), with ball checks (one ondary column if acetaldehyde is present. If pair without), located as shown in Figure used, column B is placed after column A. The 106–1. combined columns should be operated at 120 °C (250 °F). 6.1.4 Tedlar Bags. 50- to 100-liter capacity, 6.3.3 Rate Meters (2). Rotameter , or to contain sample. Aluminized Mylar bags equivalent, 100-ml/min capacity, with flow may be used if the samples are analyzed control valves. within 24 hours of collection. 6.3.4 Gas Regulators. For required gas cyl- 6.1.5 Bag Containers. Rigid leak-proof inders. containers for sample bags, with covering to 6.3.5 Temperature Sensor. Accurate to ±1 protect contents from sunlight. °C (±2 °F), to measure temperature of heated 6.1.6 Needle Valve. To adjust sample flow sample loop at time of sample injection. rates. 6.3.6 Barometer. Accurate to ±5 mm Hg, to 6.1.7 Pump. Leak-free, with minimum of measure atmospheric pressure around GC 2-liter/min capacity. during sample analysis. 6.1.8 Charcoal Tube. To prevent admission 6.3.7 Pump. Leak-free, with minimum of of vinyl chloride and other organics to the 100-ml/min capacity. atmosphere in the vicinity of samplers. 6.3.8 Recorder. Strip chart type, option- 6.1.9 Flowmeter. For observing sampling ally equipped with either disc or electronic flow rate; capable of measuring a flow range integrator. from 0.10 to 1.00 liter/min. 6.3.9 Planimeter. Optional, in place of disc 6.1.10 Connecting Tubing. Teflon, 6.4-mm or electronic integrator on recorder, to outside diameter, to assemble sampling train measure chromatograph peak areas. (Figure 106–1). 6.4 Calibration and Standardization.

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6.4.1 Tubing. Teflon, 6.4-mm outside di- centration of vinyl chloride in nitrogen in ameter, separate pieces marked for each each cylinder by (a) directly analyzing each calibration concentration. cylinder and (b) calibrating his analytical NOTE: The following items are required procedure on the day of cylinder analysis. To only if the optional standard gas preparation calibrate his analytical procedure, the man- procedures (Section 10.1) are followed. ufacturer shall use as a minimum, a three 6.4.2 Tedlar Bags. Sixteen-inch-square point calibration curve. It is recommended size, with valve; separate bag marked for that the manufacturer maintain (1) a high each calibration concentration. concentration calibration standard (between 6.4.3 Syringes. 0.5-ml and 50-μl, gas tight, 50 and 100 ppmv) to prepare his calibration individually calibrated to dispense gaseous curve by an appropriate dilution technique vinyl chloride. and (2) a low-concentration calibration 6.4.4 Dry Gas Meter with Temperature standard (between 5 and 10 ppmv) to verify and Pressure Gauges. Singer Model DTM–115 the dilution technique used. If the difference with 802 index, or equivalent, to meter nitro- between the apparent concentration read gen in preparation of standard gas mixtures, from the calibration curve and the true con- calibrated at the flow rate used to prepare centration assigned to the low-concentration standards. calibration standard exceeds 5 percent of the true concentration, the manufacturer shall 7.0 Reagents and Standards determine the source of error and correct it, then repeat the three-point calibration. 7.1 Analysis. The following reagents are required for analysis. 7.2.3.2 Verification of Manufacturer’s 7.1.1 Helium or Nitrogen. Purity 99.9995 Calibration Standards. Before using a stand- percent or greater, for chromatographic car- ard, the manufacturer shall verify each cali- rier gas. bration standard (a) by comparing it to gas 7.1.2 Hydrogen. Purity 99.9995 percent or mixtures prepared (with 99 mole percent greater. vinyl chloride) in accordance with the proce- 7.1.3 Oxygen or Air. Either oxygen (purity dure described in Section 7.2.1 or (b) cali- 99.99 percent or greater) or air (less than 0.1 brating it against vinyl chloride cylinder ppmv total hydrocarbon content), as re- Standard Reference Materials (SRM’s) pre- quired by detector. pared by the National Institute of Standards 7.2 Calibration. Use one of the following and Technology, if such SRM’s are available. options: either Sections 7.2.1 and 7.2.2, or The agreement between the initially deter- Section 7.2.3. mined concentration value and the 7.2.1 Vinyl Chloride. Pure vinyl chloride verification concentration value must be ±5 gas certified by the manufacturer to contain percent. The manufacturer must reverify all a minimum of 99.9 percent vinyl chloride. If calibration standards on a time interval con- the gas manufacturer maintains a bulk cyl- sistent with the shelf life of the cylinder inder supply of 99.9 + percent vinyl chloride, standards sold. the certification analysis may have been performed on this supply, rather than on each 8.0 Sample Collection, Preservation, Storage, gas cylinder prepared from this bulk supply. and Transport The date of gas cylinder preparation and the NOTE: Performance of this method should certified analysis must have been affixed to not be attempted by persons unfamiliar with the cylinder before shipment from the gas the operation of a gas chromatograph (GC) manufacturer to the buyer. nor by those who are unfamiliar with source 7.2.2 Nitrogen. Same as described in Sec- sampling, because knowledge beyond the tion 7.1.1. scope of this presentation is required. 7.2.3 Cylinder Standards. Gas mixture standards (50-,10-, and 5 ppmv vinyl chloride) 8.1 Bag Leak-Check. The following leak- in nitrogen cylinders may be used to directly check procedure is recommended, but not re- prepare a chromatograph calibration curve quired, prior to sample collection. The post- as described in Section 10.3 if the following test leak-check procedure is mandatory. conditions are met: (a) The manufacturer Connect a water manometer and pressurize certifies the gas composition with an accu- the bag to 5 to 10 cm H2O (2 to 4 in. H2O). racy of ±3 percent or better. (b) The manu- Allow to stand for 10 min. Any displacement facturer recommends a maximum shelf life in the water manometer indicates a leak. over which the gas concentration does not Also, check the rigid container for leaks in change by greater than ±5 percent from the this manner. certified value. (c) The manufacturer affixes NOTE: An alternative leak-check method is the date of gas cylinder preparation, cer- to pressurize the bag to 5 to 10 cm H2O and tified vinyl chloride concentration, and rec- allow it to stand overnight. A deflated bag ommended maximum shelf to the cylinder indicates a leak. For each sample bag in its before shipment to the buyer. rigid container, place a rotameter in line be- 7.2.3.1 Cylinder Standards Certification. tween the bag and the pump inlet. Evacuate The manufacturer shall certify the con- the bag. Failure of the rotameter to register

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zero flow when the bag appears to be empty direct the gas exiting the rotameter away indicates a leak. from sampling personnel. At the end of the 8.2 Sample Collection. Assemble the sam- sample period, shut off the pump, disconnect ple train as shown in Figure 106–1. Join the the sample line from the bag, and disconnect quick connects as illustrated, and determine the vacuum line from the bag container. Pro- that all connection between the bag and the tect the bag container from sunlight. probe are tight. Place the end of the probe at 8.3 Sample Storage. Keep the sample bags the centroid of the stack and start the pump out of direct sunlight. When at all possible, with the needle valve adjusted to yield a flow analysis is to be performed within 24 hours, that will fill over 50 percent of bag volume in but in no case in excess of 72 hours of sample the specific sample period. After allowing collection. Aluminized Mylar bag samples sufficient time to purge the line several must be analyzed within 24 hours. times, change the vacuum line from the con- 8.4 Post-test Bag Leak-Check. Subsequent tainer to the bag and evacuate the bag until to recovery and analysis of the sample, leak- the rotameter indicates no flow. Then reposi- check the sample bag according to the proce- tion the sample and vacuum lines and begin dure outlined in Section 8.1. the actual sampling, keeping the rate proportional to the stack velocity. At all times, 9.0 QUALITY CONTROL

Section Quality control measure Effect

10.3 ...... Chromatograph calibration...... Ensure precision and accuracy of chromatograph.

10.0 Calibration and Standardization equipment plumbing arranged identically to Section 11.2, and flush the sample loop for 30 NOTE: Maintain a laboratory log of all cali- brations. seconds at the rate of 100 ml/min with one of the vinyl chloride calibration mixtures. 10.1 Preparation of Vinyl Chloride Stand- Then activate the sample valve. Record the ard Gas Mixtures. (Optional Procedure-de- injection time. Select the peak that cor- lete if cylinder standards are used.) Evacuate a 16-inch square Tedlar bag that has passed a responds to vinyl chloride. Measure the dis- leak-check (described in Section 8.1) and tance on the chart from the injection time to meter in 5.0 liters of nitrogen. While the bag the time at which the peak maximum oc- is filling, use the 0.5-ml syringe to inject 250 curs. This quantity divided by the chart μl of 99.9 + percent vinyl chloride gas speed is defined as the retention time. Since through the wall of the bag. Upon with- other organics may be present in the sample, drawing the syringe, immediately cover the positive identification of the vinyl chloride resulting hole with a piece of adhesive tape. peak must be made. The bag now contains a vinyl chloride con- 10.3 Preparation of Chromatograph Cali- centration of 50 ppmv. In a like manner use bration Curve. Make a GC measurement of the 50 μl syringe to prepare gas mixtures each gas mixture standard (described in Sec- having 10-and 5-ppmv vinyl chloride con- tion 7.2.3 or 10.1) using conditions identical centrations. Place each bag on a smooth sur- to those listed in Sections 11.2 and 11.3. face and alternately depress opposite sides of Flush the sampling loop for 30 seconds at the the bag 50 times to further mix the gases. rate of 100 ml/min with one of the standard These gas mixture standards may be used for mixtures, and activate the sample valve. 10 days from the date of preparation, after Record the concentration of vinyl chloride which time new gas mixtures must be pre- injected (C ), attenuator setting, chart speed, pared. (Caution: Contamination may be a c peak area, sample loop temperature, column problem when a bag is reused if the new gas temperature, carrier gas flow rate, and re- mixture standard is a lower concentration than the previous gas mixture standard.) tention time. Record the barometric pres- 10.2 Determination of Vinyl Chloride Re- sure. Calculate Ac, the peak area multiplied tention Time. (This section can be performed by the attenuator setting. Repeat until two simultaneously with Section 10.3.) Establish consecutive injection areas are within 5 per- chromatograph conditions identical with cent, then plot the average of those two val- those in Section 11.3. Determine proper at- ues versus Cc. When the other standard gas tenuator position. Flush the sampling loop mixtures have been similarly analyzed and with helium or nitrogen and activate the plotted, draw a straight line through the sample valve. Record the injection time, points derived by the least squares method. sample loop temperature, column tempera- Perform calibration daily, or before and ture, carrier gas flow rate, chart speed, and after the analysis of each emission test set of attenuator setting. Record peaks and detec- bag samples, whichever is more frequent. For tor responses that occur in the absence of each group of sample analyses, use the aver- vinyl chloride. Maintain conditions with the age of the two calibration curves which

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bracket that group to determine the respec- determined in Section 10.2. Measure the tive sample concentrations. If the two cali- vinyl chloride peak area, Am, by use of a disc bration curves differ by more than 5 percent integrator, electronic integrator, or a pla- from their mean value, then report the final nimeter. Measure and record the peak results by both calibration curves. heights, Hm. Record Am and retention time. Repeat the injection at least two times or 11.0 Analytical Procedure until two consecutive values for the total 11.2 Sample Recovery. With a new piece of area of the vinyl chloride peak agree within Teflon tubing identified for that bag, con- 5 percent of their average. Use the average nect a bag inlet valve to the gas chro- value for these two total areas to compute matograph sample valve. Switch the valve to the bag concentration. receive gas from the bag through the sample 11.3.2 Compare the ratio of Hm to Am for loop. Arrange the equipment so the sample the vinyl chloride sample with the same gas passes from the sample valve to 100-ml/ ratio for the standard peak that is closest in min rotameter with flow control valve fol- height. If these ratios differ by more than 10 lowed by a charcoal tube and a 1-in. H2O percent, the vinyl chloride peak may not be pressure gauge. Maintain the sample flow ei- pure (possibly acetaldehyde is present) and ther by a vacuum pump or container pressur- the secondary column should be employed ization if the collection bag remains in the (see Section 6.3.2.2). rigid container. After sample loop purging is 11.4 Determination of Bag Water Vapor ceased, allow the pressure gauge to return to Content. Measure the ambient temperature zero before activating the gas sampling and barometric pressure near the bag. From valve. a water saturation vapor pressure table, de- 11.3 Analysis. termine and record the water vapor content 11.3.1 Set the column temperature to 100 of the bag, Bwb, as a decimal figure. (Assume °C (210 °F) and the detector temperature to the relative humidity to be 100 percent un- 150 °C (300 °F). When optimum hydrogen and less a lesser value is known.) oxygen (or air) flow rates have been determined, verify and maintain these flow rates 12.0 Calculations and Data Analysis during all chromatography operations. Using helium or nitrogen as the carrier gas, estab- 12.1 Nomenclature. lish a flow rate in the range consistent with Am = Measured peak area. the manufacturer’s requirements for satis- Af = Attenuation factor. factory detector operation. A flow rate of ap- Bwb = Water vapor content of the bag sample, proximately 40 ml/min should produce ade- as analyzed, volume fraction. quate separations. Observe the base line peri- Cb = Concentration of vinyl chloride in the odically and determine that the noise level bag, ppmv. has stabilized and that base line drift has Cc = Concentration of vinyl chloride in the ceased. Purge the sample loop for 30 seconds standard sample, ppmv. at the rate of 100 ml/min, shut off flow, allow Pi = Laboratory pressure at time of analysis, the sample loop pressure to reach atmos- mm Hg. pheric pressure as indicated by the H O ma- 2 P = Reference pressure, the laboratory pres- nometer, then activate the sample valve. r sure recorded during calibration, mm Hg. Record the injection time (the position of the pen on the chart at the time of sample Ti = Absolute sample loop temperature at ° ° injection), sample number, sample loop tem- the time of analysis, K ( R). perature, column temperature, carrier gas Tr = Reference temperature, the sample loop flow rate, chart speed, and attenuator set- temperature recorded during calibration, ° ° ting. Record the barometric pressure. From K ( R). the chart, note the peak having the reten- 12.2 Sample Peak Area. Determine the tion time corresponding to vinyl chloride as sample peak area, Ac, as follows:

= AAAcmf Eq. 106-1

12.3 Vinyl Chloride Concentration. From to Ac, the sample peak area. Calculate the the calibration curves prepared in Section concentration of vinyl chloride in the bag,

10.3, determine the average concentration Cb, as follows: value of vinyl chloride, Cc, that corresponds

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CPT C = cri Eq. 106-2 b − PTir()1 B wb

13.0 Method Performance Vinyl Chloride in Air. U.S. Environmental 13.1 Analytical Range. This method is de- Protection Agency, Research Triangle Park, signed for the 0.1 to 50 parts per million by N.C. EPA Contract No. 68–02–1408, Task Order volume (ppmv) range. However, common gas No. 2, EPA Report No. 75–VCL–1. December chromatograph (GC) instruments are capable 13, 1974. of detecting 0.02 ppmv vinyl chloride. With 3. Midwest Research Institute. Standard- proper calibration, the upper limit may be ization of Stationary Source Emission Meth- extended as needed. od for Vinyl Chloride. U.S. Environmental Protection Agency, Research Triangle Park, 14.0 Pollution Prevention, [Reserved] N.C. Publication No. EPA–600/4–77–026. May 15.0 Waste Management, [Reserved] 1977. 4. Scheil, G. and M.C. Sharp. Collaborative 16.0 References Testing of EPA Method 106 (Vinyl Chloride) 1. Brown D.W., E.W. Loy, and M.H. Ste- that Will Provide for a Standardized Sta- phenson. Vinyl Chloride Monitoring Near the tionary Source Emission Measurement B. F. Goodrich Chemical Company in Louis- Method. U.S. Environmental Protection ville, KY. Region IV, U.S. Environmental Agency, Research Triangle Park, N.C. Publi- Protection Agency, Surveillance and Anal- cation No. EPA 600/4–78–058. October 1978. ysis Division, Athens, GA. June 24, 1974. 2. G.D. Clayton and Associates. Evaluation 17.0 Tables, Diagrams Flowcharts, and of a Collection and Analytical Procedure for Validation Data.

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METHOD 107—DETERMINATION OF VINYL CHLO- sampling, because knowledge beyond the RIDE CONTENT OF IN-PROCESS WASTEWATER scope of this presentation is required. This SAMPLES, AND VINYL CHLORIDE CONTENT OF method does not include all of the specifica- POLYVINYL CHLORIDE RESIN SLURRY, WET tions (e.g., equipment and supplies) and pro- CAKE, AND LATEX SAMPLES cedures (e.g., sampling and analytical) essential to its performance. Some material is in- NOTE: Performance of this method should corporated by reference from other methods not be attempted by persons unfamiliar with in this part. Therefore, to obtain reliable re- the operation of a gas chromatograph (GC) sults, persons using this method should have nor by those who are unfamiliar with source

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a thorough knowledge of at least the fol- 1.0 Scope and Application lowing additional test methods: Method 106. 1.1 Analytes.

Analyte CAS No. Sensitivity

Vinyl Chloride (CH2:CHCl) ...... 75–01–4 Dependent upon analytical equipment.

1.2 Applicability. This method is applica- 5.0 Safety ble for the determination of the vinyl chlo- 5.1 Disclaimer. This method may involve ride monomer (VCM) content of in-process hazardous materials, operations, and equip- wastewater samples, and the residual vinyl ment. This test method may not address all chloride monomer (RCVM) content of poly- of the safety problems associated with its vinyl chloride (PVC) resins, wet, cake, slur- use. It is the responsibility of the user of this ry, and latex samples. It cannot be used for test method to establish appropriate safety polymer in fused forms, such as sheet or and health practices and determine the ap- cubes. This method is not acceptable where plicability of regulatory limitations prior to methods from section 304(h) of the Clean performing this test method. Water Act, 33 U.S.C. 1251 et seq. (the Federal 5.2 Toxic Analyte. Care must be exercised Water Pollution Control Amendments of 1972 to prevent exposure of sampling personnel to as amended by the Clean Water Act of 1977) vinyl chloride, which is a carcinogen. Do not are required. release vinyl chloride to the laboratory at- 1.3 Data Quality Objectives. Adherence to mosphere during preparation of standards. the requirements of this method will en- Venting or purging with VCM/air mixtures hance the quality of the data obtained from must be held to a minimum. When they are air pollutant sampling methods. required, the vapor must be routed to outside air. Vinyl chloride, even at low ppm lev- 2.0 Summary of Method els, must never be vented inside the laboratory. After vials have been analyzed, the gas 2.1 The basis for this method relates to must be vented prior to removal of the vial the vapor equilibrium that is established at from the instrument turntable. Vials must a constant known temperature in a closed be vented through a hypodermic needle con- system between RVCM, PVC resin, water, nected to an activated charcoal tube to pre- and air. The RVCM in a PVC resin will vent release of vinyl chloride into the lab- equilibrate rapidly in a closed vessel, pro- oratory atmosphere. The charcoal must be vided that the temperature of the PVC resin replaced prior to vinyl chloride break- is maintained above the glass transition through. temperature of that specific resin. 6.0 Equipment and Supplies 2.2 A sample of PVC or in-process wastewater is collected in a vial or bottle and is 6.1 Sample Collection. The following conditioned. The headspace in the vial or equipment is required: bottle is then analyzed for vinyl chloride 6.1.1 Glass bottles. 60-ml (2-oz) capacity, using gas chromatography with a flame ion- with wax-lined screw-on tops, for PVC sam- ization detector. ples. 6.1.2 Glass Vials. Headspace vials, with 3.0 Definitions [Reserved] Teflon-faced butyl rubber sealing discs, for water samples. 4.0 Interferences 6.1.3 Adhesive Tape. To prevent loosening 4.1 The chromatograph columns and the of bottle tops. 6.2 Sample Recovery. The following corresponding operating parameters herein equipment is required: described normally provide an adequate reso- 6.2.1 Glass Vials. Headspace vials, with lution of vinyl chloride; however, resolution butyl rubber septa and aluminum caps. Sili- interferences may be encountered on some cone rubber is not acceptable. sources. Therefore, the chromatograph oper- 6.2.2 Analytical Balance. Capable of deter- ator shall select the column and operating mining sample weight within an accuracy of parameters best suited to his particular ±1 percent. analysis requirements, subject to the ap- 6.2.3 Vial Sealer. To seal headspace vials. proval of the Administrator. Approval is 6.2.4 Syringe. 100-ml capacity. automatic provided that confirming data are 6.3 Analysis. The following equipment is produced through an adequate supplemental required: analytical technique, such as analysis with a 6.3.1 Headspace Sampler and Chro- different column or GC/mass spectroscopy, matograph. Capable of sampling and ana- and that these data are made available for lyzing a constant amount of headspace gas review by the Administrator. from a sealed vial, while maintaining that

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vial at a temperature of 90 °C ±0.5 °C (194 °F procedure on the day of cylinder analysis. To ±0.9 °F). The chromatograph shall be calibrate the analytical procedure, the man- equipped with a flame ionization detector ufacturer shall use, as a minimum, a 3-point (FID). Perkin-Elmer Corporation Models F– calibration curve. It is recommended that 40, F–42, F–45, HS–6, and HS–100, and Hew- the manufacturer maintain (1) a high-con- lett-Packard Corporation Model 19395A have centration calibration standard (between been found satisfactory. Chromatograph 4000 and 8000 ppm) to prepare the calibration backflush capability may be required. curve by an appropriate dilution technique 6.3.2 Chromatographic Columns. Stainless and (2) a low-concentration calibration steel 1 m by 3.2 mm and 2 m by 3.2 mm, both standard (between 50 and 500 ppm) to verify containing 50/80-mesh Porapak Q. Other col- the dilution technique used. If the difference umns may be used provided that the preci- between the apparent concentration read sion and accuracy of the analysis of vinyl from the calibration curve and the true con- chloride standards are not impaired and in- centration assigned to the low-concentration formation confirming that there is adequate calibration standard exceeds 5 percent of the resolution of the vinyl chloride peak are true concentration, the manufacturer shall available for review. (Adequate resolution is determine the source of error and correct it, defined as an area overlap of not more than then repeat the 3-point calibration. 10 percent of the vinyl chloride peak by an 7.2.1.2 Verification of Manufacturer’s interferant peak. Calculation of area overlap Calibration Standards. Before using, the is explained in Procedure 1 of appendix C to manufacturer shall verify each calibration this part: ‘‘Determination of Adequate standard by (a) comparing it to gas mixtures Chromatographic Peak Resolution.’’) Two prepared (with 99 mole percent vinyl chlo- 1.83 m columns, each containing 1 percent ride) in accordance with the procedure de- Carbowax 1500 on Carbopak B, have been scribed in Section 10.1 of Method 106 or by (b) found satisfactory for samples containing ac- calibrating it against vinyl chloride cylinder etaldehyde. Standard Reference Materials (SRMs) pre- 6.3.3 Temperature Sensor. Range 0 to 100 pared by the National Institute of Standards °C (32 to 212 °F) accurate to 0.1 °C. and Technology, if such SRMs are available. 6.3.4 Integrator-Recorder. To record The agreement between the initially deter- chromatograms. mined concentration value and the 6.3.5 Barometer. Accurate to 1 mm Hg. verification concentration value must be 6.3.6 Regulators. For required gas cyl- within 5 percent. The manufacturer must inders. 6.3.7 Headspace Vial Pre-Pressurizer. Ni- reverify all calibration standards on a time trogen pressurized hypodermic needle inside interval consistent with the shelf life of the protective shield. cylinder standards sold. 7.0 Reagents and Standards 8.0 Sample Collection, Preservation, Storage, and Transport 7.1 Analysis. Same as Method 106, Section 7.1, with the addition of the following: 8.1 Sample Collection. 7.1.1 Water. Interference-free. 8.1.1 PVC Sampling. Allow the resin or 7.2 Calibration. The following items are slurry to flow from a tap on the tank or silo required for calibration: until the tap line has been well purged. Ex- 7.2.1 Cylinder Standards (4). Gas mixture tend and fill a 60-ml sample bottle under the standards (50-, 500-, 2000- and 4000-ppm vinyl tap, and immediately tighten a cap on the chloride in nitrogen cylinders). Cylinder bottle. Wrap adhesive tape around the cap standards may be used directly to prepare a and bottle to prevent the cap from loosening. chromatograph calibration curve as de- Place an identifying label on each bottle, scribed in Section 10.3, if the following con- and record the date, time, and sample loca- ditions are met: (a) The manufacturer cer- tion both on the bottles and in a log book. tifies the gas composition with an accuracy 8.1.2 Water Sampling. At the sampling lo- of ±3 percent or better (see Section 7.2.1.1). cation fill the vials bubble-free to over- (b) The manufacturer recommends a max- flowing so that a convex meniscus forms at imum shelf life over which the gas con- the top. The excess water is displaced as the centration does not change by greater than sealing disc is carefully placed, with the Tef- ±5 percent from the certified value. (c) The lon side down, on the opening of the vial. manufacturer affixes the date of gas cylinder Place the aluminum seal over the disc and preparation, certified vinyl chloride con- the neck of the vial, and crimp into place. centration, and recommended maximum Affix an identifying label on the bottle, and shelf life to the cylinder before shipment to record the date, time, and sample location the buyer. both on the vials and in a log book. 7.2.1.1 Cylinder Standards Certification. 8.2 Sample Storage. All samples must be The manufacturer shall certify the con- analyzed within 24 hours of collection, and centration of vinyl chloride in nitrogen in must be refrigerated during this period. each cylinder by (a) directly analyzing each cylinder and (b) calibrating the analytical 9.0 Quality Control 281

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Section Quality control measure Effect

10.3 ...... Chromatograph calibration ...... Ensure precision and accuracy of chromatograph.

10.0 Calibration and Standardization both analyses of 500-ppm standards [2,000- ppm standards if dispersion resin (excluding NOTE: Maintain a laboratory log of all cali- latex resin) samples are being analyzed] brations. 10.1 Preparation of Standards. Calibration must be within 5 percent of the most recent standards are prepared as follows: Place 100 four-point calibration curve. If this criterion μl or about two equal drops of distilled water is not met, then a complete four-point cali- in the sample vial, then fill the vial with the bration must be performed before sample VCM/nitrogen standard, rapidly seat the sep- analyses can proceed. tum, and seal with the aluminum cap. Use a 10.3 Preparation of Chromatograph Cali- 1⁄8-in. stainless steel line from the cylinder to bration Curve. Prepare two vials each of 50- the vial. Do not use rubber or Tygon tubing. , 500-, 2,000-, and 4,000-ppm standards. Run The sample line from the cylinder must be the calibration samples in exactly the same purged (into a properly vented hood) for sev- manner as regular samples. Plot As, the inte- eral minutes prior to filling the vials. After grator area counts for each standard sample, purging, reduce the flow rate to between 500 versus Cc, the concentration of vinyl chloride and 1000 cc/min. Place end of tubing into vial in each standard sample. Draw a straight (near bottom). Position a septum on top of line through the points derived by the least the vial, pressing it against the 1⁄8-in. filling squares method. tube to minimize the size of the vent opening. This is necessary to minimize mixing air 11.0 Analytical Procedure with the standard in the vial. Each vial is to 11.1 Preparation of Equipment. Install the be purged with standard for 90 seconds, dur- chromatographic column and condition over- ing which time the filling tube is gradually night at 160 °C (320 °F). In the first operation, slid to the top of the vial. After the 90 sec- Porapak columns must be purged for 1 hour onds, the tube is removed with the septum, at 230 °C (450 °F). simultaneously sealing the vial. Practice Do not connect the exit end of the column will be necessary to develop good technique. to the detector while conditioning. Hydrogen Rubber gloves should be worn during the and air to the detector must be turned off above operations. The sealed vial must then while the column is disconnected. be pressurized for 60 seconds using the vial 11.2 Flow Rate Adjustments. Adjust flow prepressurizer. Test the vial for leakage by rates as follows: placing a drop of water on the septum at the needle hole. Prepressurization of standards is 11.2.1. Nitrogen Carrier Gas. Set regulator not required unless samples have been on cylinder to read 50 psig. Set regulator on prepressurized. chromatograph to produce a flow rate of 30.0 10.2 Analyzer Calibration. Calibration is cc/min. Accurately measure the flow rate at to be performed each 8-hour period the chro- the exit end of the column using the soap matograph is used. Alternatively, calibra- film flowmeter and a stopwatch, with the tion with duplicate 50-, 500-, 2,000-, and 4,000- oven and column at the analysis tempera- ppm standards (hereafter described as a four- ture. After the instrument program advances point calibration) may be performed on a to the ‘‘B’’ (backflush) mode, adjust the ni- monthly basis, provided that a calibration trogen pressure regulator to exactly balance confirmation test consisting of duplicate the nitrogen flow rate at the detector as was analyses of an appropriate standard is per- obtained in the ‘‘A’’ mode. formed once per plant shift, or once per chro- 11.2.2. Vial Prepressurizer Nitrogen. matograph carrousel operation (if the chro- 11.2.2.1 After the nitrogen carrier is set, matograph operation is less frequent than solve the following equation and adjust the once per shift). The criterion for acceptance pressure on the vial prepressurizer accord- of each calibration confirmation test is that ingly.

⎡ − ⎤ =−T1 PPww12− P ⎢P1 ⎥ 10kPa Eq. 107-1 T2 ⎣ 750. ⎦

Where: P1 = Gas chromatograph absolute dosing pressure (analysis mode), k Pa. T1 = Ambient temperature, °K (°R). T2 = Conditioning bath temperature, °K (°R). 282

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Pw1 = Water vapor pressure 525.8 mm Hg @ 90 11.7. Sample Treatment. All samples must °C. be recovered and analyzed within 24 hours Pw2 = Water vapor pressure 19.8 mm Hg @ 22 after collection. °C. 11.7.1 Resin Samples. The weight of the 7.50 = mm Hg per k Pa. resin used must be between 0.1 and 4.5 grams. 10 kPa = Factor to adjust the prepressurized An exact weight must be obtained (within ±1 pressure to slightly less than the dosing percent) for each sample. In the case of sus- pressure. pension resins, a volumetric cup can be pre- 11.2.2.2 Because of gauge errors, the appa- pared for holding the required amount of ratus may over-pressurize the vial. If the sample. When the cup is used, open the sam- vial pressure is at or higher than the dosing ple bottle, and add the cup volume of resin to pressure, an audible double injection will the tared sample vial (tared, including sep- occur. If the vial pressure is too low, errors will occur on resin samples because of inad- tum and aluminum cap). Obtain the exact equate time for head-space gas equilibrium. sample weight, add 100 ml or about two equal This condition can be avoided by running drops of water, and immediately seal the several standard gas samples at various pres- vial. Report this value on the data sheet; it sures around the calculated pressure, and is required for calculation of RVCM. In the then selecting the highest pressure that does case of dispersion resins, the cup cannot be not produce a double injection. All samples used. Weigh the sample in an aluminum dish, and standards must be pressurized for 60 sec- transfer the sample to the tared vial, and ac- onds using the vial prepressurizer. The vial curately weigh it in the vial. After is then placed into the 90 °C conditioning prepressurization of the samples, condition bath and tested for leakage by placing a drop them for a minimum of 1 hour in the 90 °C of water on the septum at the needle hole. A (190 °F) bath. Do not exceed 5 hours. clean, burr-free needle is mandatory. Prepressurization is not required if the sam- 11.2.3. Burner Air Supply. Set regulator ple weight, as analyzed, does not exceed 0.2 on cylinder to read 50 psig. Set regulator on gram. It is also not required if solution of chromatograph to supply air to burner at a the prepressurization equation yields an ab- rate between 250 and 300 cc/min. Check with solute prepressurization value that is within bubble flowmeter. 11.2.4. Hydrogen Supply. Set regulator on 30 percent of the atmospheric pressure. cylinder to read 30 psig. Set regulator on NOTE: Some aluminum vial caps have a chromatograph to supply approximately 35 center section that must be removed prior to ±5 cc/min. Optimize hydrogen flow to yield placing into sample tray. If the cap is not re- the most sensitive detector response without moved, the injection needle will be damaged. extinguishing the flame. Check flow with 11.7.2 Suspension Resin Slurry and Wet bubble meter and record this flow. Cake Samples. Decant the water from a wet 11.3 Temperature Adjustments. Set temperatures as follows: cake sample, and turn the sample bottle up- 11.3.1. Oven (chromatograph column), 140 side down onto a paper towel. Wait for the °C (280 °F). water to drain, place approximately 0.2 to 4.0 11.3.2. Dosing Line, 150 °C (300 °F). grams of the wet cake sample in a tared vial 11.3.3. Injection Block, 170 °C (340 °F). (tared, including septum and aluminum cap) 11.3.4. Sample Chamber, Water Tempera- and seal immediately. Then determine the ture, 90 °C ±1.0 °C (194 °F ±1.8 °F). sample weight (1 percent). All samples 11.4 Ignition of Flame Ionization Detec- weighing over 0.2 gram, must be tor. Ignite the detector according to the prepressurized prior to conditioning for 1 manufacturer’s instructions. hour at 90 °C (190 °F), except as noted in Sec- 11.5 Amplifier Balance. Balance the am- tion 11.7.1. A sample of wet cake is used to plifier according to the manufacturer’s in- determine total solids (TS). This is required structions. for calculating the RVCM. 11.6 Programming the Chromatograph. 11.7.3 Dispersion Resin Slurry and Latex Program the chromatograph as follows: Samples. The materials should not be fil- 11.6.1. I—Dosing or Injection Time. The tered. Sample must be thoroughly mixed. normal setting is 2 seconds. Using a tared vial (tared, including septum 11.6.2. A—Analysis Time. The normal set- and aluminum cap) add approximately eight ting is approximately 70 percent of the VCM drops (0.25 to 0.35 g) of slurry or latex using retention time. When this timer terminates, the programmer initiates backflushing of a medicine dropper. This should be done im- the first column. mediately after mixing. Seal the vial as soon 11.6.3. B—Backflushing Time. The normal as possible. Determine sample weight (1 per- setting is double the analysis time. cent). Condition the vial for 1 hour at 90 °C 11.6.4. W—Stabilization Time. The normal (190 °F) in the analyzer bath. Determine the setting is 0.5 min to 1.0 min. TS on the slurry sample (Section 11.10). 11.6.5. X—Number of Analyses Per Sam- 11.7.4 In-process Wastewater Samples. ple. The normal setting is one. Using a tared vial (tared, including septum

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and aluminum cap) quickly add approxi- starting and stopping a program to prevent mately 1 cc of water using a medicine drop- damage to the dosing assembly. per. Seal the vial as soon as possible. Deter- 11.10 Determination of Total Solids. For mine sample weight (1 percent). Condition wet cake, slurry, resin solution, and PVC the vial for 1 hour at 90 °C (190 °F) in the ana- latex samples, determine TS for each sample lyzer bath. by accurately weighing approximately 3 to 4 11.8 Preparation of Sample Turntable. grams of sample in an aluminum pan before 11.8.1 Before placing any sample into and after placing in a draft oven (105 to 110 turntable, be certain that the center section °C (221 to 230 °F)). Samples must be dried to of the aluminum cap has been removed. The constant weight. After first weighing, return numbered sample vials should be placed in the pan to the oven for a short period of the corresponding numbered positions in the time, and then reweigh to verify complete turntable. Insert samples in the following dryness. The TS are then calculated as the order: final sample weight divided by initial sample 11.8.1.1 Positions 1 and 2. Old 2000-ppm weight. standards for conditioning. These are necessary only after the analyzer has not been 12.0 Calculations and Data Analysis used for 24 hours or longer. 12.1 Nomenclature. 11.8.1.2 Position 3. 50-ppm standard, freshly prepared. As = Chromatogram area counts of vinyl 11.8.1.3 Position 4. 500-ppm standard, chloride for the sample, area counts. freshly prepared. As = Chromatogram area counts of vinyl 11.8.1.4 Position 5. 2000-ppm standard, chloride for the sample. freshly prepared. Cc = Concentration of vinyl chloride in the 11.8.1.5 Position 6. 4000-ppm standard, standard sample, ppm. freshly prepared. Kp = Henry’s Law Constant for VCM in PVC 11.8.1.6 Position 7. Sample No. 7 (This is 90 °C, 6.52 × 10¥6 g/g/mm Hg. the first sample of the day, but is given as 7 Kw = Henry’s Law Constant for VCM in water to be consistent with the turntable and the 90 °C, 7 × 10¥7 g/g/mm Hg. integrator printout.) Mv = Molecular weight of VCM, 62.5 g/mole. 11.8.2 After all samples have been posi- m = Sample weight, g. tioned, insert the second set of 50-, 500-, 2000- Pa = Ambient atmospheric pressure, mm Hg. , and 4000-ppm standards. Samples, including R = Gas constant, (62360 3 ml) (mm Hg)/ standards, must be conditioned in the bath (mole)(°K). of 90 °C (190 °F) for a minimum of one hour Rf = Response factor in area counts per ppm and a maximum of five hours. VCM. 11.9 Start Chromatograph Program. When Rs = Response factor, area counts/ppm. all samples, including standards, have been Tl = Ambient laboratory temperature, °K. conditioned at 90 °C (190 °F) for at least one TS = Total solids expressed as a decimal hour, start the analysis program according fraction. to the manufacturer’s instructions. These in- T2 = Equilibrium temperature, °K. structions must be carefully followed when Vg = Volume of vapor phase, ml.

mTS() m()1− TS =−V − v 136..0 9653

3 Vv = Vial volume, ml. through zero, an average response factor, Rf, 1.36 = Density of PVC at 90 °C, g/3 ml. may be used to facilitate computation of 0.9653 = Density of water at 90 °C, g/3 ml. vinyl chloride sample concentrations.

12.2 Response Factor. If the calibration 12.2.1 To compute Rf, first compute a re- curve described in Section 10.3 passes sponse factor, Rs, for each sample as follows:

= As Rs Eq. 107-2 Cc

12.2.2 Sum the individual response fac- curve does not pass through zero, use the

tors, and calculate Rf. If the calibration

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calibration curve to determine each sample omer Concentration. Calculate Crvc in ppm or concentration. mg/kg as follows: 12.3 Residual Vinyl Chloride Monomer Concentration, (Crvc) or Vinyl Chloride Mon-

⎡MV ⎤ =+APsa vg () ()− Crvc ⎢ Kpw TSTK221 TST⎥ Eq. 107-3 RTf 1 ⎣ Rm ⎦

NOTE: Results calculated using these equa- 17.0 Tables, Diagrams, Flowcharts, and tions represent concentration based on the Validation Data [Reserved] total sample. To obtain results based on dry PVC content, divide by TS. METHOD 107A—DETERMINATION OF VINYL CHLORIDE CONTENT OF SOLVENTS, RESIN- 13.0 Method Performance SOLVENT SOLUTION, POLYVINYL CHLORIDE RESIN, RESIN SLURRY, WET RESIN, AND 13.1 Range and Sensitivity. The lower LATEX SAMPLES limit of detection of vinyl chloride will vary according to the sampling and Introduction chromatographic system. The system should Performance of this method should not be be capable of producing a measurement for a attempted by persons unfamiliar with the 50-ppm vinyl chloride standard that is at operation of a gas chromatograph (GC) or by least 10 times the standard deviation of the those who are unfamiliar with source sam- system background noise level. pling because knowledge beyond the scope of 13.2 An interlaboratory comparison be- this presentation is required. Care must be tween seven laboratories of three resin sam- exercised to prevent exposure of sampling ples, each split into three parts, yielded a personnel to vinyl chloride, a carcinogen. standard deviation of 2.63 percent for a sam- 1. Applicability and Principle ple with a mean of 2.09 ppm, 4.16 percent for 1.1 Applicability. This is an alternative a sample with a mean of 1.66 ppm, and 5.29 method and applies to the measurement of percent for a sample with a mean of 62.66 the vinyl chloride content of solvents, resin ppm. solvent solutions, polyvinyl chloride (PVC) resin, wet cake slurries, latex, and fabricated 14.0 Pollution Prevention [Reserved] resin samples. This method is not acceptable where methods from Section 304(h) of the 15.0 Waste Management [Reserved] Clean Water Act, 33 U.S.C. 1251et seq., (the Federal Water Pollution Control Act Amend- 16.0 References ments of 1972 as amended by the Clean Water 1. B.F. Goodrich, Residual Vinyl Chloride Act of 1977) are required. Monomer Content of Polyvinyl Chloride Res- 1.2 Principle. The basis for this method ins, Latex, Wet Cake, Slurry and Water Sam- lies in the direct injection of a liquid sample ples. B.F. Goodrich Chemical Group Stand- into a chromatograph and the subsequent ard Test Procedure No. 1005-E. B.F. Goodrich evaporation of all volatile material into the Technical Center, Avon Lake, Ohio. October carrier gas stream of the chromatograph, 8, 1979. thus permitting analysis of all volatile material including vinyl chloride. 2. Berens, A.R. The Diffusion of Vinyl Chloride in Polyvinyl Chloride. ACS-Division 2. Range and Sensitivity of Polymer Chemistry, Polymer Preprints 15 The lower limit of detection of vinyl chlo- (2):197. 1974. ride in dry PVC resin is 0.2 ppm. For resin so- 3. Berens, A.R. The Diffusion of Vinyl lutions, latexes, and wet resin, this limit Chloride in Polyvinyl Chloride. ACS-Division rises inversely as the nonvolatile (resin) con- of Polymer Chemistry, Polymer Preprints 15 tent decreases. (2):203. 1974. With proper calibration, the upper limit 4. Berens, A.R., et. al. Analysis for Vinyl may be extended as needed. Chloride in PVC Powders by Head-Space Gas 3. Interferences Chromatography. Journal of Applied Poly- The chromatograph columns and the cor- mer Science. 19:3169–3172. 1975. responding operating parameters herein de- 5. Mansfield, R.A. The Evaluation of scribed normally provide an adequate resolu- Henry’s Law Constant (Kp) and Water En- tion of vinyl chloride. In cases where resolu- hancement in the Perkin-Elmer Multifract tion interferences are encountered, the chro- F–40 Gas Chromatograph. B.F. Goodrich. matograph operator shall select the column Avon Lake, Ohio. February 10, 1978. and operating parameters best suited to his

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particular analysis problem, subject to the 80 mesh. The analyst may use other columns approval of the Administrator. Approval is provided that the precision and accuracy of automatic, provided that the tester produces the analysis of vinyl chloride standards are confirming data through an adequate supple- not impaired and that he has available for mental analytical technique, such as anal- review information confirming that there is ysis with a different column or GC/mass adequate resolution of the vinyl chloride spectroscopy, and has the data available for peak. (Adequate resolution is defined as an review by the Administrator. area overlap of not more than 10 percent of 4. Precision and Reproducibility the vinyl chloride peak by an interfering A standard sample of latex containing 181.8 peak. Calculation of area overlap is ex- ppm vinyl chloride analyzed 10 times by the plained in Appendix C, Procedure 1: ‘‘Deter- alternative method showed a standard devi- mination of Adequate Chromatographic ation of 7.5 percent and a mean error of 0.21 Peak Resolution.’’) percent. 6.3.3 Valco Instrument Six-Port Rotary A sample of vinyl chloride copolymer resin Valve. For column back flush. solution was analyzed 10 times by the alter- 6.3.4 Septa. For chromatograph injection native method and showed a standard devi- port. ation of 6.6 percent at a level of 35 ppm. 6.3.5 Injection Port Liners. For chromatograph used. 5. Safety 6.3.6 Regulators. For required gas cyl- Do not release vinyl chloride to the labora- inders. tory atmosphere during preparation of 6.3.7 Soap Film Flowmeter. Hewlett Pack- standards. Venting or purging with vinyl ard No. 0101-0113 or equivalent. chloride monomer (VCM) air mixtures must 6.4 Calibration. The following equipment be held to minimum. When purging is re- is required: quired, the vapor must be routed to outside 6.4.1 Analytical Balance. Capable of air. Vinyl chloride, even at low-ppm levels, weighing to ±0.0001 g. must never be vented inside the laboratory. 6.4.2 Erlenmeyer Flask With Glass Stop- 6. Apparatus per. 125 ml. 6.1 Sampling. The following equipment is 6.4.3 Pipets. 0.1, 0.5, 1, 5, 10, and 50 ml. required: 6.4.4 Volumetric Flasks. 10 and 100 ml. 6.1.1 Glass Bottles. 16-oz wide mouth wide 7. Reagents polyethylene-lined, screw-on tops. 6.1.2 Adhesive Tape. To prevent loosening Use only reagents that are of chro- of bottle tops. matograph grade. 6.2 Sample Recovery. The following 7.1 Analysis. The following items are re- equipment is required: quired: 6.2.1 Glass Vials. 20-ml capacity with 7.1.1 Hydrogen Gas. Zero grade. polycone screw caps. 7.1.2 Nitrogen Gas. Zero grade. 6.2.2 Analytical Balance. Capable of 7.1.3 Air. Zero grade. weighing to ±0.01 gram. 7.1.4 Tetrahydrofuran (THF). Reagent 6.2.3 Syringe. 50-microliter size, with re- grade. movable needle. Analyze the THF by injecting 10 micro- 6.2.4 Fritted Glass Sparger. Fine porosity. liters into the prepared gas chromatograph. 6.2.5 Aluminum Weighing Dishes. Compare the THF chromatogram with that 6.2.6 Sample Roller or Shaker. To help shown in Figure 107A–1. If the chromatogram dissolve sample. is comparable to A, the THF should be 6.3 Analysis. The following equipment is sparged with pure nitrogen for approxi- required: mately 2 hours using the fritted glass sparg- 6.3.1 Gas Chromatograph. Hewlett Pack- er to attempt to remove the interfering ard Model 5720A or equivalent. peak. Reanalyze the sparged THF to deter- 6.3.2 Chromatograph Column. Stainless mine whether the THF is acceptable for use. steel, 6.1 m by 3.2 mm, packed with 20 per- If the scan is comparable to B, the THF cent Tergitol E–35 on Chromosorb W AW 60/ should be acceptable for use in the analysis.

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7.1.5 N, N-Dimethylacetamide (DMAC). termine total solids as required for calcu- Spectrographic grade. For use in place of lating the residual VCM (Section 8.3.4). THF. 8.2.3 Latex and Resin Solvent Solutions. 7.2 Calibration. The following item is re- Samples must be thoroughly mixed. Weigh quired: 1.00 ±0.01 g of the latex or resin-solvent solu- 7.2.1 Vinyl Chloride 99.9 Percent. Ideal tion into a 20-ml vial containing 9.00 ±0.01 g Gas Products lecture bottle, or equivalent. of THF or DMAC as for the resin samples For preparation of standard solutions. (8.2.1). Cap and shake until complete solution 8. Procedure is obtained. Determine the total solids of the latex or resin solution sample (Section 8.3.4). 8.1 Sampling. Allow the liquid or dried 8.2.4 Solvents and Non-viscous Liquid resin to flow from a tap on the tank, silo, or Samples. No preparation of these samples is pipeline until the tap has been purged. Fill a required. The neat samples are injected di- wide-mouth pint bottle, and immediately rectly into the GC. tightly cap the bottle. Place an identifying label on each bottle and record the date, 8.3 Analysis. time, sample location, and material. 8.3.1 Preparation of GC. Install the 8.2 Sample Treatment. Sample must be chromatographic column, and condition ° run within 24 hours. overnight at 70 C. Do not connect the exit end of the column to the detector while con- 8.2.1 Resin Samples. Weigh 9.00 ±0.01 g of ditioning. THF or DMAC in a tared 20-ml vial. Add 1.00 ±0.01 g of resin to the tared vial containing 8.3.1.1 Flow Rate Adjustments. Adjust the the THF or DMAC. Close the vial tightly flow rate as follows: with the screw cap, and shake or otherwise a. Nitrogen Carrier Gas. Set regulator on agitate the vial until complete solution of cylinder to read 60 psig. Set column flow the resin is obtained. Shaking may require controller on the chromatograph using the several minutes to several hours, depending soap film flowmeter to yield a flow rate of 40 on the nature of the resin. cc/min. 8.2.2 Suspension Resin Slurry and Wet b. Burner Air Supply. Set regulator on the Resin Sample. Slurry must be filtered using cylinder at 40 psig. Set regulator on the a small Buchner funnel with vacuum to yield chromatograph to supply air to the burner to a wet resin sample. The filtering process yield a flow rate of 250 to 300 cc/min using must be continued only as long as a steady the flowmeter. stream of water is exiting from the funnel. c. Hydrogen. Set regulator on cylinder to Excessive filtration time could result in read 60 psig. Set regulator on the chro- some loss of VCM. The wet resin sample is matograph to supply 30 to 40 cc/min using weighed into a tared 20-ml vial with THF or the flowmeter. Optimize hydrogen flow to DMAC as described earlier for resin samples yield the most sensitive detector response (8.2.1) and treated the same as the resin sam- without extinguishing the flame. Check flow ple. A sample of the wet resin is used to de- with flowmeter and record this flow.

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d. Nitrogen Back Flush Gas. Set regulator 5 grams of sample to the dish. Weigh to the on the chromatograph using the soap film nearest milligram. flowmeter to yield a flow rate of 40 cc/min. b. Where volatile solvent is the major vola- 8.3.1.2 Temperature Adjustments. Set tile component: Transfer a portion of the temperature as follows: sample to a 20-ml screw cap vial and cap im- a. Oven (chromatographic column) at 70 °C. mediately. Weigh the vial to the nearest mil- b. Injection Port at 100 °C. ligram. Uncap the vial and transfer a 3- to 5- c. Detector at 300 °C. gram portion of the sample to a tared alu- 8.3.1.3 Ignition of Flame Ionization Detec- minum weighing dish. Recap the vial and re- tor. Ignite the detector according to the weigh to the nearest milligram. The vial manufacturer’s instructions. Allow system weight loss is the sample weight. to stabilize approximately 1 hour. To continue, place the weighing pan in a 8.3.1.4 Recorder. Set pen at zero and start 130 °C oven for 1 hour. Remove the dish and chart drive. allow to cool to room temperature in a desic- 8.3.1.5 Attenuation. Set attenuation to cator. Weigh the pan to the nearest 0.1 mg. yield desired peak height depending on sam- Total solids is the weight of material in the ple VCM content. aluminum pan after heating divided by the 8.3.2 Chromatographic Analyses. net weight of sample added to the pan origi- a. Sample Injection. Remove needle from nally times 100. 50-microliter syringe. Open sample vial and 9. Calibration of the Chromatograph draw 50-microliters of THF or DMAC sample 9.1 Preparation of Standards. Prepare a 1 recovery solution into the syringe. Recap percent by weight (approximate) solution of sample vial. Attach needle to the syringe vinyl chloride in THF or DMAC by bubbling and while holding the syringe vertically vinyl chloride gas from a cylinder into a (needle uppermost), eject 40 microliters into tared 125-ml glass-stoppered flask containing an absorbent tissue. Wipe needle with tissue. THF or DMAC. The weight of vinyl chloride Now inject 10 microliters into chro- to be added should be calculated prior to this matograph system. Repeat the injection operation, i.e., 1 percent of the weight of until two consecutive values for the height THF or DMAC contained in the tared flask. of the vinyl chloride peak do not vary more This must be carried out in a laboratory than 5 percent. Use the average value for hood. Adjust the vinyl chloride flow from the these two peak heights to compute the sam- cylinder so that the vinyl chloride dissolves ple concentration. essentially completely in the THF or DMAC b. Back Flush. After 4 minutes has elapsed and is not blown to the atmosphere. Take after sample injection, actuate the back particular care not to volatize any of the so- flush valve to purge the first 4 feet of the lution. Stopper the flask and swirl the solu- chromatographic column of solvent and tion to effect complete mixing. Weigh the other high boilers. stoppered flask to nearest 0.1 mg to deter- c. Sample Data. Record on the chro- mine the exact amount of vinyl chloride matograph strip chart the data from the added. sample label. Pipet 10 ml of the approximately 1 percent d. Elution Time. Vinyl chloride elutes at solution into a 100-ml glass-stoppered volu- 2.8 minutes. Acetaldehyde elutes at 3.7 min- metric flask, and add THF or DMAC to fill to utes. Analysis is considered complete when the mark. Cap the flask and invert 10 to 20 chart pen becomes stable. After 5 minutes, times. This solution contains approximately reset back flush valve and inject next sam- 1,000 ppm by weight of vinyl chloride (note ple. the exact concentration). 8.3.3 Chromatograph Servicing. Pipet 50-, 10-, 5-, 1-, 0.5-, and 0.1-ml aliquots a. Septum. Replace after five sample injec- of the approximately 1,000 ppm solution into tions. 10 ml glass stoppered volumetric flasks. Di- b. Sample Port Liner. Replace the sample lute to the mark with THF or DMAC, cap the port liner with a clean spare after five sam- flasks and invert each 10 to 20 times. These ple injections. solutions contain approximately 500, 100, 50, c. Chromatograph Shutdown. If the chro- 10, 5, and 1 ppm vinyl chloride. Note the matograph has been shut down overnight, exact concentration of each one. These rerun one or more samples from the pre- standards are to be kept under refrigeration ceding day to test stability and precision in stoppered bottles, and must be renewed prior to starting on the current day’s work. every 3 months. 8.3.4 Determination of Total Solids (TS). 9.2 Preparation of Chromatograph Cali- For wet resin, resin solution, and PVC latex bration Curve. samples, determine the TS for each sample Obtain the GC for each of the six final so- by accurately weighing approximately 3 to 5 lutions prepared in Section 9.1 by using the grams of sample into a tared aluminum pan. procedure in Section 8.3.2. Prepare a chart The initial procedure is as follows: plotting peak height obtained from the chro- a. Where water is the major volatile com- matogram of each solution versus the known ponent: Tare the weighing dish, and add 3 to concentration. Draw a straight line through

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the points derived by the least squares meth- where: od. TS = Total solids in the sample, weight frac- 10. Calculations tion. 10.1 Response Factor. From the calibra- 10.4 Samples of solvents and in process tion curve described in Section 9.2, select the wastewater: value of Cc that corresponds to Hc for each sample. Compute the response factor, Rf, for HR each sample as follows: C = sf Eq. 107A-4 rvc 0. 888 C = c Where: Rf Eq. 107A-1 Hc 0.888 = Specific gravity of THF. where: 11. Bibliography

Rf = Chromatograph response factor, ppm/ 1. Communication from R. N. Wheeler, Jr.; mm. Union Carbide Corporation. Part 61 National Cc = Concentration of vinyl chloride in the Emissions Standards for Hazardous Air Pol- standard sample, ppm. lutants appendix B, Method 107—Alternate Hc = Peak height of the standard sample, Method, September 19, 1977. mm. 10.2 Residual vinyl chloride monomer con- METHOD 108—DETERMINATION OF PARTICULATE centration (Crvc) or vinyl chloride monomer AND GASEOUS ARSENIC EMISSIONS concentration in resin: NOTE: This method does not include all of = the specifications (e.g., equipment and sup- CHRrvc10 s f Eq.107A-2 plies) and procedures (e.g., sampling and ana- Where: lytical) essential to its performance. Some material is incorporated by reference from Crvc = Concentration of residual vinyl chloride monomer, ppm. other methods in appendix A to 40 CFR part 60. Therefore, to obtain reliable results, per- H = Peak height of sample, mm. s sons using this method should have a thor- R = Chromatograph response factor. f ough knowledge of at least the following ad- 10.3 Samples containing volatile material, ditional test methods: Method 1, Method 2, i.e., resin solutions, wet resin, and latexes: Method 3, Method 5, and Method 12. = HRsf(,1 000 ) 1.0 Scope and Application. Crvc Eq. 107A-3 TS 1.1 Analytes.

Analyte CAS No. Sensitivity

Arsenic compounds as arsenic (As) ...... 7440–38–2 Lower limit 10 μg/ml or less.

1.2 Applicability. This method is applica- 3.0 Definitions. [Reserved] ble for the determination of inorganic As emissions from stationary sources as speci- 4.0 Interferences fied in an applicable subpart of the regula- Analysis for As by flame AAS is sensitive tions. to the chemical composition and to the phys- 1.3 Data Quality Objectives. Adherence to ical properties (e.g., viscosity, pH) of the the requirements of this method will en- sample. The analytical procedure includes a hance the quality of the data obtained from check for matrix effects (Section 11.5). air pollutant sampling methods. 5.0 Safety 2.0 Summary of Method 5.1 This method may involve hazardous Particulate and gaseous As emissions are materials, operations, and equipment. This withdrawn isokinetically from the source test method may not address all of the safe- and are collected on a glass mat filter and in ty problems associated with its use. It is the water. The collected arsenic is then analyzed responsibility of the user to establish appro- by means of atomic absorption priate safety and health practices and deter- spectrophotometry (AAS). mine the applicability of regulatory limitations prior to performing this test method. 5.2 Corrosive reagents. The following reagents are hazardous. Personal protective equipment and safe procedures that prevent

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chemical splashes are recommended. If con- 6.2 Sample Recovery. The following items tact occurs, immediately flush with copious are required for sample recovery: amounts of water for at least 15 minutes. Re- 6.2.1 Probe-Liner and Probe-Nozzle Brush- move clothing under shower and decontami- es, Petri Dishes, Graduated Cylinder and/or nate. Treat residual chemical burns as ther- Balance, Plastic Storage Containers, and mal burns. Funnel and Rubber Policeman. Same as 5.2.1 Hydrochloric Acid (HCl). Highly cor- Method 5, Sections 6.2.1 and 6.2.4 to 6.2.8, re- rosive liquid with toxic vapors. Vapors are spectively. highly irritating to eyes, skin, nose, and 6.2.2 Wash Bottles. Polyethylene (2). lungs, causing severe damage. May cause 6.2.3 Sample Storage Containers. Chemi- bronchitis, pneumonia, or edema of lungs. cally resistant, polyethylene or poly- Exposure to concentrations of 0.13 to 0.2 per- propylene for glassware washes, 500- or 1000- cent can be lethal to humans in a few min- ml. utes. Provide ventilation to limit exposure. 6.3 Analysis. The following items are re- Reacts with metals, producing hydrogen gas. quired for analysis: 5.2.2 Hydrogen Peroxide (H2O2). Very 6.3.1 Spectrophotometer. Equipped with harmful to eyes. 30% H2O2 can burn skin, an electrodeless discharge lamp and a back- nose, and lungs. ground corrector to measure absorbance at 5.2.3 Nitric Acid (HNO3). Highly corrosive 193.7 nanometers (nm). For measuring sam- to eyes, skin, nose, and lungs. Vapors are ples having less than 10 μg As/ml, use a vapor highly toxic and can cause bronchitis, pneu- generator accessory or a graphite furnace. monia, or edema of lungs. Reaction to inha- 6.3.2 Recorder. To match the output of the lation may be delayed as long as 30 hours spectrophotometer. and still be fatal. Provide ventilation to 6.3.3 Beakers. 150 ml. limit exposure. Strong oxidizer. Hazardous 6.3.4 Volumetric Flasks. Glass 50-, 100-, reaction may occur with organic materials 200-, 500-, and 1000-ml; and polypropylene, 50- such as solvents. ml. 5.2.4 Sodium Hydroxide (NaOH). Causes 6.3.5 Balance. To measure within 0.5 g. severe damage to eyes and skin. Inhalation 6.3.6 Volumetric Pipets. 1-, 2-, 3-, 5-, 8-, causes irritation to nose, throat, and lungs. and 10-ml. Reacts exothermically with small amounts 6.3.7 Oven. of water. 6.3.8 Hot Plate. 6.0 Equipment and Supplies 7.0 Reagents and Standards 6.1 Sample Collection. A schematic of the Unless otherwise indicated, it is intended sampling train used in performing this meth- that all reagents conform to the specifica- od is shown in Figure 108–1; it is similar to tions established by the Committee on Ana- the Method 5 sampling train of 40 CFR part lytical Reagents of the American Chemical 60, appendix A. The following items are re- Society, where such specifications are avail- quired for sample collection: able; otherwise, use the best available grade. 6.1.1 Probe Nozzle, Probe Liner, Pitot 7.1 The following reagents are required Tube, Differential Pressure Gauge, Filter for sample collection: Holder, Filter Heating System, Temperature 7.1.1 Filters. Same as Method 5, Section Sensor, Metering System, Barometer, and 7.1.1, except that the filters need not be Gas Density Determination Equipment. unreactive to SO2. Same as Method 5, Sections 6.1.1.1 to 6.1.1.7, 7.1.2 Silica Gel, Crushed Ice, and Stopcock 6.1.1.9, 6.1.2, and 6.1.3, respectively. Grease. Same as Method 5, Sections 7.1.2, 6.1.2 Impingers. Four impingers connected 7.1.4, and 7.1.5, respectively. in series with leak-free ground-glass fittings 7.1.3 Water. Deionized distilled to meet or any similar leak-free noncontaminating ASTM D 1193–77 or 91 (incorporated by ref- fittings. For the first, third, and fourth erence-see § 61.18), Type 3. When high con- impingers, use the Greenburg-Smith design, centrations of organic matter are not ex- modified by replacing the tip with a 1.3-cm pected to be present, the KMnO4 test for oxi- ID (0.5-in.) glass tube extending to about 1.3 dizable organic matter may be omitted. cm (0.5 in.) from the bottom of the flask. For 7.2 Sample Recovery. the second impinger, use the Greenburg- 7.2.1 0.1 N NaOH. Dissolve 4.00 g of NaOH Smith design with the standard tip. Modi- in about 500 ml of water in a 1-liter volu- fications (e.g., flexible connections between metric flask. Then, dilute to exactly 1.0 liter the impingers, materials other than glass, or with water. flexible vacuum lines to connect the filter 7.3 Analysis. The following reagents and holder to the condenser) are subject to the standards are required for analysis: approval of the Administrator. 7.3.1 Water. Same as Section 7.1.3. 6.1.3 Temperature Sensor. Place a tem- 7.3.2 Sodium Hydroxide, 0.1 N. Same as in perature sensor, capable of measuring tem- Section 7.2.1. perature to within 1 °C (2 °F), at the outlet 7.3.3 Sodium Borohydride (NaBH4), 5 Per- of the fourth impinger for monitoring pur- cent Weight by Volume (W/V). Dissolve 50.0 g poses. of NaBH4 in about 500 ml of 0.1 N NaOH in a 290

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1-liter volumetric flask. Then, dilute to ex- rates below 28 liters/min (1.0 cfm). For each actly 1.0 liter with 0.1 N NaOH. run, record the data required on a data sheet 7.3.4 Hydrochloric Acid, Concentrated. similar to the one shown in Figure 108–2. 7.3.5 Potassium Iodide (KI), 30 Percent (W/ 8.6 Calculation of Percent Isokinetic. V). Dissolve 300 g of KI in 500 ml of water in Same as Method 5, Section 8.6. a 1 liter volumetric flask. Then, dilute to ex- 8.7 Sample Recovery. Same as Method 5, actly 1.0 liter with water. Section 8.7, except that 0.1 N NaOH is used as 7.3.6 Nitric Acid, Concentrated. the cleanup solvent instead of acetone and 7.3.7 Nitric Acid, 0.8 N. Dilute 52 ml of that the impinger water is treated as fol- concentrated HNO3 to exactly 1.0 liter with lows: water. 8.7.1 Container Number 4 (Impinger 7.3.8 Nitric Acid, 50 Percent by Volume Water). Clean each of the first three (V/V). Add 50 ml concentrated HNO3 to 50 ml impingers and connecting glassware in the water. following manner: 7.3.9 Stock Arsenic Standard, 1 mg As/ml. 8.7.1.1 Wipe the impinger ball joints free Dissolve 1.3203 g of primary standard grade of silicone grease, and cap the joints. As2O3 in 20 ml of 0.1 N NaOH in a 150 ml 8.7.1.2 Rotate and agitate each of the first beaker. Slowly add 30 ml of concentrated two impingers, using the impinger contents HNO3. Heat the resulting solution and evapo- as a rinse solution. rate just to dryness. Transfer the residue 8.7.1.3 Transfer the liquid from the first quantitatively to a 1-liter volumetric flask, three impingers to Container Number 4. Re- and dilute to 1.0 liter with water. move the outlet ball-joint cap, and drain the 7.3.10 Arsenic Working Solution, 1.0 μg As/ contents through this opening. Do not sepa- ml. Pipet exactly 1.0 ml of stock arsenic rate the impinger parts (inner and outer standard into an acid-cleaned, appropriately tubes) while transferring their contents to labeled 1-liter volumetric flask containing the container. about 500 ml of water and 5 ml of con- 8.7.1.4 Weigh the contents of Container centrated HNO3. Dilute to exactly 1.0 liter No. 4 to within 0.5 g. Record in the log the with water. weight of liquid along with a notation of any 7.3.11 Air. Suitable quality for AAS anal- color or film observed in the impinger catch. ysis. The weight of liquid is needed along with the 7.3.12 Acetylene. Suitable quality for AAS silica gel data to calculate the stack gas analysis. moisture content. 7.3.13 Nickel Nitrate, 5 Percent Ni (W/V). NOTE: Measure and record the total Dissolve 24.780 g of nickel nitrate amount of 0.1 N NaOH used for rinsing under hexahydrate [Ni(NO3)26H2O] in water in a 100- Sections 8.7.1.5 and 8.7.1.6. ml volumetric flask, and dilute to 100 ml 8.7.1.5 Pour approximately 30 ml of 0.1 with water. NaOH into each of the first two impingers, 7.3.14 Nickel Nitrate, 1 Percent Ni (W/V). and agitate the impingers. Drain the 0.1 N Pipet 20 ml of 5 percent nickel nitrate solu- NaOH through the outlet arm of each im- tion into a 100-ml volumetric flask, and di- pinger into Container Number 4. Repeat this lute to exactly 100 ml with water. operation a second time; inspect the 7.3.15 Hydrogen Peroxide, 3 Percent by impingers for any abnormal conditions. Volume. Pipet 50 ml of 30 percent H2O2 into 8.7.1.6 Wipe the ball joints of the glass- a 500-ml volumetric flask, and dilute to ex- ware connecting the impingers and the back actly 500 ml with water. half of the filter holder free of silicone grease, and rinse each piece of glassware 8.0 Sample Collection, Preservation, Transport, twice with 0.1 N NaOH; transfer this rinse and Storage into Container Number 4. (DO NOT RINSE or 8.1 Pretest Preparation. Follow the gen- brush the glass-fritted filter support.) Mark eral procedure given in Method 5, Section 8.1, the height of the fluid level to determine except the filter need not be weighed, and whether leakage occurs during transport. the 200 ml of 0.1N NaOH and Container 4 Label the container to identify clearly its should be tared to within 0.5 g. contents. 8.2 Preliminary Determinations. Follow 8.8 Blanks. the general procedure given in Method 5, 8.8.1 Sodium Hydroxide. Save a portion of Section 8.2, except select the nozzle size to the 0.1 N NaOH used for cleanup as a blank. maintain isokinetic sampling rates below 28 Take 200 ml of this solution directly from liters/min (1.0 cfm). the wash bottle being used and place it in a 8.3 Preparation of Sampling Train. Follow plastic sample container labeled ‘‘NaOH the general procedure given in Method 5, blank.’’ Section 8.3. 8.8.2 Water. Save a sample of the water, 8.4 Leak-Check Procedures. Same as and place it in a container labeled ‘‘H2O Method 5, Section 8.4. blank.’’ 8.5 Sampling Train Operation. Follow the 8.8.3 Filter. Save two filters from each lot general procedure given in Method 5, Section of filters used in sampling. Place these fil- 8.5, except maintain isokinetic sampling flow ters in a container labeled ‘‘filter blank.’’

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9.0 Quality Control

9.1 MISCELLANEOUS QUALITY CONTROL MEASURES.

Section Quality control measure Effect

8.4, 10.1 ...... Sampling equipment leak-checks and calibration Ensures accuracy and precision of sampling measurements. 10.4 ...... Spectrophotometer calibration ...... Ensures linearity of spectrophotometer response to standards. 11.5 ...... Check for matrix effects ...... Eliminates matrix effects.

9.2 Volume Metering System Checks. tual concentrations (e.g., 1, 3, 5, 8, and 10 mg Same as Method 5, Section 9.2. As for the high-level procedure) must be less than 7 percent for all standards. 10.0 Calibration and Standardization NOTE: For instruments equipped with di- NOTE: Maintain a laboratory log of all cali- rect concentration readout devices, prepara- brations. tion of a standard curve will not be nec- 10.1 Sampling Equipment. Same as Meth- essary. In all cases, follow calibration and od 5, Section 10.0. operational procedures in the manufacturers’ 10.2 Preparation of Standard Solutions. instruction manual. 10.2.1 For the high level procedure, pipet 1, 3, 5, 8, and 10 ml of the 1.0 mg As/ml stock 11.0 Analytical Procedure solution into separate 100 ml volumetric 11.1 Sample Loss Check. Prior to analysis, flasks, each containing 5 ml of concentrated check the liquid level in Containers Number HNO3. Dilute to the mark with water. 2 and Number 4. Note on the analytical data 10.2.2 For the low level vapor generator sheet whether leakage occurred during procedure, pipet 1, 2, 3, and 5 ml of 1.0 μg As/ transport. If a noticeable amount of leakage ml standard solution into separate reaction occurred, either void the sample or take tubes. Dilute to the mark with water. steps, subject to the approval of the Admin- 10.2.3 For the low level graphite furnace istrator, to adjust the final results. procedure, pipet 1, 5, 10 and 15 ml of 1.0 μg As/ 11.2 Sample Preparation. ml standard solution into separate flasks 11.2.1 Container Number 1 (Filter). Place along with 2 ml of the 5 percent nickel ni- the filter and loose particulate matter in a trate solution and 10 ml of the 3 percent H2O2 150 ml beaker. Also, add the filtered solid solution. Dilute to the mark with water. material from Container Number 2 (see Sec- 10.3 Calibration Curve. Analyze a 0.8 N tion 11.2.2). Add 50 ml of 0.1 N NaOH. Then HNO3 blank and each standard solution ac- stir and warm on a hot plate at low heat (do cording to the procedures outlined in section not boil) for about 15 minutes. Add 10 ml of 11.4.1. Repeat this procedure on each stand- concentrated HNO3, bring to a boil, then sim- ard solution until two consecutive peaks mer for about 15 minutes. Filter the solution agree within 3 percent of their average value. through a glass fiber filter. Wash with hot Subtract the average peak height (or peak water, and catch the filtrate in a clean 150 area) of the blank—which must be less than ml beaker. Boil the filtrate, and evaporate to 2 percent of recorder full scale—from the dryness. Cool, add 5 ml of 50 percent HNO3, averaged peak height of each standard solu- and then warm and stir. Allow to cool. tion. If the blank absorbance is greater than Transfer to a 50-ml volumetric flask, dilute 2 percent of full-scale, the probable cause is to volume with water, and mix well. As contamination of a reagent or carry-over 11.2.2 Container Number 2 (Probe Wash). of As from a previous sample. Prepare the 11.2.2.1 Filter (using a glass fiber filter) calibration curve by plotting the corrected the contents of Container Number 2 into a peak height of each standard solution versus 200 ml volumetric flask. Combine the filtered the corresponding final total As weight in (solid) material with the contents of Con- the solution. tainer Number 1 (Filter). 10.4 Spectrophotometer Calibration Qual- 11.2.2.2 Dilute the filtrate to exactly 200 ity Control. Calculate the least squares slope ml with water. Then pipet 50 ml into a 150 ml of the calibration curve. The line must pass beaker. Add 10 ml of concentrated HNO3, through the origin or through a point no fur- bring to a boil, and evaporate to dryness. ther from the origin than ±2 percent of the Allow to cool, add 5 ml of 50 percent HNO3, recorder full scale. Multiply the corrected and then warm and stir. Allow the solution peak height by the reciprocal of the least to cool, transfer to a 50-ml volumetric flask, squares slope to determine the distance each dilute to volume with water, and mix well. calibration point lies from the theoretical 11.2.3 Container Number 4 (Impinger Solu- calibration line. The difference between the tion). Transfer the contents of Container calculated concentration values and the ac- Number 4 to a 500 ml volumetric flask, and

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dilute to exactly 500-ml with water. Pipet 50 adjust the volume of the sample accordingly. ml of the solution into a 150-ml beaker. Add Pipet 15 ml of concentrated HCl into each 10 ml of concentrated HNO3, bring to a boil, tube. Add 1 ml of 30 percent KI solution. and evaporate to dryness. Allow to cool, add Place the reaction tube into a 50 °C (120 °F) 5 ml of 50 percent HNO3, and then warm and water bath for 5 minutes. Cool to room tem- stir. Allow the solution to cool, transfer to a perature. Connect the reaction tube to the 50-ml volumetric flask, dilute to volume vapor generator assembly. When the instru- with water, and mix well. ment response has returned to baseline, in- 11.2.4 Filter Blank. Cut each filter into ject 5.0 ml of 5 percent NaBH4, and integrate strips, and treat each filter individually as the resulting spectrophotometer signal over directed in Section 11.2.1, beginning with the a 30-second time period. sentence, ‘‘Add 50 ml of 0.1 N NaOH.’’ 11.4.1.1.2 Graphite Furnace Procedure. Di- 11.2.5 Sodium Hydroxide and Water lute the digested sample so that a 5 ml ali- Blanks. Treat separately 50 ml of 0.1 N NaOH quot contains less than 1.5 μg of arsenic. and 50 ml water, as directed under Section Pipet 5 ml of this digested solution into a 10- 11.2.3, beginning with the sentence, ‘‘Pipet 50 ml volumetric flask. Add 1 ml of the 1 per- ml of the solution into a 150-ml beaker.’’ cent nickel nitrate solution, 0.5 ml of 50 per- 11.3 Spectrophotometer Preparation. cent HNO3, and 1 ml of the 3 percent hydro- Turn on the power; set the wavelength, slit gen peroxide and dilute to 10 ml with water. width, and lamp current. Adjust the back- The sample is now ready for analysis. ground corrector as instructed by the manu- 11.4.1.2 Run a blank (0.8 N HNO3) and facturer’s manual for the particular atomic standard at least after every five samples to absorption spectrophotometer. Adjust the check the spectrophotometer calibration. burner and flame characteristics as nec- The peak height of the blank must pass essary. through a point no further from the origin 11.4 Analysis. Calibrate the analytical than ±2 percent of the recorder full scale. equipment and develop a calibration curve as The difference between the measured con- outlined in Sections 10.2 through 10.4. centration of the standard (the product of 11.4.1 Arsenic Samples. Analyze an appro- the corrected average peak height and the priately sized aliquot of each diluted sample reciprocal of the least squares slope) and the (from Sections 11.2.1 through 11.2.3) until two actual concentration of the standard must be consecutive peak heights agree within 3 per- less than 7 percent, or recalibration of the cent of their average value. If applicable, fol- analyzer is required. low the procedures outlined in Section 11.4.1.3 Determine the arsenic concentra- 11.4.1.1. If the sample concentration falls out- tion in the filter blank (i.e., the average of side the range of the calibration curve, make the two blank values from each lot). 11.4.2 Container Number 3 (Silica Gel). an appropriate dilution with 0.8 N HNO3 so that the final concentration falls within the This step may be conducted in the field. range of the curve. Using the calibration Weigh the spent silica gel (or silica gel plus curve, determine the arsenic concentration impinger) to the nearest 0.5 g; record this in each sample fraction. weight. 11.5 Check for matrix effects on the ar- NOTE: Because instruments vary between senic results. Same as Method 12, Section manufacturers, no detailed operating in- 11.5. structions will be given here. Instead, the instrument manufacturer’s detailed operating 12.0 Data Analysis and Calculations instructions should be followed. 11.4.1.1 Arsenic Determination at Low 12.1 NOMENCLATURE Concentration. The lower limit of flame AAS Bws = Water in the gas stream, proportion by is 10 μg As/ml. If the arsenic concentration of volume. any sample is at a lower level, use the graph- Ca = Concentration of arsenic as read from ite furnace or vapor generator which is avail- the standard curve, μg/ml. able as an accessory component. Flame, Cs = Arsenic concentration in stack gas, dry graphite furnace, or vapor generators may be basis, converted to standard conditions, used for samples whose concentrations are g/dsm3 (gr/dscf). μ between 10 and 30 g/ml. Follow the manufac- Ea = Arsenic mass emission rate, g/hr (lb/hr). turer’s instructions in the use of such equip- Fd = Dilution factor (equals 1 if the sample ment. has not been diluted). 11.4.1.1.1 Vapor Generator Procedure. I = Percent of isokinetic sampling. μ Place a sample containing between 0 and 5 g mbi = Total mass of all four impingers and of arsenic in the reaction tube, and dilute to contents before sampling, g. 15 ml with water. Since there is some trial mfi = Total mass of all four impingers and and error involved in this procedure, it may contents after sampling, g. be necessary to screen the samples by con- mn = Total mass of arsenic collected in a spe- ventional atomic absorption until an approx- cific part of the sampling train, μg. imate concentration is determined. After de- mt = Total mass of arsenic collected in the termining the approximate concentration, sampling train, μg.

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Tm = Absolute average dry gas meter tem- DH = Average pressure differential across the ° ° perature (see Figure 108–2), K ( R). orifice meter (see Figure 108–2), mm H2O Vm = Volume of gas sample as measured by (in. H2O). the dry gas meter, dry basis, m3 (ft3). 12.2 Average Dry Gas Meter Temperatures Vm(std) = Volume of gas sample as measured (Tm) and Average Orifice Pressure Drop (DH). by the dry gas meter, corrected to stand- See data sheet (Figure 108–2). ard conditions, m3 (ft3). 12.3 Dry Gas Volume. Using data from Vn = Volume of solution in which the arsenic is contained, ml. this test, calculate Vm(std) according to the procedures outlined in Method 5, Section Vw(std) = Volume of water vapor collected in the sampling train, corrected to standard 12.3. conditions, m3 (ft3). 12.4 Volume of Water Vapor.

=−() VKmmw() std 2 fi bi Eq. 108-1

Where: = 0.047012 ft3/g for English units. 3 K2 = 0.001334 m /g for metric units. 12.5 Moisture Content.

V () B = w std Eq. 108-2 ws + VVm() std w () std

12.6 Amount of Arsenic Collected. 12.6.1 Calculate the amount of arsenic collected in each part of the sampling train, as follows:

= mCFVnadn Eq. 108-3

12.6.2 Calculate the total amount of arsenic collected in the sampling train as follows:

=++ mmt ()filters m()probe m ( impingers ) Eq. 108-4 −− − mm()()()filter blank NaOH blank m water blank

12.7 Calculate the arsenic concentration in the stack gas (dry basis, adjusted to standard conditions) as follows:

= CKmVst3 ()/m() std Eq. 108-5

Where: 12.8 Stack Gas Velocity and Volumetric ¥6 Flow Rate. Calculate the average stack gas K3 = 10 g/μg for metric units = 1.54 × 10¥5 gr/μg for English units velocity and volumetric flow rate using data

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obtained in this method and the equations in 12.9 Pollutant Mass Rate. Calculate the Sections 12.2 and 12.3 of Method 2. arsenic mass emission rate as follows:

= Eassd C Q Eq. 108-6

12.10 Isokinetic Variation. Same as Meth- of seven blanks. It has been reported that for od 5, Section 12.11. mercury and those elements that form hy- drides, a continuous-flow generator coupled 13.0 Method Performance to an ICP–AES offers detection limits com- 13.1 Sensitivity. The lower limit of flame parable to cold vapor atomic absorption. AAS 10 μg As/ml. The analytical procedure 16.2 Inductively Coupled Plasma-Mass includes provisions for the use of a graphite Spectrometry (ICP–MS) Analysis. ICP–MS furnace or vapor generator for samples with may be used as an alternative to atomic ab- a lower arsenic concentration. sorption analysis. 16.3 Cold Vapor Atomic Fluorescence [Reserved] 14.0 Pollution Prevention. Spectrometry (CVAFS) Analysis. CVAFS 15.0 Waste Management. [Reserved] may be used as an alternative to atomic absorption analysis. 16.0 Alternative Procedures 17.0 References. 16.1 Inductively coupled plasma-atomic emission spectrometry (ICP–AES) Analysis. Same as References 1 through 9 of Method ICP–AES may be used as an alternative to 5, Section 17.0, with the addition of the fol- atomic absorption analysis provided the following: lowing conditions are met: 16.1.1 Sample collection, sample prepara- 1. Perkin Elmer Corporation. Analytical tion, and analytical preparation procedures Methods for Atomic Absorption are as defined in the method except as nec- Spectrophotometry. 303–0152. Norwalk, Con- essary for the ICP–AES application. necticut. September 1976. pp. 5–6. 16.1.2 Quality Assurance/Quality Control 2. Standard Specification for Reagent procedures, including audit material anal- Water. In: Annual Book of American Society ysis, are conducted as prescribed in the for Testing and Materials Standards. Part 31: method. The QA acceptance conditions must Water, Atmospheric Analysis. American So- be met. ciety for Testing and Materials. Philadel- 16.1.3 The limit of quantitation for the phia, PA. 1974. pp. 40–42. ICP–AES must be demonstrated and the 3. Stack Sampling Safety Manual (Draft). sample concentrations reported should be no U.S. Environmental Protection Agency, Of- less than two times the limit of quantita- fice of Air Quality Planning and Standard, tion. The limit of quantitation is defined as Research Triangle Park, NC. September 1978. ten times the standard deviation of the blank value. The standard deviation of the 18.0 Tables, Diagrams, Flowcharts, and blank value is determined from the analysis Validation Data

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METHOD 108A—DETERMINATION OF ARSENIC material is incorporated by reference from CONTENT IN ORE SAMPLES FROM NON- other methods in appendix A to 40 CFR part FERROUS SMELTERS 60. Therefore, to obtain reliable results, persons using this method should have a thor- NOTE: This method does not include all of ough knowledge of Method 12. the specifications (e.g., equipment and supplies) and procedures (e.g., sampling and ana- 1.0 Scope and Application lytical) essential to its performance. Some 1.1 Analytes.

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Analyte CAS No. Sensitivity

Arsenic compounds as ar- 7440–38–2 ...... Lower limit 10 μg/ml or less. senic (As).

1.2 Applicability. This method applies to 5.2.3 Hydrogen Peroxide (H2O2). Very the determination of inorganic As content of harmful to eyes. 30% H2O2 can burn skin, process ore and reverberatory matte samples nose, and lungs. from nonferrous smelters and other sources 5.2.4 Nitric Acid (HNO3). Highly corrosive as specified in an applicable subpart of the to eyes, skin, nose, and lungs. Vapors are regulations. highly toxic and can cause bronchitis, pneu- 1.3 Data Quality Objectives. Adherence to monia, or edema of lungs. Reaction to inha- the requirements of this method will en- lation may be delayed as long as 30 hours hance the quality of the data obtained from and still be fatal. Provide ventilation to air pollutant sampling methods. limit exposure. Strong oxidizer. Hazardous reaction may occur with organic materials 2.0 Summary of Method such as solvents. 5.2.5 Sodium Hydroxide (NaOH). Causes Arsenic bound in ore samples is liberated severe damage to eyes and skin. Inhalation by acid digestion and analyzed by flame causes irritation to nose, throat, and lungs. atomic absorption spectrophotometry (AAS). Reacts exothermically with limited amounts of water. 3.0 Definitions [Reserved] 6.0 Equipment and Supplies 4.0 Interferences 6.1 Sample Collection and Preparation. Analysis for As by flame AAS is sensitive The following items are required for sample to the chemical composition and to the phys- collection and preparation: ical properties (e.g., viscosity, pH) of the 6.1.1 Parr Acid Digestion Bomb. Stainless sample. The analytical procedure includes a steel with vapor-tight Teflon cup and cover. check for matrix effects (section 11.5). 6.1.2 Volumetric Pipets. 2- and 5-ml sizes. 6.1.3 Volumetric Flask. 50-ml poly- 5.0 Safety propylene with screw caps, (one needed per standard). 5.1 Disclaimer. This method may involve 6.1.4 Funnel. Polyethylene or poly- hazardous materials, operations, and equip- propylene. ment. This test method may not address all 6.1.5 Oven. Capable of maintaining a tem- of the safety problems associated with its perature of approximately 105 °C (221 °F). use. It is the responsibility of the user to es- 6.1.6 Analytical Balance. To measure to tablish appropriate safety and health prac- within 0.1 mg. tices and determine the applicability of reg- 6.2 Analysis. The following items are re- ulatory limitations prior to performing this quired for analysis: test method. 6.2.1 Spectrophotometer and Recorder. 5.2 Corrosive Reagents. The following re- Equipped with an electrodeless discharge agents are hazardous. Personal protective lamp and a background corrector to measure equipment and safe procedures that prevent absorbance at 193.7 nm. For measuring sam- chemical splashes are recommended. If con- ples having less than 10 μg As/ml, use a tact occurs, immediately flush with copious graphite furnace or vapor generator acces- amounts of water for at least 15 minutes. Re- sory. The recorder shall match the output of move clothing under shower and decontami- the spectrophotometer. nate. Treat residual chemical burns as ther- 6.2.2 Volumetric Flasks. Class A, 50-ml mal burns. (one needed per sample and blank), 500-ml, 5.2.1 Hydrochloric Acid (HCl). Highly cor- and 1-liter. rosive liquid with toxic vapors. Vapors are 6.2.3 Volumetric Pipets. Class A, 1-, 5-, 10- highly irritating to eyes, skin, nose, and , and 25-ml sizes. lungs, causing severe damage. May cause bronchitis, pneumonia, or edema of lungs. 7.0 Reagents and Standards. Exposure to concentrations of 0.13 to 0.2 per- Unless otherwise indicated, it is intended cent can be lethal to humans in a few min- that all reagents conform to the specifica- utes. Provide ventilation to limit exposure. tions established by the Committee on Ana- Reacts with metals, producing hydrogen gas. lytical Reagents of the American Chemical 5.2.2 Hydrofluoric Acid (HF). Highly cor- Society, where such specifications are avail- rosive to eyes, skin, nose, throat, and lungs. able; otherwise, use the best available grade. Reaction to exposure may be delayed by 24 7.1 Sample Collection and Preparation. hours or more. Provide ventilation to limit The following reagents are required for sam- exposure. ple collection and preparation:

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7.1.1 Water. Deionized distilled to meet 7.2.5 Hydrochloric Acid, Concentrated. ASTM D 1193–77 or 91 Type 3 (incorporated by 7.2.6 Potassium Iodide (KI), 30 Percent (W/ reference—See § 61.18). When high concentra- V). Dissolve 300 g of KI in about 500 ml of tions of organic matter are not expected to water in a 1-liter volumetric flask. Then, di- be present, the KMnO4 test for oxidizable or- lute to exactly 1.0 liter with water. ganic matter may be omitted. Use in all dilu- 7.2.7 Hydrogen Peroxide, 3 Percent by tions requiring water. Volume. Pipet 50 ml of 30 percent H2O2 into 7.1.2 Nitric Acid Concentrated. a 500-ml volumetric flask, and dilute to ex- 7.1.3 Nitric Acid, 0.5 N. In a 1-liter volu- actly 500 ml with water. metric flask containing water, add 32 ml of 7.2.8 Stock Arsenic Standard, 1 mg As/ml. concentrated HNO3 and dilute to volume Dissolve 1.3203 g of primary grade As2O3 in 20 with water. ml of 0.1 N NaOH. Slowly add 30 ml of con- 7.1.4 Hydrofluoric Acid, Concentrated. centrated HNO3, and heat in an oven at 105 °C 7.1.5 Potassium Chloride (KCl) Solution, (221 °F) for 2 hours. Allow to cool, and dilute 10 percent weight by volume (W/V). Dissolve to 1 liter with deionized distilled water. 10 g KCl in water, add 3 ml concentrated 7.2.9 Nitrous Oxide. Suitable quality for HNO , and dilute to 100 ml. 3 AAS analysis. 7.1.6 Filter. Teflon filters, 3-micron poros- 7.2.10 Acetylene. Suitable quality for AAS ity, 47-mm size. (Available from Millipore analysis. Co., type FS, Catalog Number FSLW04700.) 7.1.7 Sodium Borohydride (NaBH ), 5 Per- 7.2.11 Quality Assurance Audit Samples. 4 When making compliance determinations, cent (W/V). Dissolve 50.0 g of NaBH4 in about 500 ml of 0.1 N NaOH in a 1-liter volumetric and upon availability, audit samples may be flask. Then, dilute to exactly 1.0 liter with obtained from the appropriate EPA regional 0.1 N NaOH. Office or from the responsible enforcement 7.1.8 Nickel Nitrate, 5 Percent Ni (W/V). authority. Dissolve 24.780 g of nickel nitrate NOTE: The responsible enforcement authority should be notified at least 30 days prior hexahydrate [Ni(NO3)2 6H2O] in water in a 100-ml volumetric flask, and dilute to 100 ml to the test date to allow sufficient time for with water. sample delivery. 7.1.9 Nickel Nitrate, 1 Percent Ni (W/V). 8.0 Sample Collection, Preservation, Transport, Pipet 20 ml of 5 percent nickel nitrate solu- and Storage tion into a 100-ml volumetric flask, and dilute to 100 ml with water. 8.1 Sample Collection. A sample that is 7.2 Analysis. The following reagents and representative of the ore lot to be tested standards are required for analysis: must be taken prior to analysis. (A portion 7.2.2 Sodium Hydroxide, 0.1 N. Dissolve of the samples routinely collected for metals 2.00 g of NaOH in water in a 500-ml volu- analysis may be used provided the sample is metric flask. Dilute to volume with water. representative of the ore being tested.) 7.2.3 Nitric Acid, 0.5 N. Same as in Sec- 8.2 Sample Preparation. The sample must tion 7.1.3. be ground into a finely pulverized state. 7.2.4 Potassium Chloride Solution, 10 percent. Same as in Section 7.1.5. 9.0 QUALITY CONTROL

Section Quality control measure Effect

10.2 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.5 ...... Check for matrix effects ...... Eliminate matrix effects.

10.0 Calibration and Standardizations 10.2 Calibration Curve. Analyze the reagent blank and each standard solution ac- NOTE: Maintain a laboratory log of all cali- cording to the procedures outlined in Section brations. 11.3. Repeat this procedure on each standard 10.1 Preparation of Standard Solutions. solution until two consecutive peaks agree Pipet 1, 5, 10, and 25 ml of the stock As solu- within 3 percent of their average value. Sub- tion into separate 100-ml volumetric flasks. tract the average peak height (or peak area) Add 10 ml KCl solution and dilute to the of the blank—which must be less than 2 per- mark with 0.5 N HNO3. This will give stand- cent of recorder full scale—from the aver- ard concentrations of 10, 50, 100, and 250 μg aged peak heights of each standard solution. As/ml. For low-level arsenic samples that re- If the blank absorbance is greater than 2 per- quire the use of a graphite furnace or vapor cent of full-scale, the probable cause is Hg generator, follow the procedures in Section contamination of a reagent or carry-over of 11.3:1. Dilute 10 ml of KCl solution to 100 ml As from a previous sample. Prepare the calibration curve by plotting the corrected peak with 0.5 N HNO3 and use as a reagent blank. height of each standard solution versus the

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corresponding final total As weight in the structions will be given here. Instead, the in- solution. strument manufacturer’s detailed operating 10.3 Spectrophotometer Calibration Qual- instructions should be followed. ity Control. Calculate the least squares slope 11.3.1 Arsenic Determination at Low Con- of the calibration curve. The line must pass centration. The lower limit of flame AAS is through the origin or through a point no fur- 10 μg As/ml. If the arsenic concentration of ther from the origin than ±2 percent of the any sample is at a lower level, use the vapor recorder full scale. Multiply the corrected generator or graphite furnace which is avail- peak height by the reciprocal of the least able as an accessory component. Flame, squares slope to determine the distance each graphite furnace, or vapor generators may be calibration point lies from the theoretical used for samples whose concentrations are calibration line. The difference between the between 10 and 30 μg/ml. Follow the manufac- calculated concentration values and the ac- turer’s instructions in the use of such equip- tual concentrations must be less than 7 per- ment. cent for all standards. 11.3.1.1 Vapor Generator Procedure. Place NOTE: For instruments equipped with di- μ rect concentration readout devices, prepara- a sample containing between 0 and 5 g of ar- tion of a standard curve will not be nec- senic in the reaction tube, and dilute to 15 essary. In all cases, follow calibration and ml with water. Since there is some trial and operational procedures in the manufacturer’s error involved in this procedure, it may be instruction manual. necessary to screen the samples by conventional AAS until an approximate concentra- 11.0 Analytical Procedure tion is determined. After determining the approximate concentration, adjust the volume 11.1 Sample Preparation. Weigh 50 to 500 of the sample accordingly. Pipet 15 ml of mg of finely pulverized sample to the nearest 0.1 mg. Transfer the sample into the Teflon concentrated HCl into each tube. Add 1 ml of cup of the digestion bomb, and add 2 ml each 30 percent KI solution. Place the reaction tube into a 50 °C (120 °F) water bath for 5 of concentrated HNO3 and HF. Seal the bomb immediately to prevent the loss of any vola- minutes. Cool to room temperature. Connect tile arsenic compounds that may form. Heat the reaction tube to the vapor generator as- in an oven at 105 °C (221 °F) for 2 hours. Re- sembly. When the instrument response has move the bomb from the oven and allow to returned to baseline, inject 5.0 ml of 5 per- cool. Using a Teflon filter, quantitatively fil- cent NaBH4 and integrate the resulting spec- ter the digested sample into a 50-ml poly- trophotometer signal over a 30-second time propylene volumetric flask. Rinse the bomb period. three times with small portions of 0.5 N 11.3.1.2 Graphite Furnace Procedure. HNO3, and filter the rinses into the flask. Pipet 5 ml of the digested solution into a 10- Add 5 ml of KCl solution to the flask, and di- ml volumetric flask. Add 1 ml of the 1 per- lute to 50 ml with 0.5 N HNO3. cent nickel nitrate solution, 0.5 ml of 50 per- 11.2 Spectrophotometer Preparation. cent HNO3, and 1 ml of the 3 percent H2O2, 11.2.1 Turn on the power; set the wave- and dilute to 10 ml with water. The sample is length, slit width, and lamp current. Adjust now ready to inject in the furnace for anal- the background corrector as instructed by ysis. the manufacturer’s manual for the par- 11.4 Run a blank and standard at least ticular atomic absorption spectrophotom- after every five samples to check the spec- eter. Adjust the burner and flame character- trophotometer calibration. The peak height istics as necessary. of the blank must pass through a point no 11.2.2 Develop a spectrophotometer cali- further from the origin than ±2 percent of bration curve as outlined in Sections 10.2 and the recorder full scale. The difference be- 10.3. tween the measured concentration of the 11.3 Arsenic Determination. Analyze an standard (the product of the corrected aver- appropriately sized aliquot of each diluted age peak height and the reciprocal of the sample (from Section 11.1) until two consecu- least squares slope) and the actual con- tive peak heights agree within 3 percent of centration of the standard must be less than their average value. If applicable, follow the 7 percent, or recalibration of the analyzer is procedures outlined in Section 11.3.1. If the required. sample concentration falls outside the range 11.5 Mandatory Check for Matrix Effects of the calibration curve, make an appro- on the Arsenic Results. Same as Method 12, priate dilution with 0.5 N HNO so that the 3 Section 11.5. final concentration falls within the range of the curve. Using the calibration curve, deter- 12.0 Data Analysis and Calculations mine the As concentration in each sample. NOTE: Because instruments vary between 12.1 Calculate the percent arsenic in the manufacturers, no detailed operating in- ore sample as follows:

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5C F % As= ad Eq. 108A-1 W

Where: to an ICP–AES offers detection limits comparable to cold vapor atomic absorption. Ca = Concentration of As as read from the standard curve, μg/ml. 17.0 References Fd = Dilution factor (equals to 1 if the sample has not been diluted). Same as References 1 through 9 of Section W = Weight of ore sample analyzed, mg. 17.0 of Method 5, with the addition of the fol- 5 = (50 ml sample ‘‘ 100)/(103 μg/mg). lowing: 13.0 Method Performance 1. Perkin Elmer Corporation. Analytical Methods of Atomic Absorption 13.1 Sensitivity. The lower limit of flame Spectrophotometry. 303–0152. Norwalk, Con- μ AAS is 10 g As/ml. The analytical procedure necticut. September 1976. pp 5–6. includes provisions for the use of a graphite 2. Ringwald, D. Arsenic Determination on furnace or vapor generator for samples with Process Materials from ASARCO’s Copper a lower arsenic concentration. Smelter in Tacoma, Washington. Unpub- 14.0 Pollution Prevention. [Reserved] lished Report. Prepared for Emission Meas- urement Branch, Emission Standards and 15.0 Waste Management. [Reserved] Engineering Division, U.S. Environmental Protection Agency, Research Triangle Park, 16.0 Alternative Procedures North Carolina. August 1980. 35 pp. 16.1 Alternative Analyzer. Inductively 3. Stack Sampling Safety Manual (Draft). coupled plasma-atomic emission spectrom- U.S. Environmental Protection Agency, Of- etry (ICP–AES) may be used as an alter- fice of Air Quality Planning and Standard, native to atomic absorption analysis pro- Research Triangle Park, NC. September 1978. vided the following conditions are met: 18.0 Tables, Diagrams, Flowcharts, and 16.1.1 Sample collection, sample prepara- Validation Data. [Reserved] tion, and analytical preparation procedures are as defined in the method except as nec- METHOD 108B—DETERMINATION OF ARSENIC essary for the ICP–AES application. CONTENT IN ORE SAMPLES FROM NON- 16.1.2 Quality Assurance/Quality Control FERROUS SMELTERS procedures, including audit material analysis, are conducted as prescribed in the NOTE: This method does not include all of method. The QA acceptance conditions must the specifications (e.g., equipment and sup- be met. plies) and procedures (e.g., sampling and ana- 16.1.3 The limit of quantitation for the lytical) essential to its performance. Some ICP–AES must be demonstrated and the material is incorporated by reference from sample concentrations reported should be no other methods in this appendix and in appen- less than two times the limit of quantita- dix A to 40 CFR part 60. Therefore, to obtain tion. The limit of quantitation is defined as reliable results, persons using this method ten times the standard deviation of the should have a thorough knowledge of at least blank value. The standard deviation of the the following additional test methods: Meth- blank value is determined from the analysis od 12 and Method 108A. of seven blanks. It has been reported that for 1.0 Scope and Application mercury and those elements that form hy- drides, a continuous-flow generator coupled 1.1 Analytes.

Analyte CAS No. Sensitivity

Arsenic compounds as ar- 7440–38–2 ...... Lower limit 10 μg/ml. senic (As).

1.2 Applicability. This method applies to level arsenic samples, Method 108C should be the determination of inorganic As content of used. process ore and reverberatory matte samples 1.3 Data Quality Objectives. Adherence to from nonferrous smelters and other sources the requirements of this method will en- as specified in an applicable subpart of the hance the quality of the data obtained from regulations. Samples resulting in an analyt- air pollutant sampling methods. ical concentration greater than 10 μg As/ml may be analyzed by this method. For lower

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2.0 Summary of Method 6.0 Equipment and Supplies Arsenic bound in ore samples is liberated 6.1 Sample Preparation. The following by acid digestion and analyzed by flame items are required for sample preparation: atomic absorption spectrophotometry (AAS). 6.1.1 Teflon Beakers. 150-ml. 6.1.2 Graduated Pipets. 5-ml disposable. 3.0 Definitions [Reserved] 6.1.3 Graduated Cylinder. 50-ml. 6.1.4 Volumetric Flask. 100-ml. 4.0 Interferences 6.1.5 Analytical Balance. To measure Analysis for As by flame AAS is sensitive within 0.1 mg. to the chemical composition and to the phys- 6.1.6 Hot Plate. ical properties (e.g., viscosity, pH) of the 6.1.7 Perchloric Acid Fume Hood. sample. The analytical procedure includes a 6.2 Analysis. The following items are re- check for matrix effects (Section 11.4). quired for analysis: 6.2.1 Spectrophotometer. Equipped with 5.0 Safety an electrodeless discharge lamp and a back- 5.1 Disclaimer. This method may involve ground corrector to measure absorbance at hazardous materials, operations, and equip- 193.7 nm. ment. This test method may not address all 6.2.2 Beaker and Watch Glass. 400-ml. of the safety problems associated with its 6.2.3 Volumetric Flask. 1-liter. use. It is the responsibility of the user to es- 6.2.4 Volumetric Pipets. 1-, 5-, 10-, and 25- tablish appropriate safety and health prac- ml. tices and determine the applicability of reg- 7.0 Reagents and Standards ulatory limitations prior to performing this test method. Unless otherwise indicated, it is intended 5.2 Corrosive Reagents. The following re- that all reagents conform to the specifica- agents are hazardous. Personal protective tions established by the Committee on Ana- equipment and safe procedures that prevent lytical Reagents of the American Chemical chemical splashes are recommended. If con- Society, where such specifications are avail- tact occurs, immediately flush with copious able; otherwise, use the best available grade. amounts of water for at least 15 minutes. Re- 7.1 Sample Preparation. The following remove clothing under shower and decontami- agents are required for sample preparation: nate. Treat residual chemical burns as ther- 7.1.1 Water. Deionized distilled to meet mal burns. ASTM D 1193–77 or 91 Type 3 (incorporated by 5.2.1 Hydrochloric acid (HCl). Highly cor- reference—see § 61.18). rosive liquid with toxic vapors. Vapors are 7.1.2 Nitric Acid, Concentrated. highly irritating to eyes, skin, nose, and 7.1.3 Hydrofluoric Acid, Concentrated. lungs, causing severe damage. May cause 7.1.4 Perchloric Acid, 70 Percent. bronchitis, pneumonia, or edema of lungs. 7.1.5 Hydrochloric Acid, Concentrated. Exposure to concentrations of 0.13 to 0.2 per- 7.2 Analysis. The following reagents and cent can be lethal to humans in a few min- standards are required for analysis: utes. Provide ventilation to limit exposure. 7.2.1 Water. Same as in Section 7.1.1. Reacts with metals, producing hydrogen gas. 7.2.2 Stock Arsenic Standard, 1.0 mg As/ 5.2.2 Hydrofluoric Acid (HF). Highly cor- ml. Dissolve 1.3203 g of primary grade As203 rosive to eyes, skin, nose, throat, and lungs. [dried at 105 °C (221 °F)] in a 400-ml beaker Reaction to exposure may be delayed by 24 with 10 ml of HNO3 and 5 ml of HCl. Cover hours or more. Provide ventilation to limit with a watch glass, and heat gently until dis- exposure. solution is complete. Add 10 ml of HNO3 and 5.2.3 Nitric Acid (HNO3). Highly corrosive 25 ml of HClO4, evaporate to strong fumes of to eyes, skin, nose, and lungs. Vapors are HClO4, and reduce to about 20 ml volume. highly toxic and can cause bronchitis, pneu- Cool, add 100 ml of water and 100 ml of HCl, monia, or edema of lungs. Reaction to inha- and transfer quantitatively to a 1-liter volu- lation may be delayed as long as 30 hours metric flask. Dilute to volume with water and still be fatal. Provide ventilation to and mix. limit exposure. Strong oxidizer. Hazardous 7.2.3 Acetylene. Suitable quality for AAS reaction may occur with organic materials analysis. such as solvents. 7.2.4 Air. Suitable quality for AAS anal- 5.2.4 Perchloric Acid (HClO4). Corrosive to ysis. eyes, skin, nose, and throat. Provide ventilation to limit exposure. Very strong oxidizer. 8.0 Sample Collection, Preservation, Transport, Keep separate from water and oxidizable ma- and Storage terials to prevent vigorous evolution of heat, Same as in Method 108A, Sections 8.1 and spontaneous combustion, or explosion. Heat 8.2. solutions containing HClO4 only in hoods specifically designed for HClO4. 9.0 QUALITY CONTROL

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Section Quality control measure Effect

10.2 ...... Spectrophotometer calibration ...... Ensure linearity of spectrophotometer response to standards. 11.4 ...... Check for matrix effects ...... Eliminate matrix effects.

10.0 Calibration and Standardization photometer calibration. The peak height of the blank must pass through a point no fur- NOTE: Maintain a laboratory log of all cali- ther from the origin than ±2 percent of the brations. recorder full scale. The difference between 10.1 Preparation of Standard Solutions. the measured concentration of the standard Pipet 1, 5, 10, and 25 ml of the stock As solu- (the product of the corrected average peak tion into separate 100-ml volumetric flasks. height and the reciprocal of the least squares Add 2 ml of HClO , 10 ml of HCl, and dilute 4 slope) and the actual concentration of the to the mark with water. This will provide standard must be less than 7 percent, or re- standard concentrations of 10, 50, 100, and 250 calibration of the analyzer is required. μg As/ml. 10.2 Calibration Curve and Spectro- 11.4 Mandatory Check for Matrix Effects photometer Calibration Quality Control. on the Arsenic Results. Same as Method 12, Same as Method 108A, Sections 10.2 and 10.3 Section 11.5. 11.0 Analytical Procedure 12.0 Data Analysis and Calculations 11.1 Sample Preparation. Weigh 100 to 1000 Same as in Method 108A, Section 12.0. mg of finely pulverized sample to the nearest 13.0 Method Performance 0.1 mg. Transfer the sample to a 150-ml Tef- lon beaker. Dissolve the sample by adding 15 13.1 Sensitivity. The lower limit of flame μ ml of HNO3, 10 ml of HCl, 10 ml of HF, and 10 AAS is 10 g As/ml. ml of HClO in the exact order as described, 4 14.0 Pollution Prevention [Reserved] and let stand for 10 minutes. In a HClO4 fume hood, heat on a hot plate until 2–3 ml of 15.0 Waste Management [Reserved] HClO4 remain, then cool. Add 20 ml of water and 10 ml of HCl. Cover and warm until the 16.0 References soluble salts are in solution. Cool, and transfer quantitatively to a 100-ml volumetric Same as in Method 108A, Section 16.0. flask. Dilute to the mark with water. 17.0 Tables, Diagrams, Flowcharts, and 11.2 Spectrophotometer Preparation. Validation Data [Reserved] Same as in Method 108A, Section 11.2. 11.3 Arsenic Determination. If the sample METHOD 108C—DETERMINATION OF ARSENIC concentration falls outside the range of the CONTENT IN ORE SAMPLES FROM NON- calibration curve, make an appropriate dilu- FERROUS SMELTERS (MOLYBDENUM BLUE tion with 2 percent HClO4/10 percent HCl PHOTOMETRIC PROCEDURE) (prepared by diluting 2 ml concentrated NOTE: This method does not include all of HClO4 and 10 ml concentrated HCl to 100 ml with water) so that the final concentration the specifications (e.g., equipment and sup- falls within the range of the curve. Using the plies) and procedures (e.g., sampling and ana- calibration curve, determine the As con- lytical) essential to its performance. Some centration in each sample. material is incorporated by reference from NOTE: Because instruments vary between other methods in this part. Therefore, to ob- manufacturers, no detailed operating in- tain reliable results, persons using this structions will be given here. Instead, the in- method should have a thorough knowledge of strument manufacturer’s detailed operating at least Method 108A. instructions should be followed. 1.0 Scope and Application Run a blank and standard at least after every five samples to check the spectro- 1.1 Analytes.

Analyte CAS No. Sensitivity

Arsenic compounds as ar- 7440–38–2 ...... Lower limit 0.0002 percent As by weight. senic (As).

1.2 Applicability. This method applies to as specified in an applicable subpart of the the determination of inorganic As content of regulations. process ore and reverberatory matte samples from nonferrous smelters and other sources

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1.3 Data Quality Objectives. Adherence to ness. Inhalation may be fatal from spasm of the requirements of this method will en- the larynx, usually within 30 minutes. May hance the quality of the data obtained from cause lung tissue damage with edema. 3 mg/ air pollutant sampling methods. m3 will cause lung damage in uninitiated. 1 mg/m3 for 8 hours will cause lung damage or, 2.0 Summary of Method in higher concentrations, death. Provide ven- Arsenic bound in ore samples is liberated tilation to limit inhalation. Reacts violently by acid digestion and analyzed by the molyb- with metals and organics. denum blue photometric procedure. 6.0 Equipment and Supplies 3.0 Definitions. [Reserved] 6.1 Sample Preparation. The following 4.0 Interferences. [Reserved] items are required for sample preparation: 6.1.1 Analytical Balance. To measure to 5.0 Safety within 0.1 mg. 6.1.2 Erlenmeyer Flask. 300-ml. 5.1 Disclaimer. This method may involve 6.1.3 Hot Plate. hazardous materials, operations, and equip- 6.1.4 Distillation Apparatus. No. 6, in ment. This test method may not address all ASTM E 50–82, 86, or 90 (Reapproved of the safety problems associated with its 1995)(incorporated by reference—see § 61.18); use. It is the responsibility of the user to es- detailed in Figure 108C–1. tablish appropriate safety and health prac- 6.1.5 Graduated Cylinder. 50-ml. tices and determine the applicability of reg- 6.1.6 Perchloric Acid Fume Hood. ulatory limitations prior to performing this 6.2 Analysis. The following items are re- test method. quired for analysis: 5.2 Corrosive Reagents. The following re- 6.2.1 Spectrophotometer. Capable of meas- agents are hazardous. Personal protective uring at 660 nm. equipment and safe procedures that prevent 6.2.2 Volumetric Flasks. 50- and 100-ml. chemical splashes are recommended. If contact occurs, immediately flush with copious 7.0 Reagents and Standards amounts of water for at least 15 minutes. Re- move clothing under shower and decontami- Unless otherwise indicated, it is intended nate. Treat residual chemical burns as ther- that all reagents conform to the specifica- mal burns. tions established by the Committee on Ana- 5.2.1 Hydrochloric Acid (HCl). Highly cor- lytical Reagents of the American Chemical rosive liquid with toxic vapors. Vapors are Society, where such specifications are avail- highly irritating to eyes, skin, nose, and able; otherwise, use the best available grade. lungs, causing severe damage. May cause 7.1 Sample Preparation. The following re- bronchitis, pneumonia, or edema of lungs. agents are required for sample preparation: Exposure to concentrations of 0.13 to 0.2 per- 7.1.1 Water. Deionized distilled to meet cent can be lethal to humans in a few min- ASTM D 1193–77 or 91 Type 3 (incorporated by utes. Provide ventilation to limit exposure. reference—see § 61.18). When high concentra- Reacts with metals, producing hydrogen gas. tions of organic matter are not expected to 5.2.2 Hydrofluoric Acid (HF). Highly cor- be present, the KMnO4 test for oxidizable or- rosive to eyes, skin, nose, throat, and lungs. ganic matter may be omitted. Use in all dilu- Reaction to exposure may be delayed by 24 tions requiring water. hours or more. Provide ventilation to limit 7.1.2 Nitric Acid, Concentrated. exposure. 7.1.3 Hydrofluoric Acid, Concentrated. 5.2.3 Nitric Acid (HNO4). Highly corrosive 7.1.4 Sulfuric Acid, Concentrated. to eyes, skin, nose, and lungs. Vapors are 7.1.5 Perchloric Acid, 70 Percent. highly toxic and can cause bronchitis, pneu- 7.1.6 Hydrochloric Acid, Concentrated. monia, or edema of lungs. Reaction to inha- 7.1.7 Dilute Hydrochloric Acid. Add one lation may be delayed as long as 30 hours part concentrated HCl to nine parts water. and still be fatal. Provide ventilation to 7.1.8 Hydrazine Sulfate ((NH2)2·H2SO4). limit exposure. Strong oxidizer. Hazardous 7.1.9 Potassium Bromide (KBr). reaction may occur with organic materials 7.1.10 Bromine Water, Saturated. such as solvents. 7.2 Analysis. The following reagents and 5.2.4 Perchloric Acid (HClO4). Corrosive to standards are required for analysis: eyes, skin, nose, and throat. Provide ventila- 7.2.1 Water. Same as in Section 7.1.1. tion to limit exposure. Very strong oxidizer. 7.2.2 Methyl Orange Solution, 1 g/liter. Keep separate from water and oxidizable ma- 7.2.3 Ammonium Molybdate Solution, 5 g/ terials to prevent vigorous evolution of heat, liter. Dissolve 0.5 g (NH4)Mo7O24·4H2O in spontaneous combustion, or explosion. Heat water in a 100-ml volumetric flask, and di- solutions containing HClO4 only in hoods lute to the mark. This solution must be specifically designed for HClO4. freshly prepared. 5.2.5 Sulfuric acid (H2SO4). Rapidly de- 7.2.4 Standard Arsenic Solution, 10 μg As/ structive to body tissue. Will cause third de- ml. Dissolve 0.13203 g of As2O3 in 100 ml HCl gree burns. Eye damage may result in blind- in a 1-liter volumetric flask. Add 200 ml of

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water, cool, dilute to the mark with water, 7.2.7 Ammonium Hydroxide (NH4OH), Con- and mix. Transfer 100 ml of this solution to centrated. a 1-liter volumetric flask, add 40 ml HCl, 7.2.8 Boiling Granules. cool, dilute to the mark, and mix. 7.2.9 Hydrochloric Acid, 50 percent by vol- 7.2.5 Hydrazine Sulfate Solution, 1 g/liter. ume. Dilute equal parts concentrated HCl with water. Dissolve 0.1 g of [(NH2)2·H2SO4] in water, and dilute to 100 ml in a volumetric flask. This 8.0 Sample Collection, Preservation, Transport, solution must be freshly prepared. and Storage 7.2.6 Potassium Bromate (KBrO3) Solu- tion, 0.03 Percent Weight by Volume (W/V). Same as in Method 108A, Sections 8.1 and 8.2. Dissolve 0.3 g KBrO3 in water, and dilute to 1 liter with water. 9.0 QUALITY CONTROL

Section Quality control measure Effect

10.2 ...... Calibration curve preparation ...... Ensure linearity of spectrophotometric response to standards.

10.0 Calibration and Standardizations several boiling granules. Cool to room temperature. NOTE: Maintain a laboratory log of all cali- 11.1.2 Add 1 g of KBr, 1 g hydrazine sul- brations. fate, and 50 ml HCl. Immediately attach the 10.1 Preparation of Standard Solutions. distillation head with thermometer and dip Transfer 1.0, 2.0, 4.0, 8.0, 12.0, 16.0, and 20.0 ml the side arm into a 50-ml graduated cylinder of standard arsenic solution (10 μg/ml) to containing 25 ml of water and 2 ml of bro- each of seven 50-ml volumetric flasks. Dilute mine water. Keep the graduated cylinder im- to 20 ml with dilute HCl. Add one drop of mersed in a beaker of cold water during dis- methyl orange solution and neutralize to the tillation. Distill until the temperature of the yellow color with dropwise addition of vapor in the flask reaches 107 °C (225 °F). NH OH. Just bring back to the red color by 4 When distillation is complete, remove the dropwise addition of dilute HCl, and add 10 flask from the hot plate, and simultaneously ml in excess. Proceed with the color develop- wash down the side arm with water as it is ment as described in Section 11.2. removed from the cylinder. 10.2 Calibration Curve. Plot the 11.1.3 If the expected arsenic content is in spectrophotometric readings of the calibra- the range of 0.0020 to 0.10 percent, dilute the tion solutions against μg As per 50 ml of so- distillate to the 50-ml mark of the cylinder lution. Use this curve to determine the As with water, stopper, and mix. Transfer a 5.0- concentration of each sample. ml aliquot to a 50-ml volumetric flask. Add 10.3 Spectrophotometer Calibration Qual- 10 ml of water and a boiling granule. Place ity Control. Calculate the least squares slope the flask on a hot plate, and heat gently of the calibration curve. The line must pass until the bromine is expelled and the color of through the origin or through a point no fur- methyl orange indicator persists upon the ± ther from the origin than 2 percent of the addition of 1 to 2 drops. Cool the flask to recorder full scale. Multiply the corrected room temperature. Neutralize just to the peak height by the reciprocal of the least yellow color of the indicator with dropwise squares slope to determine the distance each additions of NH4OH. Bring back to the red calibration point lies from the theoretical color by dropwise addition of dilute HCl, and calibration line. The difference between the add 10 ml excess. Proceed with the molyb- calculated concentration values and the ac- denum blue color development as described tual concentrations must be less than 7 per- in Section 11.2. cent for all standards. 11.1.4 If the expected arsenic content is in 11.0 Analytical Procedure the range of 0.0002 to 0.0010 percent As, transfer either the entire initial distillate or the 11.1 Sample Preparation. measured remaining distillate from Section 11.1.1 Weigh 1.0 g of finely pulverized sam- 11.1.2 to a 250-ml beaker. Wash the cylinder ple to the nearest 0.1 mg. Transfer the sam- with two successive portions of concentrated ple to a 300 ml Erlenmeyer flask and add 15 HNO3, adding each portion to the distillate ml of HNO3, 4 ml HCl, 2 ml HF, 3 ml HClO4, in the beaker. Add 4 ml of concentrated and 15 ml H2SO4, in the order listed. In a HClO4, a boiling granule, and cover with a HClO4 fume hood, heat on a hot plate to de- flat watch glass placed slightly to one side. compose the sample. Then heat while swirl- Boil gently on a hot plate until the volume ing over an open flame until dense white is reduced to approximately 10 ml. Add 3 ml fumes evolve. Cool, add 15 ml of water, swirl of HNO3, and continue the evaporation until to hydrate the H2SO4 completely, and add HClO4 is refluxing on the beaker cover. Cool 305

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briefly, rinse the underside of the watch fate solution, dilute until the solution comes glass and the inside of the beaker with about within the neck of the flask, and mix. Place 3–5 ml of water, cover, and continue the the flask in a 400 ml beaker, 80 percent full evaporation to expel all but 2 ml of the of boiling water, for 10 minutes. Enough heat HClO4. must be supplied to prevent the water bath NOTE: If the solution appears cloudy due to from cooling much below the boiling point a small amount of antimony distilling over, upon inserting the volumetric flask. Remove add 4 ml of 50 percent HCl and 5 ml of water, the flask, cool to room temperature, dilute cover, and warm gently until clear. If cloudi- to the mark, and mix. ness persists, add 5 ml of HNO3 and 2 ml 11.2.2 Transfer a suitable portion of the H2SO4. Continue the evaporation of volatile reference solution to an absorption cell, and acids to solubilize the antimony until dense adjust the spectrophotometer to the initial white fumes of H2SO4 appear. Retain at least setting using a light band centered at 660 1 ml of the H2SO4. nm. While maintaining this spectrophotometer adjustment, take the readings of the 11.1.5 To the 2 ml of HClO4 solution or 1 calibration solutions followed by the sam- ml of H2SO4 solution, add 15 ml of water, boil gently for 2 minutes, and then cool. Proceed ples. with the molybdenum blue color development by neutralizing the solution directly in 12.0 Data Analysis and Calculations the beaker just to the yellow indicator color Same as in Method 108A, Section 12.0. by dropwise addition of NH4OH. Obtain the red color by dropwise addition of dilute HCl. 13.0 Method Performance. [Reserved] Transfer the solution to a 50-ml volumetric flask. Rinse the beaker successively with 10 14.0 Pollution Prevention. [Reserved] ml of dilute HCl, followed by several small portions of water. At this point the volume 15.0 Waste Management. [Reserved] of solution in the flask should be no more 16.0 References than 40 ml. Continue with the color development as described in Section 11.2. 1. Ringwald, D. Arsenic Determination on 11.2 Analysis. Process Materials from ASARCO’s Copper 11.2.1 Add 1 ml of KBrO3 solution to the Smelter in Tacoma, Washington. Unpub- flask and heat on a low-temperature hot lished Report. Prepared for the Emission plate to about 50 °C (122 °F) to oxidize the ar- Measurement Branch, Technical Support Di- senic and methyl orange. Add 5.0 ml of am- vision, U.S. Environmental Protection Agen- monium molybdate solution to the warm so- cy, Research Triangle Park, North Carolina. lution and mix. Add 2.0 ml of hydrazine sul- August 1980. 35 pp.

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17.0 TABLES, DIAGRAMS, FLOWCHARTS, AND VALIDATION DATA

METHOD 111—DETERMINATION OF POLONIUM– Therefore, to obtain reliable results, persons 210 EMISSIONS FROM STATIONARY SOURCES using this method should have a thorough knowledge of at least the following addi- NOTE: This method does not include all of tional test methods: Method 1, Method 2, the specifications (e.g., equipment and sup- Method 3, and Method 5. plies) and procedures (e.g., sampling and analytical) essential to its performance. Some 1.0 Scope and Application material is incorporated by reference from methods in appendix A to 40 CFR part 60. 1.1 Analytes.

Analyte CAS No. Sensitivity

Polonium ...... 7440–08–6 ...... Not specified.

1.2 Applicability. This method is applica- 2.0 Summary of Method ble for the determination of the polonium-210 A particulate matter sample, collected ac- content of particulate matter samples col- cording to Method 5, is analyzed for polo- lected from stationary source exhaust nium-210 content: the polonium-210 in the stacks, and for the use of these data to cal- sample is put in solution, deposited on a culate polonium-210 emissions from indi- metal disc, and the radioactive disintegra- vidual sources and from all affected sources tion rate measured. Polonium in acid solu- at a facility. tion spontaneously deposits on surfaces of 1.3 Data Quality Objectives. Adherence to metals that are more electropositive than the requirements of this method will en- polonium. This principle is routinely used in hance the quality of the data obtained from the radiochemical analysis of polonium-210. air pollutant sampling methods. Data reduction procedures are provided, allowing the calculation of polonium-210 emissions from individual sources and from all

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affected sources at a facility, using data ob- 6.3 Polished Silver Discs. 3.8 cm diameter, tained from Methods 2 and 5 and from the 0.4 mm thick with a small hole near the analytical procedures herein. edge. 6.4 Glass Beakers. 400 ml, 150 ml. 3.0 Definitions [Reserved] 6.5 Hot Plate, Electric. 4.0 Interferences [Reserved] 6.6 Fume Hood. 6.7 Teflon Beakers, 150 ml. 5.0 Safety 6.8 Magnetic Stirrer. 6.9 Stirring Bar. 5.1 Disclaimer. This method may involve 6.10 Hooks. Plastic or glass, to suspend hazardous materials, operations, and equip- plating discs. ment. This test method may not address all of the safety problems associated with its 6.11 Internal Proportional Counter. For use. It is the responsibility of the user of this measuring alpha particles. test method to establish appropriate safety 6.12 Nucleopore Filter Membranes. 25 mm and health practices and determine the ap- diameter, 0.2 micrometer pore size or equiva- plicability of regulatory limitations prior to lent. performing this test method. 6.13 Planchets. Stainless steel, 32 mm di- 5.2 Corrosive Reagents. The following re- ameter with 1.5 mm lip. agents are hazardous. Personal protective 6.14 Transparent Plastic Tape. 2.5 cm wide equipment and safe procedures are useful in with adhesive on both sides. preventing chemical splashes. If contact oc- 6.15 Epoxy Spray Enamel. curs, immediately flush with copious 6.16 Suction Filter Apparatus. For 25 mm amounts of water at least 15 minutes. Re- diameter filter. move clothing under shower and decontami- 6.17 Wash Bottles, 250 ml capacity. nate. Treat residual chemical burns as ther- 6.18 Graduated Cylinder, plastic, 25 ml ca- mal burns. pacity. 5.2.1 Hydrochloric Acid (HCl). Highly cor- 6.19 Volumetric Flasks, 100 ml, 250 ml. rosive liquid with toxic vapors. Vapors are highly irritating to eyes, skin, nose, and 7.0 Reagents and Standards lungs, causing severe damage. May cause Unless otherwise indicated, it is intended bronchitis, pneumonia, or edema of lungs. that all reagents conform to the specifica- Exposure to concentrations of 0.13 to 0.2 per- tions established by the Committee on Ana- cent can be lethal to humans in a few min- lytical Reagents of the American Chemical utes. Provide ventilation to limit exposure. Society, where such specifications are avail- Reacts with metals, producing hydrogen gas. able; otherwise, use the best available grade. 5.2.2 Hydrofluoric Acid (HF). Highly cor- 7.1 Ascorbic Acid. rosive to eyes, skin, nose, throat, and lungs. Reaction to exposure may be delayed by 24 7.2 Ammonium Hydroxide (NH4OH), 15 M. hours or more. Provide ventilation to limit 7.3 Water. Deionized distilled, to conform exposure. to ASTM D 1193–77 or 91 (incorporated by reference—see § 61.18), Type 3. Use in all dilu- 5.2.3 Nitric Acid (HNO3). Highly corrosive to eyes, skin, nose, and lungs. Vapors cause tions requiring water. bronchitis, pneumonia, or edema of lungs. 7.4 Ethanol (C2H5OH), 95 percent. Reaction to inhalation may be delayed as 7.5 Hydrochloric Acid, 12 M. long as 30 hours and still be fatal. Provide 7.6 Hydrochloric Acid, 1 M. Dilute 83 ml of ventilation to limit exposure. Strong oxi- the 12 M HCl to 1 liter with distilled water. dizer. Hazardous reaction may occur with or- 7.7 Hydrofluoric Acid, 29 M. ganic materials such as solvents. 7.8 Hydrofluoric Acid, 3 M. Dilute 52 ml of

5.2.4 Perchloric Acid (HClO4). Corrosive to the 29 M HF to 500 ml with distilled water. eyes, skin, nose, and throat. Provide ventila- Use a plastic graduated cylinder and storage tion to limit exposure. Keep separate from bottle. water and oxidizable materials to prevent 7.9 Lanthanum Carrier, 0.1 mg La∂3/ml. vigorous evolution of heat, spontaneous com- Dissolve 0.078 gram lanthanum nitrate, bustion, or explosion. Heat solutions con- La(NO3)3·6H2O in 250 ml of 1 M HCl. taining HClO4 only in hoods specifically de- 7.10 Nitric Acid, 16 M. signed for HClO4. 7.11 Perchloric Acid, 12 M. 7.12 Polonium-209 Solution. 6.0 Equipment and Supplies 7.13 Silver Cleaner. Any mild abrasive 6.1 Alpha Spectrometry System. Con- commercial silver cleaner. sisting of a multichannel analyzer, biasing 7.14 Degreaser. electronics, silicon surface barrier detector, 7.15 Standard Solution. Standardized so- vacuum pump and chamber. lution of an alpha-emitting actinide ele- 6.2 Constant Temperature Bath at 85 °C ment, such as plutonium-239 or americium- (185 °F). 241.

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8.0 Sample Collection, Preservation, Transport, 9.1.1 All analysts using this method are and Storage. [Reserved] required to demonstrate their ability to use the method and to define their respective ac- 9.0 Quality Control curacy and precision criteria.

9.1 General Requirement. 9.2 MISCELLANEOUS QUALITY CONTROL MEASURES

Section Quality control measure Effect

10.1 ...... Standardization of alpha spectrometry system .... Ensure precision of sample analyses. 10.3 ...... Standardization of internal proportional counter .. Ensure precise sizing of sample aliquot. 11.1, 11.2 ...... Determination of procedure background and in- Minimize background effects. strument background.

10.0 Calibration and Standardization 10.2.3 Calculate the activity of each aliquot of the polonium-209 tracer solution 10.1 Standardization of Alpha Spectrom- using Eq. 111–2 in Section 12.3. etry System. 10.1.1 Add a quantity of the actinide 10.2.4 Determine the average activity of standard solution to a 100 ml volumetric the polonium-209 tracer solution, F, by aver- flask so that the final concentration when aging the results of the six determinations. diluted to a volume of 100 ml will be approxi- 10.3 Standardization of Internal Propor- tional Counter mately 1 pCi/ml. 10.1.2 Add 10 ml of 16 M HNO3 and dilute 10.3.1 Add a quantity of the actinide to 100 ml with water. standard solution to a 100 ml volumetric 10.1.3 Add 20 ml of 1 M HCl to each of six flask so that the final concentration when 150 ml beakers. Add 1.0 ml of lanthanum car- diluted to a 100 ml volume will be approxi- rier, 0.1 mg lanthanum per ml, to the acid so- mately 100 pCi/ml. lution in each beaker. 10.3.2 Follow the procedures outlined in 10.1.4 Add 1.0 ml of the 1 pCi/ml working Sections 10.1.2 through 10.1.6, except sub- solution (from Section 10.1.1) to each beaker. stitute the 100 pCi/ml actinide working solu- Add 5.0 ml of 3 M HF to each beaker. tion for the 1 pCi/ml solution, place the plan- 10.1.5 Cover beakers and allow solutions chet in an internal proportional counter (in- to stand for a minimum of 30 minutes. Filter stead of an alpha spectrometry system), and the contents of each beaker through a sepa- count for 100 minutes (instead of 1000 min- rate filter membrane using the suction filter utes). apparatus. After each filtration, wash the fil- 10.3.3 Calculate the counting efficiency of ter membrane with 10 ml of distilled water the internal proportional counter for each and 5 ml of ethanol, and allow the filter aliquot of the 100 pCi/ml actinide working so- membrane to air dry on the filter apparatus. lution using Eq. 111–3 in 12.4. 10.1.6 Carefully remove the filter mem- 10.3.4 Determine the average counting ef- brane and mount it, filtration side up, with ficiency of the internal proportional counter, double-side tape on the inner surface of a EI, by averaging the results of the six deter- planchet. Place planchet in an alpha spec- minations. trometry system and count each planchet for 1000 minutes. 11.0 ANALYTICAL PROCEDURE 10.1.7 Calculate the counting efficiency of the detector for each aliquot of the 1 pCi/ml NOTE: Perform duplicate analyses of all actinide working solution using Eq. 111–1 in samples, including background counts and Section 12.2. Method 5 samples. Duplicate measurements 10.1.8 Determine the average counting ef- are considered acceptable when the dif- ficiency of the detector, Ec, by calculating ference between them is less than two stand- the average of the six determinations. ard deviations as described in EPA 600/4–77– 10.2 Preparation of Standardized Solution 001 or subsequent revisions. of Polonium-209. 11.1 Determination of Procedure Back- 10.2.1 Add a quantity of the Po-209 solu- ground. Background counts used in all equation to a 100 ml volumetric flask so that the tions are determined by performing the spe- final concentration when diluted to a 100 ml cific analysis required using the analytical volume will be approximately 1 pCi/ml. reagents only. All procedure background 10.2.2 Follow the procedures outlined in counts and sample counts for the internal Sections 10.1.2 through 10.1.6, except sub- proportional counter should utilize a count- stitute 1.0 ml of polonium-209 tracer solution ing time of 100 minutes; for the alpha spec- (Section 10.2.1) and 3.0 ml of 15 M ammonium trometry system, 1000 minutes. These back- hydroxide for the 1 pCi/ml actinide working ground counts should be performed no less solution and the 3 M HF, respectively. frequently than once per 10 sample analyses.

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11.2 Determination of Instrument Back- 11.5.1 Add 20 ml of 1 M HCl, 1 ml of the ground. Instrument backgrounds of the in- lanthanum carrier solution (0.1 mg La/ml), a ternal proportional counter and the alpha 1 ml aliquot of the sample solution from Sec- spectrometry system should be determined tion 11.4.10, and 3 ml of 15 M ammonium hy- on a weekly basis. Instrument background droxide to a 250-ml beaker in the order list- should not exceed procedure background. If ed. Allow this solution to stand for a min- this occurs, it may be due to a malfunction imum of 30 minutes. or contamination, and should be corrected 11.5.2 Filter the solution through a filter before use. membrane using the suction filter apparatus. 11.4 Sample Preparation. Treat the Meth- Wash the filter membrane with 10 ml of od 5 samples [i.e., the glass fiber filter (Con- water and 5 ml of ethanol, and allow the fil- tainer No. 1) and the acetone rinse (Con- ter membrane to air dry on the filter appa- tainer No. 2)] as follows: ratus. 11.4.1 Container No. 1. Transfer the filter 11.5.3 Carefully remove the filter mem- and any loose particulate matter from the brane and mount it, filtration side up, with sample container to a 150-ml Teflon beaker. double-side tape on the inner surface of a 11.4.2 Container No. 2. Note the level of planchet. Place the planchet in an internal liquid in the container, and confirm on the proportional counter, and count for 100 min- analysis sheet whether leakage occurred dur- utes. ing transport. If a noticeable amount of 11.5.4 Calculate the activity of the sample leakage has occurred, either void the sample using Eq. 111–4 in Section 12.5. or use methods, subject to the approval of the Administrator, to correct the final re- 11.5.5 Determine the aliquot volume of sults. Transfer the contents to a 400-ml glass the sample solution from Section 11.4.10 to beaker. Add polonium-209 tracer solution to be analyzed for polonium-210, such that the the glass beaker in an amount approxi- aliquot contains an activity between 1 and 4 mately equal to the amount of polonium-210 picocuries. Use Eq. 111–5 in Section 12.6. expected in the total particulate sample. 11.6 Preparation of Silver Disc for Sponta- Record the activity of the tracer solution neous Electrodeposition. added. Add 16 M nitric acid to the beaker to 11.6.1 Clean both sides of the polished sil- digest and loosen the residue. ver disc with silver cleaner and with 11.4.3 Transfer the contents of the glass degreaser. beaker to the Teflon beaker containing the 11.6.2 Place disc on absorbent paper and glass fiber filter. Rinse the glass beaker with spray one side with epoxy spray enamel. This 16 M HNO3. If necessary, reduce the volume should be carried out in a well-ventilated in the beaker by evaporation until all of the area, with the disc lying flat to keep paint nitric acid HNO3 from the glass beaker has on one side only. Allow paint to dry for 24 been transferred to the Teflon beaker. hours before using disc for deposition. 11.4.4 Add 30 ml of 29 M HF to the Teflon 11.7 Sample Analysis. beaker and evaporate to near dryness on a 11.7.1 Add the aliquot of sample solution hot plate in a properly operating hood. from Section 11.4.10 to be analyzed for polo- NOTE: Do not allow the residue to go to nium-210, the volume of which was deter- dryness and overheat; this will result in loss mined in Section 11.5.5, to a suitable 200-ml of polonium. container to be placed in a constant temperature bath. 11.4.5 Repeat step 11.4.4 until the filter is dissolved. NOTE: Aliquot volume may require a larger 11.4.6 Add 100 ml of 16 M HNO3 to the res- container. idue in the Teflon beaker and evaporate to 11.7.2 If necessary, bring the volume to 100 near dryness. ml with 1 M HCl. If the aliquot volume ex- NOTE: Do not allow the residue to go to ceeds 100 ml, use total aliquot. dryness. 11.7.3 Add 200 mg of ascorbic acid and heat solution to 85 °C (185 °F) in a constant tem- 11.4.7 Add 50 ml of 16 M HNO3 and 10 ml of 12 M perchloric acid to the Teflon beaker and perature bath. heat until dense fumes of perchloric acid are 11.7.4 Suspend a silver disc in the heated evolved. solution using a glass or plastic rod with a 11.4.8 Repeat steps 11.4.4 to 11.4.7 as nec- hook inserted through the hole in the disc. essary until sample is completely dissolved. The disc should be totally immersed in the 11.4.9 Add 10 ml of 12 M HCl to the Teflon solution, and the solution must be stirred beaker and evaporate to dryness. Repeat ad- constantly, at all times during the plating ditions and evaporations several times. operation. Maintain the disc in solution for 3 11.4.10 Transfer the sample to a 250-ml hours. volumetric flask and dilute to volume with 3 11.7.5 Remove the silver disc, rinse with M HCl. deionized distilled water, and allow to air 11.5 Sample Screening. To avoid contami- dry at room temperature. nation of the alpha spectrometry system, 11.7.6 Place the disc, with deposition side check each sample as follows: (unpainted side) up, on a planchet and secure

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with double-side plastic tape. Place the plan- F= Average activity of polonium-209 in sam- chet with disc in alpha spectrometry system ple (from Section 10.2.4), in pCi. and count for 1000 minutes. Fi = activity of aliquot i of the polonium-209 tracer solution, in pCi. 12.0 Data Analysis and Calculations. L = Dilution factor (unitless). This is the 12.1 Nomenclature. volume of sample solution prepared (specified as 250 ml in Section 11.1.10) divided by A = Picocuries of polonium-210 in the Method the volume of the aliquot of sample solu- 5 sample (from Section 12.8). tion analyzed for polonium-210 (from Sec- AA = Picocuries of actinide added. tion 11.7.1). A = Volume of sample aliquot used, in ml L Mi = Phosphorous rock processing rate of the (specified in Section 11.5.1 as 1 ml). source being tested, during run i, Mg/hr. A = Aliquot to be analyzed, in ml. S Mk = Phosphate rock processed annually by BB = Procedure background counts measured source k, in Mg/yr. in polonium-209 spectral region. n = Number of calciners at the elemental BT = Polonium-209 tracer counts in sample. phosphorus plant. CT = Total counts in polonium-210 spectral P = Total activity of sample solution from region. Section 11.4.10, in pCi (see Eq. 111–4). D = Decay correction for time ‘‘t’’ (in days) Qsd = Volumetric flow rate of effluent from sample collection to sample counting, stream, as determined by Method 2, in given by: D = e¥0.005t dscm/hr. EC = Average counting efficiency of detector S = Annual polonium-210 emissions from the (from Section 10.1.8), as counts per disinte- entire facility, in curies/yr. gration. Vm(std) = Volume of air sample, as determined ECi = Counting efficiency of the detector for by Method 5, in dscm. aliquot i of the actinide working solution, Xk = Emission rate from source k, from Sec- counts per disintegration. tion 12.10, in curies/Mg. ¥12 EI = Average counting efficiency of the inter- 10 = Curies per picocurie. nal proportional counter, as determined in 2.22 = Disintegrations per minute per Section 10.3.4, counts per disintegration. picocurie. 250 = Volume of solution from Section 11.4.10, EIi = Counting efficiency of the internal proportional counter for aliquot i of the 100 in ml. pCi/ml actinide working solution, counts 12.2 Counting Efficiency. Calculate the per disintegration. counting efficiency of the detector for each EY = The fraction of polonium-209 recovered aliquot of the 1 pCi/ml actinide working soon the planchet (from Section 12.7). lution using Eq. 111–1.

− = CCSB ECi Eq. 111-1 222. AAT

Where: 12.3 Polonium-209 Tracer Solution Activ-

CB = Background counts in same peak area ity. Calculate the activity of each aliquot of as CS. the polonium-209 tracer solution using Eq. CS = Gross counts in actinide peak. 111–2. T = Counting time in minutes, specified in Section 10.1.6 as 1000 minutes.

− = CCSB Fi Eq. 111-2 222. ECiT

Where: CS = Gross counts of polonium-209 in the 4.88 MeV region of the spectrum in the count- CB = Background counts in the 4.88 MeV region of spectrum the in the counting ing time T. time T. T = Counting time, specified in Section 10.1.6 as 1000 minutes.

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12.4 Control Efficiency of Internal Propor- for each aliquot of the 100 pCi/ml actinide tional Counter. Calculate the counting effi- working solution using Eq. 111–3. ciency of the internal proportional counter

− = CCSB EIi Eq. 111-3 222. AAT

Where: T = Counting time in minutes, specified in Section 10.3.2 as 100 minutes. CB = Gross counts of procedure background. 12.5 Calculate the activity of the sample CS = Gross counts of standard. using Eq. 111–4.

250 ()CC− P = SB Eq. 111-4 222. EIATL

Where: 12.6 Aliquot Volume. Determine the ali-

CB = Total counts of procedure background. quot volume of the sample solution from (See Section 11.1). Section 11.4.10 to be analyzed for polonium- CS = Total counts of screening sample. 210 , such that the aliquot contains an activ- T = Counting time for sample and back- ity between 1 and 4 picocuries using Eq. 111– ground (which must be equal), in minutes 5. (specified in Section 11.5.3 as 100 minutes).

250 (desired picocuries in aliquot) A= Eq. 111-5 s P

12.7 Polonium-209 Recovery. Calculate the fraction of polonium-209 recovered on the planchet, EY, using Eq. 111–6.

− = BBTB EY Eq. 111-6 222. F EC T

Where: 12.8 Polonium-210 Activity. Calculate the T = Counting time, specified in Section 11.1 activity of polonium-210 in the Method 5 as 1000 minutes. sample (including glass fiber filter and acetone rinse) using Eq. 111–7.

()CC− L A = TB Eq. 111-7 222. Ey ETDC

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Where: 12.9 Emission Rate from Each Stack.

CB = Procedure background counts in polo- 12.9.1 For each test run, i, on a stack, cal- nium-210 spectral region. culate the measured polonium-210 emission T = Counting time, specified in Section 11.1 rate, RSi, using Eq. 111–8. as 1000 minutes for all alpha spectrometry sample and background counts.

− ()10 12 A Q = sd RSi Eq. 111-8 VMm() std i

12.9.2 Determine the average polonium-210 rate, Xk, from each source, k, by taking the emission rate from the stack, RS, by taking sum of the average emission rates from all the sum of the measured emission rates for stacks to which the source exhausts. all runs, and dividing by the number of runs 12.11 Annual Polonium-210 Emission Rate performed. from Entire Facility. Determine the annual 12.9.3 Repeat steps 12.9.1 and 12.9.2 for elemental phosphorus plant emissions of po- each stack of each calciner. lonium-210, S, using Eq. 111–9. 12.10 Emission Rate from Each Source. Determine the total polonium-210 emission

n ∑()XMkk S = k=1 Eq. 111-9 n

13.0 Method Performance. [Reserved] Many different types of facilities release radionuclides into air. These radionuclides 14.0 Pollution Prevention. [Reserved] differ in the chemical and physical forms, half-lives and type of radiation emitted. The 15.0 Waste Management. [Reserved] appropriate combination of sample extraction, collection and analysis for an indi- 16.0 References vidual radionuclide is dependent upon many 1. Blanchard, R.L. ‘‘Rapid Determination interrelated factors including the mixture of of Lead-210 and Polonium-210 in Environ- other radionuclides present. Because of this mental Samples by Deposition on Nickel.’’ wide range of conditions, no single method Anal. Chem., 38:189, pp. 189–192. February for monitoring or sample collection and 1966. analysis of a radionuclide is applicable to all types of facilities. Therefore, a series of 17.0 Tables, Diagrams, Flowcharts, and methods based on ‘‘principles of measure- Validation Data [Reserved] ment’’ are described for monitoring and sample collection and analysis which are appli- METHOD 114—TEST METHODS FOR MEASURING cable to the measurement of radionuclides RADIONUCLIDE EMISSIONS FROM STATIONARY found in effluent streams at stationary SOURCES sources. This approach provides the user 1. Purpose and Background with the flexibility to choose the most appropriate combination of monitoring and This method provides the requirements for: sample collection and analysis methods (1) Stack monitoring and sample collection which are applicable to the effluent stream methods appropriate for radionuclides; (2) to be measured. radiochemical methods which are used in determining the amounts of radionuclides col- 2. Stack Monitoring and Sample Collection lected by the stack sampling and; (3) quality Methods assurance methods which are conducted in Monitoring and sample collection methods conjunction with these measurements. These are described based on ‘‘principles of moni- methods are appropriate for emissions for toring and sample collection’’ which are ap- stationary sources. A list of references is plicable to the measurement of radionuclides provided. from effluent streams at stationary sources.

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Radionuclides of most elements will be in fluent stream. This may involve either gross the particulate form in these effluent radioactivity measurements or specific streams and can be readily collected using a radionuclide measurements. Gross measure- suitable filter media. Radionuclides of hy- ments shall be made in conformance with drogen, oxygen, carbon, nitrogen, the noble the conditions specified in Methods A–4, B–2 gases and in some circumstances iodine will and G–4. be in the gaseous form. Radionuclides of Sample collection means a procedure in these elements will require either the use of which the radionuclides are removed from an an in-line or off-line monitor to directly extracted sample of the effluent using a col- measure the radionuclides, or suitable lection media. These collection media in- sorbers, condensers or bubblers to collect the clude filters, absorbers, bubblers and con- radionuclides. densers. The collected sample is analyzed 2.1 Radionuclides as Particulates. The ex- using the methods described in Section 3. tracted effluent stream is passed through a 3. Radionuclide Analysis Methods filter media to remove the particulates. The filter must have a high efficiency for re- A series of methods based on ‘‘principles of moval of sub-micron particles. The guidance measurement’’ are described which are appli- in ANSI/HPS N13.1–1999 (section 6.6.2 Filter cable to the analysis of radionuclides col- media) shall be followed in using filter media lected from airborne effluent streams at sta- to collect particulates (incorporated by ref- tionary sources. These methods are applica- erence—see § 61.18 of this part). ble only under the conditions stated and 2.2 Radionuclides as Gases. within the limitations described. Some 2.2.1 The Radionuclide Tritium (H–3). methods specify that only a single radio- Tritium in the form of water vapor is col- nuclide be present in the sample or the lected from the extracted effluent sample by chemically separated sample. This condition sorption, condensation or dissolution tech- should be interpreted to mean that no other niques. Appropriate collectors may include radionuclides are present in quantities which silica gel, molecular sieves, and ethylene would interfere with the measurement. glycol or water bubblers. Also identified (Table 1) are methods for a Tritium in the gaseous form may be meas- selected list of radionuclides. The listed ured directly in the sample stream using radionuclides are those which are most com- Method B–1, collected as a gas sample or monly used and which have the greatest po- may be oxidized using a metal catalyst to tential for causing dose to members of the tritiated water and collected as described public. Use of methods based on principles of above. measurement other than those described in 2.2.2 Radionuclides of Iodine. Iodine is this section must be approved in advance of collected from an extracted sample by sorp- use by the Administrator. For radionuclides tion or dissolution techniques. Appropriate not listed in Table 1, any of the described collectors may include charcoal, impreg- methods may be used provided the user can nated charcoal, metal zeolite and caustic so- demonstrate that the applicability condi- lutions. tions of the method have been met. 2.2.3 Radionuclides of Argon, Krypton and The type of method applicable to the anal- Xenon. Radionuclides of these elements are ysis of a radionuclide is dependent upon the either measured directly by an in-line or off- type of radiation emitted, i.e., alpha, beta or line monitor, or are collected from the ex- gamma. Therefore, the methods described tracted sample by low temperature sorption below are grouped according to principles of techniques, Appropriate sorbers may include measurements for the analysis of alpha, beta charcoal or metal zeolite. and gamma emitting radionuclides. 2.2.4 Radionuclides of Oxygen, Carbon, Ni- 3.1 Methods for Alpha Emitting Radio- trogen and Radon. Radionuclides of these nuclides elements are measured directly using an in- 3.1.1 Method A–1, Radiochemistry-Alpha line or off-line monitor. Radionuclides of Spectrometry. carbon in the form of carbon dioxide may be Principle: The element of interest is sepa- collected by dissolution in caustic solutions. rated from other elements, and from the 2.3 Definition of Terms sample matrix using radiochemical tech- In-line monitor means a continuous meas- niques. The procedure may involve precipita- urement system in which the detector is tion, ion exchange, or solvent extraction. placed directly in or adjacent to the effluent Carriers (elements chemically similar to the stream. This may involve either gross radio- element of interest) may be used. The ele- activity measurements or specific radio- ment is deposited on a planchet in a very nuclide measurements. Gross measurements thin film by electrodeposition or by co- shall be made in conformance with the con- precipitation on a very small amount of car- ditions specified in Methods A–4, B–2 and G– rier, such as lanthanum fluoride. The depos- 4. ited element is then counted with an alpha Off-line monitor means a measurement sys- spectrometer. The activity of the nuclide of tem in which the detector is used to continu- interest is measured by the number of alpha ously measure an extracted sample of the ef- counts in the appropriate energy region. A

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correction for chemical yield and counting Applicability: Gross alpha determinations efficiency is made using a standardized ra- may be used to measure emissions of specific dioactive nuclide (tracer) of the same ele- radionuclides only (1) when it is known that ment. If a radioactive tracer is not available the sample contains only a single radio- for the element of interest, a predetermined nuclide, or the identity and isotopic ratio of chemical yield factor may be used. the radionuclides in the sample are well- Applicability: This method is applicable for known, and (2) measurements using either determining the activity of any alpha-emit- Method A–1, A–2 or A–5 have shown that this ting radionuclide, regardless of what other method provides a reasonably accurate radionuclides are present in the sample pro- measurement of the emission rate. Gross vided the chemical separation step produces alpha measurements are applicable to un- a very thin sample and removes all other identified mixtures of radionuclides only for radionuclides which could interfere in the the purposes and under the conditions de- spectral region of interest. APHA–605(2), scribed in section 3.7. APHA–601(3), ASTM– ASTM–D–3972(13). D–1943(10). 3.1.2 Method A–2, Radiochemistry-Alpha 3.1.5 Method A–5, Chemical Determina- Counting. tion of Uranium. Principle: The element of interest is sepa- Principle: Uranium may be measured rated from other elements, and from the chemically by either colorimetry or sample matrix using radiochemistry. The fluorometry. In both procedures, the sample procedure may involve precipitation, ion ex- is dissolved, the uranium is oxidized to the change, or solvent extraction. Carriers (ele- hexavalent form and extracted into a suit- ments chemically similar to the element of able solvent. Impurities are removed from interest) may be used. The element is depos- the solvent layer. For colorimetry, ited on a planchet in a thin film and counted dibenzoylmethane is added, and the uranium with an alpha counter. A correction for is measured by the absorbance in a colorim- chemical yield (if necessary) is made. The eter. For fluorometry, a portion of the solu- alpha count rate measures the total activity tion is fused with a sodium fluoride-lithium of all emitting radionuclides of the separated fluoride flux and the uranium is determined element. by the ultraviolet activated fluorescence of Applicability: This method is applicable for the fused disk in a fluorometer. the measurement of any alpha-emitting Applicability: This method is applicable to radionuclide, provided no other alpha emit- the measurements of emission rates of ura- ting radionuclide is present in the separated nium when the isotopic ratio of the uranium sample. It may also be applicable for deter- radionuclides is well known. ASTM–E– mining compliance, when other radio- 318(15), ASTM–D–2907(14). nuclides of the separated element are 3.1.6 Method A–6, Radon-222—Continuous present, provided that the calculated emis- Gas Monitor. sion rate is assigned to the radionuclide Principle: Radon-222 is measured directly in which could be present in the sample that a continuously extracted sample stream by has the highest dose conversion factor. IDO– passing the air stream through a calibrated 12096(18). scintillation cell. Prior to the scintillation 3.1.3 Method A–3, Direct Alpha Spectrom- cell, the air stream is treated to remove par- etry. ticulates and excess moisture. The alpha par- Principle: The sample, collected on a suit- ticles from radon-222 and its decay products able filter, is counted directly on an alpha strike a zinc sulfide coating on the inside of spectrometer. The sample must be thin the scintillation cell producing light pulses. enough and collected on the surface of the The light pulses are detected by a filter so that any absorption of alpha par- photomultiplier tube which generates elec- ticle energy in the sample or the filter, trical pulses. These pulses are processed by which would degrade the spectrum, is mini- the system electronics and the read out is in mal. pCi/l of radon-222. Applicability: This method is applicable to Applicability: This method is applicable to simple mixtures of alpha emitting radio- the measurement of radon-222 in effluent nuclides and only when the amount of par- streams which do not contain significant ticulates collected on the filter paper are rel- quantities of radon-220. Users of this method atively small and the alpha spectra is ade- should calibrate the monitor in a radon cali- quately resolved. Resolutions should be 50 bration chamber at least twice per year. The keV (FWHM) or better, ASTM–D–3084(16). background of the monitor should also be 3.1.4 Method A–4, Direct Alpha Counting checked periodically by operating the instru- (Gross alpha determination). ment in a low radon environment. EPA 520/1– Principle: The sample, collected on a suit- 89–009(24). able filter, is counted with an alpha counter. 3.1.7 Method A–7, Radon-222-Alpha Track The sample must be thin enough so that self- Detectors absorption is not significant and the filter Principle: Radon-222 is measured directly in must be of such a nature that the particles the effluent stream using alpha track detec- are retained on the surface. tors (ATD). The alpha particles emitted by

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radon-222 and its decay products strike a This method is applicable to unidentified small plastic strip and produce submicron mixtures of gaseous radionuclides only for damage tracks. The plastic strip is placed in the purposes and under the conditions de- a caustic solution that accentuates the dam- scribed in section 3.7. age tracks which are counted using a micro- 3.3 Methods for Non-Gaseous Beta Emit- scope or automatic counting system. The ting Radionuclides. number of tracks per unit area is correlated 3.3.1 Method B–3, Radiochemistry-Beta to the radon concentration in air using a Counting. conversion factor derived from data gen- Principle: The element of interest is sepa- erated in a radon calibration facility. rated from other elements, and from the Applicability: Prior approval from EPA is sample matrix by radiochemistry. This may required for use of this method. This method involve precipitation, distillation, ion ex- is only applicable to effluent streams which change, or solvent extraction. Carriers (ele- do not contain significant quantities of ments chemically similar to the element of radon-220, unless special detectors are used interest) may be used. The element is depos- to discriminate against radon-220. This ited on a planchet, and counted with a beta method may be used only when ATDs have counter. Corrections for chemical yield, and been demonstrated to produce data com- decay (if necessary) are made. The beta parable to data obtained with Method A–6. count rate determines the total activity of Such data should be submitted to EPA when all radionuclides of the separated element. requesting approval for the use of this meth- This method may also involve the od. EPA 520/1–89–009(24). radiochemical separation and counting of a 3.2 Methods for Gaseous Beta Emitting daughter element, after a suitable period of Radionuclides. ingrowth, in which case it is specific for the 3.2.1 Method B–1, Direct Counting in parent nuclide. Flow-Through Ionization Chambers. Applicability: This method is applicable for Principle: An ionization chamber con- measuring the activity of any beta-emitting taining a specific volume of gas which flows radionuclide, with a maximum energy great- at a given flow rate through the chamber is er than 0.2 MeV, provided no other radio- used. The sample (effluent stream sample) nuclide is present in the separated sample. acts as the counting gas for the chamber. APHA–608(5). The activity of the radionuclide is deter- 3.3.2 Method B–4, Direct Beta Counting mined from the current measured in the ion- (Gross beta determination). ization chamber. Principle: The sample, collected on a suit- Applicability: This method is applicable for able filter, is counted with a beta counter. measuring the activity of a gaseous beta- The sample must be thin enough so that self- emitting radionuclide in an effluent stream absorption corrections can be made. that is suitable as a counting gas, when no Applicability: Gross beta measurements are other beta-emitting nuclides are present. applicable only to radionuclides with max- DOE/EP–0096(17), NCRP–58(23). imum beta particle energies greater than 0.2 3.2.2 Method B–2, Direct Counting With MeV. Gross beta measurements may be used In-line or Off-line Beta Detectors. to measure emissions of specific radio- Principle: The beta detector is placed di- nuclides only (1) when it is known that the rectly in the effluent stream (in-line) or an sample contains only a single radionuclide, extracted sample of the effluent stream is and (2) measurements made using Method B– passed through a chamber containing a beta 3 show reasonable agreement with the gross detector (off-line). The activities of the beta measurement. Gross beta measurements radionuclides present in the effluent stream are applicable to mixtures of radionuclides are determined from the beta count rate, and only for the purposes and under the condi- a knowledge of the radionuclides present and tions described in section 3.7. APHA–602(4), the relationship of the gross beta count rate ASTM–D–1890(11). and the specific radionuclide concentration. 3.3.3 Method B–5, Liquid Scintillation Applicability: This method is applicable Spectrometry. only to radionuclides with maximum beta Principle: An aliquot of a collected sample particle energies greater then 0.2 MeV. This or the result of some other chemical separa- method may be used to measure emissions of tion or processing technique is added to a specific radionuclides only when it is known liquid scintillation ‘‘cocktail’’ which is that the sample contains only a single radio- viewed by photomultiplier tubes in a liquid nuclide or the identity and isotopic ratio of scintillation spectrometer. The spectrometer the radionuclides in the effluent stream are is adjusted to establish a channel or ‘‘win- well known. Specific radionuclide analysis of dow’’ for the pulse energy appropriate to the periodic grab samples may be used to iden- nuclide of interest. The activity of the nu- tify the types and quantities of radionuclides clide of interest is measured by the counting present and to establish the relationship be- rate in the appropriate energy channel. Cor- tween specific radionuclide analyses and rections are made for chemical yield where gross beta count rates. separations are made.

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Applicability: This method is applicable to stream by passing the gas stream through a any beta-emitting nuclide when no other chamber or cell containing the detector. radionuclide is present in the sample or the ASTM–D–2459(12), EMSL–LV–0539–17(19). separated sample provided that it can be in- 3.4.3 Method G–3, Single Channel Gamma corporated in the scintillation cocktail. This Spectrometry. method is also applicable for samples which Principle: The sample is counted with a contain more than one radionuclide but only thallium activated sodium iodide crystal. when the energies of the beta particles are The detector is coupled to a photomultiplier sufficiently separated so that they can be re- tube connected to a single channel analyzer. solved by the spectrometer. This method is The activity of a gamma emitting radio- most applicable to the measurement of low- nuclide is determined from the gamma energy beta emitters such as tritium and counts in the energy range for which the carbon-14. APHA–609(6), EML–LV–539–17(19). counter is set. 3.4 Gamma Emitting Radionuclides Applicability: This method is applicable to 3.4.1 Method G–1, High Resolution Gamma the measurement of a single gamma emit- Spectrometry. ting radionuclide. It is not applicable to mix- Principle: The sample is counted with a tures of radionuclides. The samples counted high resolution gamma detector, usually ei- may be in the form of particulate filters, ab- ther a Ge(Li) or a high purity Ge detector, sorbers, liquids or gas. The method can be connected to a multichannel analyzer or applied to the analysis of gaseous radio- computer. The gamma emitting radionuclides directly in an effluent stream by nuclides in the sample are measured from passing the gas stream through a chamber or the gamma count rates in the energy regions cell containing the detector. characteristic of the individual radionuclide. 3.4.4 Method G–4, Gross Gamma Counting. Corrections are made for counts contributed Principle: The sample is counted with a by other radionuclides to the spectral re- gamma detector usually a thallium acti- gions of the radionuclides of interest. vated sodium iodine crystal. The detector is Radiochemical separations may be made coupled to a photomultiplier tube and prior to counting but are usually not nec- gamma rays above a specific threshold en- essary. ergy level are counted. Applicability: This method is applicable to Applicability: Gross gamma measurements the measurement of any gamma emitting may be used to measure emissions of specific radionuclide with gamma energies greater radionuclides only when it is known that the than 20 keV. It can be applied to complex sample contains a single radionuclide or the mixtures of radionuclides. The samples identity and isotopic ratio of the radio- counted may be in the form of particulate nuclides in the effluent stream are well filters, absorbers, liquids or gases. The meth- known. When gross gamma measurements od may also be applied to the analysis of gas- are used to determine emissions of specific eous gamma emitting radionuclides directly radionuclides periodic measurements using in an effluent stream by passing the stream Methods G–1 or G–2 should be made to dem- through a chamber or cell containing the de- onstrate that the gross gamma measure- tector. ASTM–3649(9), IDO–12096(18). ments provide reliable emission data. This 3.4.2 Method G–2, Low Resolution Gamma method may be applied to analysis of gas- Spectrometry. eous radionuclides directly in an effluent Principle: The sample is counted with a low stream by placing the detector directly in or resolution gamma detector, a thallium acti- adjacent to the effluent stream or passing an vated sodium iodide crystal. The detector is extracted sample of the effluent stream coupled to a photomultiplier tube and con- through a chamber or cell containing the de- nected to a multichannel analyzer. The tector. gamma emitting radionuclides in the sample 3.5 Counting Methods. All of the above are measured from the gamma count rates in methods with the exception of Method A–5 the energy regions characteristic of the indi- involve counting the radiation emitted by vidual radionuclides. Corrections are made the radionuclide. Counting methods applica- for counts contributed by other radio- ble to the measurement of alpha, beta and nuclides to the spectral regions of the radio- gamma radiations are listed below. The nuclides of interest. Radiochemical separa- equipment needed and the counting prin- tion may be used prior to counting to obtain ciples involved are described in detail in less complex gamma spectra if needed. ASTM–3648(8). Applicability: This method is applicable to 3.5.1 Alpha Counting: the measurement of gamma emitting radio- • Gas Flow Proportional Counters. The alpha nuclides with energies greater than 100 keV. particles cause ionization in the counting It can be applied only to relatively simple gas and the resulting electrical pulses are mixtures of gamma emitting radionuclides. counted. These counters may be windowless The samples counted may be in the form of or have very thin windows. particulate filters, absorbers, liquids or gas. • Scintillation Counters. The alpha particles The method can be applied to the analysis of transfer energy to a scintillator resulting in gaseous radionuclides directly in an effluent a production of light photons which strike a

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photomultiplier tube converting the light • Single Channel Analyzers. Thallium acti- photons to electrical pulses which are count- vated sodium iodide crystals used with a sin- ed. The counters may involve the use of solid gle window analyzer. Pulses from the scintillation materials such as zinc sulfide or photomultiplier tubes are separated in a sin- liquid scintillation solutions. gle predetermined energy range. • Solid-State Counters. Semiconductor ma- 3.5.4 Calibration of Counters. Counters terials, such as silicon surface-barrier p-n are calibrated for specific radionuclide meas- junctions, act as solid ionization chambers. urements using a standard of the radio- The alpha particles interact which the detec- nuclide under either identical or very simi- tor producing electron hole pairs. The lar conditions as the sample to be counted. charged pair is collected by an applied elec- For gamma spectrometers a series of stand- trical field and the resulting electrical ards covering the energy range of interest pulses are counted. may be used to construct a calibration curve • Alpha Spectrometers. Semiconductor detectors used in conjunction with multi- relating gamma energy to counting effi- channel analyzers for energy discrimination. ciency. 3.5.2 Beta Counting: In those cases where a standard is not • Ionization Chambers. These chambers con- available for a radionuclide, counters may be tain the beta-emitting nuclide in gaseous calibrated using a standard with energy form. The ionization current produced is characteristics as similar as possible to the measured. radionuclide to be measured. For gross alpha • Geiger-Muller (GM) Counters-or Gas Flow and beta measurements of the unidentified Proportional Counters. The beta particles mixtures of radionuclides, alpha counters are cause ionization in the counting gas and the calibrated with a natural uranium standard resulting electrical pulses are counted. Pro- and beta counters with a cesium-137 stand- portional gas flow counters which are heav- ard. The standard must contain the same ily shielded by lead or other metal, and pro- weight and distribution of solids as the sam- vided with an anti-coincidence shield to re- ples, and be mounted in an identical manner. ject cosmic rays, are called low background If the samples contain variable amounts of beta counters. solids, calibration curves relating weight of • Scintillation Counters. The beta particles solids present to counting efficiency are pre- transfer energy to a scintillator resulting in pared. Standards other than those prescribed a production of light photons, which strike a may be used provided it can be shown that photomultiplier tube converting the light such standards are more applicable to the photon to electrical pulses which are count- radionuclide mixture measured. ed. This may involve the use of anthracene 3.6 Radiochemical Methods for Selected crystals, plastic scintillator, or liquid scin- Radionuclides. Methods for a selected list of tillation solutions with organic phosphors. radionuclides are listed in Table 1. The • Liquid Scintillation Spectrometers. Liquid radionuclides listed are those which are most scintillation counters which use two commonly used and which have the greatest photomultiplier tubes in coincidence to re- potential for causing doses to members of duce background counts. This counter may the public. For radionuclides not listed in also electronically discriminate among Table 1, methods based on any of the applica- pulses of a given range of energy. ble ‘‘principles of measurement’’ described in 3.5.3 Gamma Counting: section 3.1 through 3.4 may be used. • Low-Resolution Gamma Spectrometers. The gamma rays interact with thallium acti- 3.7 Applicability of Gross Alpha and Beta vated sodium iodide or cesium iodide crystal Measurements to Unidentified Mixtures of resulting in the release of light photons Radionuclides. Gross alpha and beta meas- which strike a photomultiplier tube con- urements may be used as a screening meas- verting the light pulses to electrical pulses urement as a part of an emission measure- proportional to the energy of the gamma ment program to identify the need to do spe- ray. Multi-channel analyzers are used to sep- cific radionuclide analyses or to confirm or arate and store the pulses according to the verify that unexpected radionuclides are not energy absorbed in the crystal. being released in significant quantities. • High-Resolution gamma Spectrometers. Gross alpha (Method A–4) or gross beta Gamma rays interact with a lithium-drifted (Methods B–2 or B–4) measurements may also (Ge(Li)) or high-purity germanium (HPGe) be used for the purpose of comparing the semiconductor detectors resulting in a pro- measured concentrations in the effluent duction of electron-hole pairs. The charged stream with the limiting ‘‘Concentration pair is collected by an applied electrical Levels for Environmental Compliance’’ in field. A very stable low noise preamplifier table 2 of appendix E. For unidentified mix- amplifies the pulses of electrical charge re- tures, the measured concentration value sulting from the gamma photon interactions. shall be compared with the lowest environ- Multichannel analyzers or computers are mental concentration limit for any radio- used to separate and store the pulses accord- nuclide which is not known to be absent ing to the energy absorbed in the crystal. from the effluent stream.

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TABLE 1—LIST OF APPROVED METHODS FOR 4.1 The organizational structure, func- SPECIFIC RADIONUCLIDES tional responsibilities, levels of authority and lines of communications for all activi- Radionuclide Approved methods of analysis ties related to the emissions measurement program shall be identified and documented. Am-241 ...... A–1, A–2, A–3, A–4 4.2 Administrative controls shall be pre- Ar-41 ...... B–1, B–2, G–1, G–2, G–3, G–4 scribed to ensure prompt response in the Ba-140 ...... G–1, G–2, G–3, G–4 Br-82 ...... G–1, G–2, G–3, G–4 event that emission levels increase due to C-11 ...... B–1, B–2, G–1, G–2, G–3, G–4 unplanned operations. C-14 ...... B–5 4.3 The sample collection and analysis Ca-45 ...... B–3, B–4, B–5 procedures used in measuring the emissions Ce-144 ...... G–1, G–2, G–3, G–4 shall be described including where applica- Cm-244 ...... A–1, A–2, A–3, A–4 ble: Co-60 ...... G–1, G–2, G–3, G–4 4.3.1 Identification of sampling sites and Cr-51 ...... G–1, G–2, G–3, G–4 Cs-134 ...... G–1, G–2, G–3, G–4 number of sampling points, including the ra- Cs-137 ...... G–1, G–2, G–3, G–4 tionale for site selections. Fe-55 ...... B–5, G–1 4.3.2 A description of sampling probes and Fe-59 ...... G–1, G–2, G–3, G–4 representativeness of the samples. Ga-67 ...... G–1, G–2, G–3, G–4 4.3.3 A description of any continuous H-3 (H2O) ...... B–5 monitoring system used to measure emis- H-3 (gas) ...... B–1 sions, including the sensitivity of the sys- I-123 ...... G–1, G–2, G–3, G–4 tem, calibration procedures and frequency of I-125 ...... G–1 I-131 ...... G–1, G–2, G–3, G–4 calibration. In-113m ...... G–1, G–2, G–3, G–4 4.3.4 A description of the sample collec- Ir-192 ...... G–1, G–2, G–3, G–4 tion systems for each radionuclide measured, Kr-85 ...... B–1, B–2, B–5, G–1, G–2, G–3, G–4 including frequency of collection, calibration Kr-87 ...... B–1, B–2, G–1, G–2, G–3, G–4 procedures and frequency of calibration. Kr-88 ...... B–1, B–2, G–1, G–2, G–3, G–4 4.3.5 A description of the laboratory anal- Mn-54 ...... G–1, G–2, G–3, G–4 ysis procedures used for each radionuclide Mo-99 ...... G–1, G–2, G–3, G–4 N-13 ...... B–1, B–2, G–1, G–2, G–3, G–4 measured, including frequency of analysis, O-15 ...... B–1, B–2, G–1, G–2, G–3, G–4 calibration procedures and frequency of cali- P-32 ...... B–3, B–4, B–5 bration. Pm-147 ...... B–3, B–4, B–5 4.3.6 A description of the sample flow rate Po-210 ...... A–1, A–2, A–3, A–4 measurement systems or procedures, includ- Pu-238 ...... A–1, A–2, A–3, A–4 ing calibration procedures and frequency of Pu-239 ...... A–1, A–2, A–3, A–4 calibration. Pu-240 ...... A–1, A–2, A–3, A–4 Ra–226 ...... A–1, A–2, G–1, G–2 4.3.7 A description of the effluent flow S-35 ...... B–5 rate measurement procedures, including fre- Se-75 ...... G–1, G–2, G–3, G–4 quency of measurements, calibration proce- Sr-90 ...... B–3, B–4, B–5 dures and frequency of calibration. Tc-99 ...... B–3, B–4, B–5 4.4 The objectives of the quality assur- Te-201 ...... G–1, G–2, G–3, G–4 ance program shall be documented and shall Uranium (total A–1, A–2, A–3, A–4 alpha). state the required precision, accuracy and Uranium (Isotopic) .. A–1, A–3 completeness of the emission measurement Uranium (Natural) .. A–5 data including a description of the proce- Xe-133 ...... G–1 dures used to assess these parameters. Accu- Yb-169 ...... G–1, G–2, G–3, G–4 racy is the degree of agreement of a meas- Zn-65 ...... G–1, G–2, G–3, G–4 urement with a true or known value. Preci- sion is a measure of the agreement among 4. Quality Assurance Methods individual measurements of the same param- Each facility required to measure their eters under similar conditions. Completeness radionuclide emissions shall conduct a qual- is a measure of the amount of valid data ob- ity assurance program in conjunction with tained compared to the amount expected the radionuclide emission measurements. under normal conditions. This program shall assure that the emission 4.5 A quality control program shall be es- measurements are representative, and are of tablished to evaluate and track the quality known precision and accuracy and shall in- of the emissions measurement data against clude administrative controls to assure preset criteria. The program should include prompt response when emission measure- where applicable a system of replicates, ments indicate unexpectedly large emis- spiked samples, split samples, blanks and sions. The program shall consist of a system control charts. The number and frequency of of policies, organizational responsibilities, such quality control checks shall be identi- written procedures, data quality specifica- fied. tions, audits, corrective actions and reports. 4.6 A sample tracking system shall be es- This quality assurance program shall include tablished to provide for positive identifica- the following program elements: tion of samples and data through all phases

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of the sample collection, analysis and report- 4.7 Regular maintenance, calibration and ing system. Sample handling and preserva- field checks shall be performed for each sam- tion procedures shall be established to main- pling system in use by satisfying the require- tain the integrity of samples during collec- ments found in Table 2: Maintenance, Cali- tion, storage and analysis. bration and Field Check Requirements.

TABLE 2—MAINTENANCE, CALIBRATION AND FIELD CHECK REQUIREMENTS

Sampling system components Frequency of activity

Cleaning of thermal anemometer elements ...... As required by application. Inspect pitot tubes for contaminant deposits ...... At least annually. Inspect pitot tube systems for leaks ...... At least annually. Inspect sharp-edged nozzles for damage ...... At least annually or after maintenance that could cause damage. Check nozzles for alignment, presence of deposits, or other Annually. potentially degrading factors. Check transport lines of HEPA-filtered applications to deter- Annually. mine if cleaning is required. Clean transport lines ...... Visible deposits for HEPA-filtered applications. Mean mass of deposited material exceeds 1g/m2 for other applications. Inspect or test the sample transport system for leaks ...... At least annually. Check mass flow meters of sampling systems with a sec- At least quarterly. ondary or transfer standard. Inspect rotameters of sampling systems for presence of foreign At the start of each sampling period. matter. Check response of stack flow rate systems ...... At least quarterly. Calibration of flow meters of sampling systems ...... At least annually. Calibration of effluent flow measurement devices ...... At least annually. Calibration of timing devices ...... At least annually.

4.8 Periodic internal and external audits (3) Ibid, Method 601, ‘‘Tentative Method of shall be performed to monitor compliance Analysis for Gross Alpha Radioactivity Con- with the quality assurance program. These tent of the Atmosphere’’. audits shall be performed in accordance with (4) Ibid, Method 602, ‘‘Tentative Method of written procedures and conducted by per- the Analysis for Gross Beta Radioactivity sonnel who do not have responsibility for Content of the Atmosphere’’. performing any of the operations being au- (5) Ibid, Method 608, ‘‘Tentative Method of dited. Analysis for Strontium-90 Content of Atmos- 4.9 A corrective action program shall be pheric Particulate Matter’’. established including criteria for when cor- (6) Ibid, Method 609, ‘‘Tentative Method of rective action is needed, what corrective ac- Analysis for Tritium Content of the Atmos- tions will be taken and who is responsible for phere’’. taking the corrective action. (7) Ibid, Method 603, ‘‘Tentative Method of 4.10 Periodic reports to responsible man- Analysis for Iodine-131 Content of the At- agement shall be prepared on the perform- mosphere’’. ance of the emissions measurements pro- (8) American Society for Testing and Mate- gram. These reports should include assess- rials, 1986 Annual Book ASTM Standards, ment of the quality of the data, results of Designation D–3648–78, ‘‘Standard Practices audits and description of corrective actions. for the Measurement of Radioactivity’’. 4.11 The quality assurance program American Society for Testing and Materials, should be documented in a quality assurance Philadelphia, PA (1986). project plan that should address each of the (9) Ibid, Designation D–3649–85, ‘‘Standard above requirements. Practice for High Resolution Gamma Spec- trometry’’. 5. References (10) Ibid, Designation D–1943–81, ‘‘Standard (1) American National Standards Institute Test Method for Alpha Particle Radioac- ‘‘Guide to Sampling Airborne Radioactive tivity of Water’’. Materials in Nuclear Facilities’’, ANSI– (11) Ibid, Designation D–1890–81, ‘‘Standard N13.1–1969, American National Standards In- Test Method for Beta Particle Radioactivity stitute, New York, New York (1969). of Water’’. (2) American Public Health Association, (12) Ibid, Designation D–2459–72, ‘‘Standard ‘‘Methods of Air Sampling’’, 2nd Edition, Test Method for Gamma Spectrometry of Method 605, ‘‘Tentative Method of Analysis Water’’. for Plutonium Content of Atmospheric Par- (13) Ibid, Designation D–3972–82, ‘‘Standard ticulate Matter’’. American Public Health Test Method for Isotopic Uranium in Water Association, New York, NY (1977). by Radiochemistry’’.

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(14) Ibid, Designation D–2907–83, ‘‘Standard (b) Each mine vent exhaust flow rate shall Test Methods for Microquantities of Ura- be measured at least 4 times per year. nium in Water by Fluorometry’’. (c) A weekly radon-222 emission rate for (15) Ibid, Designation E–318, ‘‘Standard the mine shall be calculated and recorded Test Method for Uranium in Aqueous Solu- weekly as follows:

tions by Colorimetry’’. Aw= C1Q1T1 + C2Q2T2 + . . . CiQiTi (16) Ibid, Designation D–3084–75, ‘‘Standard Where: Practice for Alpha Spectrometry of Water’’. Aw = Total radon-222 emitted from the mine (17) Corley, J.P. and C.D. Corbit, ‘‘A Guide during week (Ci) for Effluent Radiological Measurements at Ci = Average radon-222 concentration in mine DOE Installations’’, DOE/EP–0096, Pacific vent i(Ci/m3) Northwest Laboratories, Richland, Wash- Qi = Volumetric flow rate from mine vent ington (1983). i(m3/hr) (18) Department of Energy, ‘‘RESL Analyt- Ti = Hours of mine ventilation system oper- ical Chemistry Branch Procedures Manual’’, ation during week for mine vent i(hr) IDO–12096, U.S. Department of Energy, Idaho (d) The annual radon-222 emission rate is Falls, Idaho (1982). the sum of the weekly emission rates during (19) Environmental Protection Agency, a calendar year. ‘‘Radiochemical Analytical Procedures for 1.1.2 Periodic Measurement. This method Analysis of Environmental Samples’’, is applicable only to mines that continu- EMSL–LV–0539–17, U.S. Environmental Pro- ously operate their ventilation system ex- tection Agency, Environmental Monitoring cept for extended shutdowns. Mines which and Support Laboratory, Las Vegas, Nevada start up and shut down their ventilation sys- (1979). tem frequently must use the continuous (20) Environmental Protection Agency, measurement method describe in Section ‘‘Radiochemistry Procedures Manual’’, EPA 1.1.1 above. Emission rates determined using 520/5–84–006, Eastern Environmental Radi- periodic measurements shall be measured ation Facility, Montgomery, Alabama (1984). and calculated as follows: (21) National Council on Radiation Protec- (a) The radon-222 shall be continuously tion and Measurements, NCRP Report No. 50, measured at each mine vent for at least one ‘‘Environmental Radiation Measurements’’, week every three months. National Council on Radiation Protection (b) Each mine vent exhaust flow rate shall and Measurement, Bethesda, Maryland be measured at least once during each of the (1976). radon-222 measurement periods. (22) Ibid, Report No. 47, ‘‘Tritium Measure- (c) A weekly radon-222 emission rate shall ment Techniques’’. (1976). be calculated for each weekly period accord- (23) Ibid, Report No. 58 ‘‘A Handbook of Ra- ing to the method described in Section 1.1.1. dioactivity Measurement Procedures’’ (1985). In this calculation T = 168 hr. (24) Environmental Protection Agency, (d) The annual radon-222 emission rate ‘‘Indoor Radon and Radon Decay Product from the mine should be calculated as fol- Measurement Protocols’’, EPA 520/1–89–009, lows: U.S. Environmental Protection Agency, − Washington, DC (1989). = 52 Ws + + ⋅⋅⋅ Ay ()AAww12 A wi METHOD 115—MONITORING FOR RADON-222 n EMISSIONS Where: A = Annual radon-222 emission rate from This appendix describes the monitoring y the mine(Ci) methods which must be used in determining A = Weekly radon-222 emission rate during the radon-222 emissions from underground wi the measurement period i (Ci) uranium mines, uranium mill tailings piles, n = Number of weekly measurement periods phosphogypsum stacks, and other piles of per year waste material emitting radon. Ws = Number of weeks during the year that 1. Radon-222 Emissions from Underground Ura- the mine ventilation system is shut down nium Mine Vents in excess of 7 consecutive days, i.e. the 1.1 Sampling Frequency and Calculation sum of the number of weeks each shut of Emissions. Radon-222 emissions from un- down exceeds 7 days derground uranium mine vents shall be de- 1.2 Test Methods and Procedures termined using one of the following methods: Each underground mine required to test its 1.1.1 Continuous Measurement. These emissions, unless an equivalent or alter- measurements shall be made and the emis- native method has been approved by the Ad- sions calculated as follows: ministrator, shall use the following test (a) The radon-222 concentration shall be methods: continuously measured at each mine vent 1.2.1 Test Method 1 of appendix A to part whenever the mine ventilation system is 60 shall be used to determine velocity tra- operational. verses. The sampling point in the duct shall

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be either the centroid of the cross section or measurements in some areas of a region. The the point of average velocity. minimum number of flux measurements con- 1.2.2 Test Method 2 of appendix A to part sidered necessary to determine a representa- 60 shall be used to determine velocity and tive mean radon flux value for each type of volumetric flow rates. region on an operating pile is: 1.2.3 Test Methods A–6 or A–7 of appendix (a) Water covered area—no measurements B, Method 114 to part 61 shall be used for the required as radon flux is assumed to be analysis of radon–222. Use of Method A–7 re- zero, quires prior approval of EPA based on condi- (b) Water saturated beaches—100 radon flux tions described in appendix B. measurements, 1.2.4 A quality assurance program shall be (c) Loose and dry top surface—100 radon conducted in conformance with the programs flux measurements, described for Continuous Radon Monitors (d) Sides—100 radon flux measurements, ex- and Alpha Track Detectors in EPA 520/1–89– cept where earthern material is used in 009. (2) dam construction. 2. Radon–222 Emissions from Uranium Mill For a mill tailings pile after disposal Tailings Piles which consists of only one region a minimum 2.1 Measurement and Calculation of of 100 measurements are required. Radon Flux from Uranium Mill Tailings 2.1.4 Restrictions to Radon Flux Measure- Piles. ments. The following restrictions are placed 2.1.1 Frequency of Flux Measurement. A on making radon flux measurements: single set of radon flux measurements may (a) Measurements shall not be initiated be made, or if the owner or operator chooses, within 24 hours of a rainfall. more frequent measurements may be made (b) If a rainfall occurs during the 24 hour over a one year period. These measurements measurements period, the measurement may involve quarterly, monthly or weekly is invalid if the seal around the lip of the intervals. All radon measurements shall be collector has washed away or if the col- made as described in paragraphs 2.1.2 lector is surrounded by water. through 2.1.6 except that for measurements (c) Measurements shall not be performed if made over a one year period, the require- the ambient temperature is below 35 °F ment of paragraph 2.1.4(c) shall not apply. or if the ground is frozen. The mean radon flux from the pile shall be 2.1.5 Areas of Pile Regions. The approxi- the arithmetic mean of the mean radon flux mate area of each region of the pile shall be for each measurement period. The weather determined in units of square meters. conditions, moisture content of the tailings 2.1.6 Radon Flux Measurement. Measuring and area of the pile covered by water exist- radon flux involves the adsorption of radon ing at the time of the measurement shall be on activated charcoal in a large-area col- chosen so as to provide measurements rep- lector. The radon collector is placed on the resentative of the long term radon flux from surface of the pile area to be measured and the pile and shall be subject to EPA review allowed to collect radon for a time period of and approval. 24 hours. The radon collected on the charcoal 2.1.2 Distribution of Flux Measurements. is measured by gamma-ray spectroscopy. The distribution and number of radon flux The detailed measurement procedure pro- measurements required on a pile will depend vided in appendix A of EPA 520/5–85–0029(1) on clearly defined areas of the pile (called re- shall be used to measure the radon flux on gions) that can have significantly different uranium mill tailings, except the surface of radon fluxes due to surface conditions. The the tailings shall not be penetrated by the mean radon flux shall be determined for each lip of the radon collector as directed in the individual region of the pile. Regions that procedure, rather the collector shall be care- shall be considered for operating mill fully positioned on a flat surface with soil or tailings piles are: tailings used to seal the edge. (a) Water covered areas, 2.1.7 Calculations. The mean radon flux (b) Water saturated areas (beaches), for each region of the pile and for the total (c) Dry top surface areas, and pile shall be calculated and reported as fol- (d) Sides, except where earthen material is lows: used in dam construction. (a) The individual radon flux calculations For mill tailings after disposal the pile shall be made as provided in appendix A shall be considered to consist of only one re- EPA 86 (1). The mean radon flux for each gion. region of the pile shall be calculated by 2.1.3 Number of Flux Measurements. summing all individual flux measure- Radon flux measurements shall be made ments for the region and dividing by the within each region on the pile, except for total number of flux measurements for those areas covered with water. Measure- the region. ments shall be made at regularly spaced lo- (b) The mean radon flux for the total ura- cations across the surface of the region, real- nium mill tailings pile shall be cal- izing that surface roughness will prohibit culated as follows.

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+ ⋅⋅⋅ ⋅⋅⋅ a representative mean radon flux value for = JA11 JA 2 2 JAii each type of region is: Js (a) Water covered area—no measurements At required as radon flux is assumed to be Where: zero, 2 (b) Water saturated beaches—50 radon flux Js = Mean flux for the total pile (pCi/m -s) 2 measurements, Ji = Mean flux measured in region i (pCi/m - s) (c) Loose and dry top surface—100 radon flux measurements, A = Area of region i (m2) i (d) Hard-packed roadways—50 radon flux A = Total area of the pile (m2) t measurements, and 2.1.8 Reporting. The results of individual (e) Sides—100 radon flux measurements. flux measurements, the approximate loca- A minimum of 300 measurements are re- tions on the pile, and the mean radon flux quired. A stack that has no water cover can for each region and the mean radon flux for be considered to consist of two regions, top the total stack shall be included in the emis- and sides, and will require a minimum of sion test report. Any condition or unusual only 200 measurements. event that occurred during the measure- 3.1.4 Restrictions to Radon Flux Measure- ments that could significantly affect the re- ments. The following restrictions are placed sults should be reported. on making radon flux measurements: 3.0 Radon-222 Emissions from Phosphogypsum Stacks. (a) Measurements shall not be initiated within 24 hours of a rainfall. 3.1 Measurement and Calculation of the (b) If a rainfall occurs during the 24 hour Mean Radon Flux. Radon flux measurements measurement period, the measurement is shall be made on phosphogypsum stacks as invalid if the seal around the lip of the described below: collector has washed away or if the col- 3.1.1 Frequency of Measurements. A sin- lector is surrounded by water. gle set of radon flux measurements may be (c) Measurements shall not be performed if made after the phosphogypsum stack be- the ambient temperature is below 35 °F comes inactive, or if the owner or operator or if the ground is frozen. chooses, more frequent measurements may be made over a one year period. These meas- 3.1.5 Areas of Stack Regions. The approxi- urements may involve quarterly, monthly or mate area of each region of the stack shall weekly intervals. All radon measurements be determined in units of square meters. shall be made as described in paragraphs 3.1.2 3.1.6 Radon Flux Measurements. Meas- through 3.1.6 except that for measurements uring radon flux involves the adsorption of radon on activated charcoal in a large-area made over a one year period, the require- collector. The radon collector is placed on ment of paragraph 3.1.4(c) shall not apply. the surface of the stack area to be measured For measurements made over a one year pe- and allowed to collect radon for a time period, the radon flux shall be the arithmetic riod of 24 hours. The radon collected on the mean of the mean radon flux for each meas- charcoal is measured by gamma-ray spec- urement period. troscopy. The detailed measurement proce- 3.1.2 Distribution and Number of Flux dure provided in appendix A of EPA 520/5–85– Measurements. The distribution and number 0029(1) shall be used to measure the radon of radon flux measurements required on a flux on phosphogypsum stacks, except the stack will depend on clearly defined areas of surface of the phosphogypsum shall not be the stack (called regions) that can have sig- penetrated by the lip of the radon collector nificantly different radon fluxes due to sur- as directed in the procedure, rather the col- face conditions. The mean radon flux shall be lector shall be carefully positioned on a flat determined for each individual region of the surface with soil or phosphogypsum used to stack. Regions that shall be considered are: seal the edge. (a) Water covered areas, 3.1.7 Calculations. The mean radon flux (b) Water saturated areas (beaches), for each region of the phosphogypsum stack (c) Loose and dry top surface areas, and for the total stack shall be calculated (d) Hard-packed roadways, and and reported as follows: (e) Sides. (a) The individual radon flux calculations 3.1.3 Number of Flux Measurements. shall be made as provided in appendix A Radon flux measurements shall be made EPA 86 (1). The mean radon flux for each within each region on the phosphogypsum region of the stack shall be calculated by stack, except for those areas covered with summing all individual flux measure- water. Measurements shall be made at regu- ments for the region and dividing by the larly spaced locations across the surface of total number of flux measurements for the region, realizing that surface roughness the region. will prohibit measurements in some areas of (b) The mean radon flux for the total a region. The minimum number of flux meas- phosphogypsum stack shall be calculated urements considered necessary to determine as follows.

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+ + ⋅⋅⋅ check for inadvertent contamination of the = JA11 JA 2 2 JAii detector or other changes affecting the back- Js ground. The unexposed charcoal comprising At the blank is changed with each new batch of Where: charcoal used. J = Mean flux for the total stack (pCi/m2-s) s D. INTERNAL QUALITY CONTROL CHECKS AND J = Mean flux measured in region i (pCi/m2- i FREQUENCY s) 2 Ai = Area of region i (m ) The charcoal from every tenth exposed At = Total area of the stack canister shall be recounted. Five percent of 3.1.8 Reporting. The results of individual the samples analyzed shall be either blanks flux measurements, the approximate loca- (charcoal having no radioactivity added) or tions on the stack, and the mean radon flux samples spiked with known quantities of ra- for each region and the mean radon flux for dium-226. the total stack shall be included in the emis- E. DATA PRECISION, ACCURACY, AND sion test report. Any condition or unusual COMPLETENESS event that occurred during the measurements that could significantly affect the re- The precision, accuracy, and completeness sults should be reported. of measurements and analyses shall be with- 4.0 Quality Assurance Procedures for in the following limits for samples meas- Measuring Rn–222 Flux uring greater than 1.0 pCi/m2¥s. (a) Precision: 10% A. SAMPLING PROCEDURES (b) Accuracy: ±10% Records of field activities and laboratory (c) Completeness: at least 85% of the meas- measurements shall be maintained. The fol- urements must yield useable results. lowing information shall be recorded for 5.0 REFERENCES each charcoal canister measurement: (a) Site (1) Hartley, J.N. and Freeman, H.D., (b) Name of pile ‘‘Radon Flux Measurements on Gardinier (c) Sample location and Royster phosphogypsum Piles Near (d) Sample ID number Tampa and Mulberry, Florida,’’ U.S. Envi- (e) Date and time on ronmental Protection Agency Report, EPA (f) Date and time off 520/5–85–029, January 1986. (g) Observations of meteorological condi- (2) Environmental Protection Agency, tions and comments ‘‘Indoor Radon and Radon Decay Product Measurement Protocols’’, EPA 520/1–89–009, Records shall include all applicable infor- U.S. Environmental Protection Agency, mation associated with determining the Washington, DC. (1989). sample measurement, calculations, observations, and comments. [38 FR 8826, Apr. 6, 1973] EDITORIAL NOTE: For FEDERAL REGISTER ci- AMPLE CUSTODY B. S tations affecting appendix B, see the List of Custodial control of all charcoal samples CFR Sections Affected, which appears in the exposed in the field shall be maintained in Finding Aids section of the printed volume accordance with EPA chain-of-custody field and at www.govinfo.gov. procedures. A control record shall document all custody changes that occur between the APPENDIX C TO PART 61—QUALITY field and laboratory personnel. ASSURANCE PROCEDURES

C. CALIBRATION PROCEDURES AND FREQUENCY Procedure 1—Determination of Adequate Chromatographic Peak Resolution The radioactivity of two standard charcoal sources, each containing a carefully deter- In this method of dealing with resolution, mined quantity of radium-226 uniformly dis- the extent to which one chromatographic tributed through 180g of activated charcoal, peak overlaps another is determined. shall be measured. An efficiency factor is For convenience, consider the range of the computed by dividing the average measured elution curve of each compound as running radioactivity of the two standard charcoal from ¥2s to + 2s. This range is used in other sources, minus the background, in cpm by resolution criteria, and it contains 95.45 per- the known radioactivity of the charcoal cent of the area of a normal curve. If two sources in dpm. The same two standard char- peaks are separated by a known distance, b, coal sources shall be counted at the begin- one can determine the fraction of the area of ning and at the end of each day’s counting as one curve that lies within the range of the a check of the radioactivity counting equip- other. The extent to which the elution curve ment. A background count using unexposed of a contaminant compound overlaps the charcoal should also be made at the begin- curve of a compound that is under analysis is ning and at the end of each counting day to found by integrating the contaminant curve

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