GC/MS Analysis (Semi-Volatiles) (Method 625/8270C)

Description

Method 625/8270C is used to determine Semi-Volatile organic components in a variety of matrices. (See SOP #6010, 6020 for preparatory information) These methods are applicable to nearly all types of samples, including sludges, oily wastes, soils, sediments, extracts and waters.

Semi-Volatile components are introduced into the GC by direct injection post solvent extraction or dilution. The GC is temperature programmed to allow a narrow bore capillary column to separate the compounds, which are measured, via a quadruple mass spectrometer (MS).

Method sensitivity varies by matrix. The estimated quantitation limits on average are 0.5 mg/Kg (wet weight) for soils, 1-200mg/Kg (wet weight) for wastes and 10 g/L for waters and extracts.

Precautions

Compressed gases (see procedure 0040) Corrosive (see procedure 0020) General Requirements (see procedure 0010) Solvents (see procedure 0030)

Sample Preservation and Preparation:

Samples to be analyzed for semi-volatiles must be collected in a glass container with a Teflon-lined lid. Samples for semi-volatiles must be transported and retained under refrigeration at 4°C. Soil samples may be held for 14 days under refrigeration. Aqueous samples may be held for 7 days prior to extraction and 40 days prior to analysis. Store the sample extracts at –10°C, protected from light, in sealed vials.

Interferences

Interferences can exist as a result of poor extraction techniques, contaminated reagents and instrumentation cleanliness. All glassware associated with the extraction and concentration processes must be thoroughly cleaned and oven baked prior to use. Caution must be taken to avoid any plastic sample or reagent containers to avoid possible phthalate contamination. A rigorous preventative maintenance routine is mandatory to maintain instrument performance.

1 Procedure 6600 Revised 04/07

Apparatus and Materials

-Mass Spectrometer: HP 5973 Quadrapole, 6890 GC, 7683 ALS -Column: RTX-5ms, 30M, 0.25mmID and 0.5m film thickness -Gas Chromatograph: HP 6890, with 7683 AutoSampler -GC/MS interface: Direct coupling of column to mass spectrometer -Data System: HP Chemstation 1701B -10L syringes

Reagents and Standards

-Methylene Chloride

Sodium Hydroxide,pellets

Sulfuric Acid,concentrated

-Standards are purchased as certified solutions

-Surrogates:

. Nitrobenzene-d5 100g/mL . 2-Fluorobiphenyl 100g/mL

. Terphenyl-d14 100g/mL

. Phenol-d6 200g/mL . 2-Fluorophenol 200g/mL . 2,4,6- Tribromphenol 200g/mL

-Internal Standards: Prepare standard from purchased stock Prior to injection a 1mL extract is spiked with 10L of a 4000 spiked with 10L of a standard resulting in 40g/mL of: . 1,4-Dichlorobenzene-d4 . Naphthalene-d8 . Acenaphthene-d10 . Phenanthrene-d10 . Chrysene-d12 . Perylene-d12

-DFTPP Standard: Prepare standard from purchased stock by diluting 1.0mL of 1.0mg/mL with MeCl2 to 20mL. 50g/mL in Methylene Chloride is used as tuning standard. 1.0mL is injected.

-Calibration Standards: Calibration standards at a minimum five concentration levels are prepared. One standard must be at or near, but above the method detection limit. Calibration standards are prepared weekly as required and are spiked with 10L of I.S. 2 Procedure 6600 Revised 04/07

-Prepare calibration standards from purchased stock of 2000g/mL by diluting

1.0mL to 10mL in MeCl2 to deliver 200g/L secondary stock solution. Table I provides dilution details for the following calibration standards: F-Scan TCLP Herbicides and/or Pesticides Base Neutral Acid Benzidines PAH’s 437 Additional Compounds

-Matrix Spike Standard: Matrix Spike compounds are spiked prior to extraction include:

Phenol 200g/mL 1,2,4-Trichlorobenzene 100mg/mL 2-Chlorophenol 200g/mL Acenaphthene 100mg/mL 4-Methyl-3-Chlorophenol 200g/mL 2,4-Dinitrotoluene 100mg/mL 4-Nitrophenol 200g/mL Pyrene 100mg/mL Pentachlorophenol 200g/mL N-Nitrosodi-n-Propylamine 100mg/mL 1,4-Dichlorobenzene 100mg/mL Di-n-Butylphthate 100mg/mL

-MS Tune Standard –Prepare from purchased stock by diluting 1.0mL of

1.0mg/mL with MeCl2 to 20mL. The standard will contain 50g/mL of: . Benzidine . DFTPP . 4,4-DDT . Pentachlorophenol 1.0L is injected.

-Laboratory Control Sample (LCS). Matrix spiking standard is used for LCS

-SPCC Standard – See calibration standard 50g/L

-CCC Standard – See calibration standard 50g/L

Note: All standards are stored at –10°C to –20°C in amber bottles with Teflon- lined screw caps. All stock standards are stable for one year.

3 Procedure 6600 Revised 04/07

Procedure

1.0 Initial Calibration

1.1 Perform required preventative maintenance including injector liner, septa and guard column replacement or cleaning.

1.2 Check MS for leaks under optitune, if OK put PTA on and check mass calibrations. Recalibrate as necessary.

1.2.1 Set the operating conditions of the GC/MS as follows Mass Range 35-500amu Scan Time 1 sec/scan Source Temperature 225°C Injector Temperature 250°C Transfer Line Temperature 280°C Carrier Gas Helium at 30cm/second

1.3 Check MS tune by injecting 1.0L of a 50g/mL DFTPP standard. If conditions pass QC acceptance criteria go to next step, otherwise repeat step 1.3 until pass. See Table II and VI for specifications and instrument operating conditions.

1.4 Inject system performance check compounds (SPCC) to ensure the minimum average RF is met. See Table III and VI.

1.5 Run calibration standards at a minimum of five different concentrations. The resulting % RSD should be < 15%. See Table IV.

1.5.1 In addition, the % RSD for each calibration check compound (CCC) should be <30% (see Table V). The relative RT of each compound in each calibration run should agree within 0.06 minutes.

2.0 Daily Calibration

2.1 Perform required preventative maintenance checks including replacement and cleaning of injector liner, septa and guard column.

2.2 Run DFTPP/MS tune, establish QC acceptance. (See Table II and VI)

4 Procedure 6600 Revised 04/07

2.3 Analyze mid level calibration check standard (50g/mL) and surrogates (200g/mL). Compare instrument RF with SPCC and CCC acceptance criteria. (see Tables III and V).

2.4 Compare CCC compounds for % drift. If % difference for each compound is <20% calibration curve is validated. If the CCC analytes are not included in the calibration list, subject the entire compound list to the required drift criteria (ex. TCLP).

2.5 Check I.S. for chance in RT and EICP area. RT should not change by more than 30 seconds and EICP area should not change more than a factor of two (-50% +100%) from the last initial calibration check.

3.0 Sample Analysis

3.1 Spike 1mL of the sample extract with 10L of IS solution prior to analysis.

3.2 Inject 1L of extract into GC/MS. (See Table VI)

4.0 Data Analysis

4.1 Each sample inject is reviewed and quantitated against the surrogate and calibration libraries

4.2 The concentration of analytes and surrogate compounds are calculated and recorded. Surrogate recoveries must be compared to acceptability criteria. (See Table VIII)

4.3 If response to any quantitation is greater than the initial calibration curve extract dilution and reanalysis will be required.

5.0 Batch Acceptance Criteria

5.1 All parameter detailed in the initial calibration (section 1.0-1.5) and daily calibration (section 2.0-2.5) must be met.

5.2 In addition to the instrument performance outlined in the pervious step, the batch QC parameters for spike/spike duplicate and sample duplicates must be evaluated. The current acceptable limits are presented in Table VII and attachment 0140.

6.0 Reporting of Results

6.1 All results for QC parameters and samples are reported on the batch list.

6.1.1 All results are reported to three significant figures.

5 Procedure 6600 Revised 04/07

6.2 Analytical results generated from the GC/MS software report ppb (g/L). All results require correction for preparatory or analytical dilutions. Dilution factors must be recorded in the preparation log and on the raw data printout. All reportable data must fall within the calibration curve post dilution.

7.0 Calculations

7.1 For Water Samples Concentration (g/L) = {[(A)(B)]/[(C)(D)(E)]} * Dilution Factor

7.2 For Soil Samples Concentration (g/Kg) = {[(A)(B)(F)]/[(C)(D)(G)(H)(I)]} * Dilution Factor

7.3 Definition of Variables . A = Area of characteristic ion for compound being tested . B = Amount of internal standard injected (ng) . C = Area of characteristic ion for the internal standard . D = Mean relative response factor for the compound being measured . E = Volume of water purged (mL) taking into consideration any dilution made . F = Volume of total extract (g/L) (used 10,000g/L or a factor of this when dilutions are made.) . G = Volume of extract added (g/L) for purging . H = Weight of sample extracted or purged (g) . I = % dry weight of sample/100, or 1 for a wet-weight basis

7.4 Record instrument performance QC data on the daily validation report sheet. File all raw data along with completed form by date of analysis.

6 Procedure 6600 Revised 04/07

Quality Control

 Initial Calibration parameters must be met after major maintenance, failed QC or yearly  A daily check is required of the MS tune, SPCC and CCC compounds to validate calibration. The standard checks must be run every 12 hours.  Each analytical batch analyzed for semi-volatiles must be accompanied by a blank consisting of ultra-pure water taken through all analytical steps.  All weights, volumes, comments, etc. for each batch must be entered in notebook form for data review.  As determined by notebook order, every 10th sample of similar matrix shall be analyzed in duplicate, every 20th sample shall be analyzed as a duplicate spike. (Calculations for RPD and % Recoveries must be calculated for each parameter, see procedure 0110 for calculations)  A laboratory control sample (LCS) must be analyzed per batch of 20 samples of the same matrix  Required recoveries for duplicate and spike duplicate recoveries shall be determined using historical data. The current acceptable limits for the parameters are listed in procedure 0140 and Table VIII.  Failure to meet quality control acceptable limits requires corrective action (see procedure 0150). Require, locate, and correct the source of the problem and repeat the test. Failure to meet the quality control acceptable limits again will require new calibration curve

References:

SW 846 Method 8270C-1 to 8270C-54 Revision 3 December 1996

40 CFR PT 136 App. A Method 625 pp. 204-231 Revised July 1, 199

7 Procedure 6600 Revised 04/07

Table I Calibration Preparation Secondary Stock = 200mg/L

L STD LMeCl2 g/mL Final 50 950 10 100 900 20 250 750 50 500 500 100 1000 0 200

Table II MS Tune Criteria (DFTPP)

Mass Ion Abundance Criteria 51 30-60% of mass 198 68 <2% of mass 69 70 <2% of mass 70 127 40-60% of mass 198 197 <1% of mass 198 198 Base peak, 100% of relative abundance 199 5-9% of mass 198 275 10-30% of mass 198 365 >1% of mass 198 441 Present but < mass 443 442 >40% of mass 198 443 17-23% of mass 442

Table III System Performance Check Compounds (SPCC) The minimum average relative response factor for SPCC's N-nitroso-di-n-propylamine 0.05 Hexachlorocyclopentadiene 0.05 2,4-Dinitrophenol 0.05 4-Nitrophenol 0.05

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Table IV Initial Calibration

Tablulate the area response of the characteristic ions against the concentration of each compound and internal standard of a minimum of 5 calibration standards. Calculate and record the response factors (RF) for each compound relative to the appropriate internal standard. Using the RF's from the initial

Calculations RF = [(Ax)(Cis)]/[(Ais)(Cx)] where Ax=Area of characteristic ion for compound Ais =Area of characteristic ion for internal standard Cis = Concentration of the internal standard Cx = Concentration of the compound standard

%RSD = [SD/Rfm] * 100 should be < 15% for each compound where RSD = Relative Standard Deviation Rfm = Mean of 5 initial RF's SD = Standard Deviation of 5 initial RF's

Table V Calibration Check Compounds (CCC) Initial Calibration: Evaluate the % RSD for the CCC analytes. If the %RSD > 30%, corrective action is required before recalibration.

Daily Calibration: Calculate the % Drift of the CCC compound. % Drift = [(Cl - Cc)/Cl ]* 100 where Cl = Calibration check compound concentration Cc = Measured concentration

The % Drift for each of the following CCC Compounds must be less than 20%: Acenaphthene 4-Chloro-3-methylphenol 1,4-Dichlorobenzene 2,4-Dichlorophenol Hexachlorobutadiene 2-Nitrophenol N-Nitrosodiamine Phenol Di-n-octyl phthalate Pentachlorophenol Fluoranthene 2,4,6-Trichlorophenol 9 Benzo (a) pyrene Procedure 6600 Revised 04/07

Table VI GC Conditions for Analysis DFTPP/MS Tune Sample Analysis 50°C hold for 1minute Ramp at 8°/minute to 310°C hold for 6.5 minutes

Table VIII Surrogate Acceptance Limits

Surrogate Compounds Each sample analyzed for semi-volatiles must be spiked with the surrogate spiking solution. Results for surrogate recoveries are reported as percent. The compounds and their acceptable recoveries are listed below.

Water Soil/Sediment TCLP Extracts Nitrobenzene-d5 35-114 13-133 9-123 2-Fluorobiphenyl 43-116 12-118 11-117 Terphenyl-d14 33-141 18-137 33-120 Phenol-d6 10-94 24-113 10-94 2-Fluorophenol 21-100 10-130 4-94 2,4,6-Tribromophenol 10-123 19-122 10-123

Table VII Batch Acceptance Spike/Spike Duplicate

Spike/Spike Duplicate Every 20th sample analyzed for semi-volatiles must be run as a spike/spike duplicate. The required compounds and acceptance limits are indicated below. %RPD Recovery Limit 1,2,4-Trichlorobenzene 23 38-107 Acenaphthene 19 31-137 2,4-Dinitrotoluene 47 28-89 Pyrene 36 35-142 n-Nitrosodi-n-Propylamine 38 41-126 1,4-Dichlorobenzene 27 28-104 Pentachlorophenol 47 17-109 Phenol 35 26-90 2-Chlorophenol 50 25-102 4-Chloro-3-Methylphenol 33 26-103 4-Nitrophenol 50 11-114 Di-n-butylphthalate 31 11-117

10 Procedure 6600 Revised 04/07

11 Procedure 6600 Revised 04/07