Volatile Organic Compounds in Water, Soil and Solids by

Caduceon Environmental Laboratories Page: 1 of 3 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB

Volatile Organic Compounds in Water, Soil and Solids by Purge & Trap GC/MS 1.0 Scope 1.1 This method is designed to measure the concentration of volatile organic compounds in a variety

of matrices, including groundwater, surface water, TCLP/mSPLP Extracts, aqueous effluents, soils, sludge’s, sediments and various other applicable solids.

1.2 This method is designed to quantify most volatile organic compounds that have boiling points

below 200°C and that are insoluble or slightly soluble in water. Volatile water-soluble compounds can be included in this analytical technique, however, for the more soluble compounds, quantitation limits are approximately ten times higher because of poor purging efficiency.

1.3 This method is based upon a purge-and-trap, gas chromatographic/mass spectrometric (GC/MS)

procedure and is restricted to use by, or under the supervision of, analysts experienced in the use of purge-and-trap systems, gas chromatograph/mass spectrometers, and skilled in the interpretation of mass spectra.

2.0 Principle and Theory 2.1 Principles

2.1.1 The volatile compounds are introduced into the gas chromatograph by a purge and trap method. Purged sample components are trapped in a tube containing suitable sorbent materials. When purging is complete, the sorbent tube is heated and back flushed with helium to desorb the trapped sample components into a capillary gas chromatography (GC) column interfaced to a mass spectrometer (ion-trap detector). The column is temperature programmed to facilitate the separation of the method analytes, which are then detected by the MS.

2.1.2 Compounds eluting from the GC column are identified by comparing their measured

mass spectra and retention times in a database. Reference spectra and retention times for each analyte are obtained by the measurement of calibration standards under the same conditions used for samples. The concentration of each identified component is measured by relating the MS response of the quantitation ion (or ions) produced by that compound to the MS response of the quantitation ion produced by a compound that is used as an internal standard. Surrogate analytes, whose concentrations are known in every sample, are measured with the same internal calibration procedure.

2.1.3 Analytes that are not separated chromatographically, but which have different mass

spectra and non-interfering quantification ions, can be identified and measured in the same calibration mixture or water sample as long as their concentrations are somewhat similar. Analytes that have very similar mass spectra cannot be individually identified and measured in the same calibration mixture or water sample unless they have different retention times. Co-eluting compounds with very similar mass spectra, typically many structural isomers, must be reported as an isomeric pair (i.e. m,p-Xylenes).

2.1.4 Soil samples are first extracted into a known volume of glass distilled methanol. A

portion of the methanol extract is spiked into a vial containing 10mL of organic-free water. The diluted sample is subsequently analyzed by purge-and-trap GC/MS under the same conditions as for water samples.

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Caduceon Environmental Laboratories Page: 2 of 3 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB 2.2 Interferences

2.2.1 Major contaminant sources are volatile materials in the laboratory and impurities in the inert purging gas and in the sorbent trap. The use of non-polytetrafluoroethylene (PTFE) thread sealants, plastic tubing, or flow controllers with rubber components should be avoided as such materials outgas organic compounds which will be concentrated in the trap during the purge operation. Analyses of calibration and reagent blanks provide information about the presence of contaminants.

2.2.2 High purity solvents (i.e. Methanol) must be used to minimize interference problems.

2.2.3 Contamination by carryover can occur whenever high-level and low-level samples are

sequentially analyzed. When an unusually concentrated sample is encountered, it should be followed by the rinsing of the purging apparatus and sample syringes with two portions of organic-free reagent water between samples. In addition, the purging vessel should be put through a bake cycle prior to reuse. One or more blanks should then be analyzed to check for cross-contamination. For samples containing elevated levels of water soluble organics, suspended solids, high boiling compounds or high concentrations of compounds being determined, it may be necessary to wash the purging vessel with a soap solution, rinse with organic-free reagent water, followed by drying in an oven at 105°C. The ATOMX Autosampler Purge and Trap system has unique methanol and water rinsing capabilities as well as a short sample path which aid in the reduction of carryover contamination.

2.2.4 Special precautions must be taken to analyze for methylene chloride. The analytical and

sample storage area should be isolated from all atmospheric sources of methylene chloride, otherwise random background levels will result. Laboratory clothing worn by the analyst should be clean since clothing previously exposed to methylene chloride fumes during liquid/liquid extraction procedures may contribute to sample contamination. In addition, all gas chromatograph carrier lines and purge gas plumbing should be constructed from stainless steel or copper tubing as methylene chloride may permeate through PTFE tubing.

2.2.5 Samples can be contaminated by diffusion of volatile organics (particularly methylene

chloride and fluorocarbons) through the septum seal into the sample during shipment and storage. A trip blank prepared from organic-free reagent water and carried through the sampling and handling protocol can serve as a check on such contamination.

3.0 Safety 3.1 Refer to Caduceon Safety Manual 3.2 Waste generated from these protocols fall under waste class 241H (Halogenated solvents), 212H

(Aliphatic solvents) and 221I (Light Fuels). Each chemical compound should be treated as a potential health hazard. A reference file of Safety Data Sheets (SDS) shall be made available to all personnel in the chemical analysis. Refer to the Laboratory Safety Manual for instructions for handling organics.

4.0 Sampling Procedure and Storage 4.1 Non-Chlorinated Water Sources: Samples are collected in 40mL amber glass vials with Teflon-

lined septum seals and stored at 4±3°C.

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Caduceon Environmental Laboratories Page: 3 of 4 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB 4.2 Chlorinated Drinking Water Sources: Samples are collected in 40mL amber glass vials with

Teflon-lined septum seals and pre-charged with Sodium thiosulphate. The samples are stored at 4±3°C from the time of collection until extraction. The holding time is 14 days from date of collection.

Note: Some compounds are adversely affected by the Sodium thiosulphate however none of them are on the Canadian or Ontario Drinking Water list of parameters. The THM analytes are not affected therefore only drinking water samples should be preserved in this manner.

4.3 Soil Samples: Samples are collected in amber glass jars (120-180 mL) with Teflon-lined lids. The

samples are stored at 4±3°C from the time of collection until extraction. Soil samples must be extracted within 7 days of collection and stored at 4±3°C. Extracts must be analyzed within 14 days of extraction.

4.4 Regulatory Soil Samples: Samples (~5g) are collected into pre-weighed 40mL glass vials

containing 10mL of methanol known to be free of contamination. The sample vials are sealed with lids containing Teflon septa and stored at 4±3°C. Samples collected in this manner are stable for up to 14 days.

4.4.1 To meet certain regulatory quality control requirements, at least two vials must be submitted for each sample to perform the VOC extraction and analyses.

4.4.2 As well, a separate jar of unpreserved sample must be submitted for moisture content determination.

4.4.3 Since the VOC and PHC-F1 analysis is performed at the same time, additional methanol

may need to be added to the vial to ensure the 2:1 (volume of methanol: wet weight of soil) ratio is met as dictated by CCME.

4.4.4 Soil samples submitted without methanol preservation must be extracted within 48 hours

of receipt.

4.5 TCLP/SPLP Extracts. Samples are collected in amber glass jars (120-180 mL) with Teflon-lined lids. The samples are stored at 4±3°C from the time of collection until extraction. Soil samples must be extracted as per TCLP/SPLP-001 within 14 days of collection and stored at 4±3°C. The extract is to be collected in a 40mL amber glass jar without headspace and stored under refrigeration (4 ± 3°C). Extracts must be analyzed within 7 days of extraction.

5.0 Equipment 5.1 Glassware

5.1.1 Mini inert valve vials - 1.5mL with septums. Used for storing standards

5.1.2 Volumetric flasks, Class A - 10mL with ground glass stoppers

5.1.3 ProClean 40mL amber vials precleaned, demonstrated to be suitable for the sampling of Volatile Organic Compounds as per MISA and U.S EPA protocols

5.2 Balances (verification as per CP-021)

5.2.1 Analytical Balance, capable of weighing accurately to nearest 0.0001g

5.2.2 Top-Loading Balance, capable of weighing accurately to nearest 0.1g

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Caduceon Environmental Laboratories Page: 4 of 5 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB 5.3 Syringes (verification as per CP-022)

5.3.1 Microsyringes - Gas-tight: 1µL, 2µL, 5µL, 10µL, 25µL, 50µL, 100µL, 250µL, 1000µL

5.3.2 Gas-tight Syringe: 5 and 10mL Teflon with luer-lock adapter 5.4 Disposable Pasteur pipettes 5.5 Spatula - stainless steel 5.6 Drying oven (verified as per CP-023)

5.7 TCLP/SPLP equipment Listed in procedure TCLP/SPLP-001 5.8 Autosampler and Purge-and-Trap Devices

The purge-and-trap consists of the sample purger, the trap and the desorber.

5.8.1 ATOMX by Teledyne Tekmar - Autosampler/Purge and Trap 5.8.2 Sorbent Trap: VOCarb 3000 Sorbent Trap

5.9 Gas Chromatographic/Mass Spectrometer/Data System

5.9.1 Gas Chromatograph: HP 6890/N equipped with HP GC/MS MSD Chemstation version D.03.00.611, and E.02.02.1431

5.9.2 Column: Restek Rtx-VMS 30m x 0.25 mm ID, 1.4µm film thickness. (No cryogenic oven cooling is required as this column separates all analytes listed in this method starting at ambient temperature.)

5.9.3 Mass Spectrometer: HP 5973/N MSD.

6.0 Reagents 6.1 Methanol – purge and trap grade, Fisher or equivalent, demonstrated to be free of analytes.

Store apart from other solvents. Stored at room temperature. See supplier details for expiry. 6.2 Organic-free reagent water - Deionized water obtained through Culligan, checked for purity as

part of QC checks. 6.3 Ottawa sand, purchased from an approved supplier.

6.4 TCLP/SPLP solutions. Refer to TCLP/SPLP-001 method, current revision 6.5 Internal and Surrogate Standards

6.5.1 Stock Internal Standard, 2500µg/mL (Restek 30074): 8260 Internal Standards Mix. Store according to manufacturer’s instructions. Discard by the expiry date printed on the label. Stored in freezer.

6.5.2 Stock Surrogate Standard, 2500µg/mL (Restek 30240): 8260A Surrogate Mix. Store

according to manufacturer’s instructions. Discard by the expiry date printed on the label. Stored in freezer.

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6.5.3 Working Internal Standard and Surrogate Solution, 200µg/mL: 800µL of both Stock Internal Standard (6.5.1), and Stock Surrogate Standard (6.5.2) is injected into a 10mL Volumetric Flask and filled to the mark with methanol (6.1). This is transferred to the appropriate vial in the Atomx Autosampler. Solution expires after 6 months or when compounds show degradation. Record the preparation on Form F-11. Stored in freezer.

6.6 Calibration Standards

6.6.1 VOC Standard Calibration Stock 1, 2.0mg/mL (Agilent CUS-00003056 or equivalent): Transfer from flame sealed ampule to Mini Inert Valve VOC or GC vial. Store in the freezer for up to 3 months.

6.6.2 VOC Standard Calibration Stock 2, 2.0mg/mL (Agilent DWM-588-1 or equivalent):

Transfer from flame sealed ampule to Mini Inert Valve VOC or GC Vial. Store in the freezer for up to 3 months.

6.6.3 1,4-Dioxane Calibration Stock (Sigma Aldrich ALR-062N or equivalent): Transfer

from flame sealed ampule to Mini Inert Valve VOC or GC vial. Store in the freezer. Discard by the expiry date printed on the Certificate of Analysis.

6.6.4 High Level Intermediate Calibration Standard, 50µg/mL: Transfer 25µL of the

Calibration Stock 1 (6.6.1), 25µL of the VOC Standard Calibration Stock 2 (6.6.2), 0.97µL of 1,4-Dioxane Calibration Stock (6.6.3), and 949µL of methanol (6.1) into a Mini Inert Valve VOC or GC vial. Store in the freezer for up to 1 month or when compounds show degradation. Record the preparation on Form VOC-04.

6.6.5 Low Level Intermediate Calibration Standard, 5.0µg/mL: Transfer 100µL of High

Level Working Calibration Standard (6.6.4) and 900µL of methanol (6.1) into a Mini Inert Valve VOC or GC vial. Store in the freezer for up to 1 month or when compounds show degradation. Record the preparation on Form VOC-04.

6.6.6 Freon Calibration Stock 1, 2.0mg/mL (Spex Standard VO-CALCN-54 or equivalent):

Transfer from flame sealed ampule to Mini Inert Valve VOC or GC Vial. Store in freezer for up to 3 months.

6.6.7 Freon High Level Intermediate Calibration Standard, 50µg/mL: Transfer 25µL of the

calibration stock (6.6.6) and 975µL of Methanol into a Mini Inert Valve VOC or GC Vial. Store in the freezer for up to 1 month, or when compounds show degradation. Record the preparation on Form VOC-06.

6.6.8 Freon Low Level Intermediate Calibration Standard, 5.0µg/mL: Transfer 100µL of

High Level Working Calibration Standard (6.6.7) and 900µL of methanol (6.1) into a Mini Inert Valve VOC or GC vial. Store in the freezer for up to 1 month or when compounds show degradation. Record the preparation on Form VOC-06.

6.6.9 Working Calibration Standards: Following Table 1, transfer the volume of the stock

solution indicated into a VOC vial containing 10mL of organic free DI. Prepare fresh daily. Record the preparation on Form VOC-01.

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Table 1 – Working Calibration Standards

Working Calibration Standard I.D.

Working Calibration Standard (µg/L)

Intermediate Standard ID

Intermediate Standard Concentration (µg/mL)

Volume of Stock Standard (µL)

S1 0.5 Low Level (6.6.5 or 6.6.8)

5.0 1.0

S2 1.0 Low Level (6.6.5 or 6.6.8)

5.0 2.0

S3 2.0 Low Level (6.6.5 or 6.6.8)

5.0 4.0

S4 5.0 Low Level (6.6.5 or 6.6.8)

5.0 10.0

S5 10.0 Low Level (6.6.5 or 6.6.8)

5.0 20.0

S6 20.0 Low Level (6.6.5 or 6.6.8)

5.0 40.0

S7 50.0 High Level (6.6.4 or 6.6.7)

50.0 10.0

S8 100 High Level (6.6.4 or 6.6.7)

50.0 20.0

S9 200 High Level (6.6.4 or 6.6.7)

50.0 40.0

6.7 Quality Control Standards

6.7.1 VOC Standard QC Stocks 1, 2.0mg/mL (Absolute Standards 35011 or equivalent): EPA Method 524.2 Compounds. Transfer from flame sealed ampules to Mini Inert Valve VOC or GC vials. Store in the freezer for up to 3 months.

6.7.2 VOC Standard QC Stocks 2, 2.0mg/mL (Absolute Standards 98211 or equivalent):

EPA Method 502.2 Compounds. Transfer from flame sealed ampules to Mini Inert Valve VOC or GC vials. Store in the freezer for up to 3 months.

6.7.3 1,4-Dioxane QC Stock (Agilent RCC-180 or equivalent): Transfer from flame sealed

ampule to Mini Inert Valve VOC or GC vial. Store in the freezer. Discard by expiry date printed on the label.

6.7.4 Intermediate QC Standard, 50µg/mL: Transfer 25µL of the Standard QC Stock 1

(6.7.1), 25µL of the Standard QC Stock 2 (6.7.2), 0.97µL of 1,4-Dioxane Stock (6.7.3), and 949µL of methanol (6.1) into a 1mL Mini Inert Valve VOC or GC vial. Store in the freezer for up to 1 month or when compounds show degradation. Record the preparation on Form VOC-03.

6.7.5 Freon QC Stock, 2.0mg/mL (Absolute Standards 99649 or equivalent): Transfer

from flame sealed ampule to Mini Inert Valve VOC or GC Vial. Store in freezer for up to 3 months.

6.7.6 Freon Intermediate QC Standard, 50ug/mL: Transfer 25µL of the QC stock (6.7.5)

and 975µL of Methanol into a Mini Inert Valve VOC or GC Vial. Store in the freezer for up to 1 month, or when compounds show degradation. Record the preparation on Form VOC-05

6.7.7 Working QC Standards: Following Table 2, transfer the volume of the stock solution

indicated into a VOC vial containing 10mL of organic free DI. Prepare fresh daily. Record the preparation on Form VOC-02.

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Table 2 – Working Quality Control Standards

Working QC Standard I.D.

Working QC Standard (µg/L)

QC Intermediate Standard I.D.

QC Intermediate Standard

Concentration (µg/mL)

Volume of Stock Standard (µL)

QC1 10.0 6.7.4 or 6.7.6 50.0 2.0QC2 50.0 6.7.4 or 6.7.6 50.0 10.0

6.8 Quality Control Samples - Water

6.8.1 Matrix Spike, Water, 50µg/L: 10µL of Intermediate QC Standard (6.7.4) is added to 10mL of a predetermined triplicate water sample if available.

6.8.2 Method Blank, Water: 10mL of organic free water is loaded onto the autosampler and

analyzed as a routine sample. This result should be less than the MDL for all analytes. 6.8.3 Duplicate Sample, Water: 10mL of a predetermined sample is placed in a 40mL septa

vial. The relative percent difference of the duplicates should fall within the acceptable QC limits.

6.9 Quality Control Samples - Soil

6.9.1 Duplicate Sample, Soil: 5g of a predetermined soil sample is placed in a vial and then 10mL of Methanol (6.1) is added. If sample is already in methanol charged vials, use the second vial of a predetermined sample for the duplicate. The relative percent difference of the duplicates should fall within the acceptable QC limits.

6.9.2 Method Spike, Soil, 0.50µg: Transfer 10µL of Intermediate QC Standard (6.7.4) and

50µL of Methanol (6.1) into 10mL of organic free DI in a 40mL septa vial. 6.9.3 Matrix Spike, Soil, 0.50µg: Transfer 10µL of Intermediate QC Standard (6.7.4) and 50µL

of predetermined sample into 10mL of organic free DI in a 40mL septa vial.

6.9.4 Method Blank Soil: Transfer 50µL of Methanol (6.1) into 10mL of organic free DI in a 40mL septa vial. If sample is in a jar and not a client supplied methanol vial then transfer 5g of Ottawa sand and 10mL of Methanol (6.1) to a 40mL septa vial. Then take 50µL of the extract into 10mL of organic free DI in a 40mL septa vial. This result should be less than the MDL for all analytes.

7.0 Procedure 7.1 Purge and Trap Conditions (for reference only, individual instruments may vary slightly)

7.1.1 Conditions – Purge

7.1.1.1 Purge Time: 11 minutes 7.1.1.2 Dry Purge Time: 2 minutes 7.1.1.3 Purge Flow: 40 mL/min. 7.1.1.4 Oven Valve Temp: 140°C 7.1.1.5 Transfer Line: 140°C 7.1.1.6 Mount: 90°C

7.1.2 Conditions - Desorb (VOCarb 3000 Adsorbent U Shaped Trap)

7.1.2.1 Desorb: 2 minutes 7.1.2.2 Bake: 8 minutes at 280°C

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7.1.3 Sample Conditions 7.1.3.1 Organic Free Water Addition 5.0 mL 7.1.3.2 Volume of Internal/Surrogate 5.0 L

7.2 Chromatographic Conditions (for reference only, individual instruments may vary slightly) 7.2.1 Column: Restek Rtx-VMS, 30m x 0.25 mm ID, 1.4μm film

7.2.2 Flow Rate: 0.8 mL/min.

7.2.3 Split Ratio: 50:1

7.2.4 Inlet Temp: 220°C

7.2.5 Transfer Line Temp: 170°C

7.2.6 Column Program

7.2.6.1 Initial Temp: 36°C 7.2.6.2 Initial Time: 4 min. 7.2.6.3 Rate 1: 8°C/min 7.2.6.4 Final Temp 1: 130°C 7.2.6.5 Rate 2: 40°C/min 7.2.6.6 Final Temp 2: 220°C 7.2.6.7 Final Time: 3 min.

7.3 MS Conditions (for reference only, individual instruments may vary slightly)

7.3.1 Quad MSD Setup

7.3.1.1 Source Temperature: 230°C 7.3.1.2 Emission Current: As per Auto-tune (typically 34.6) 7.3.1.3 Mode: SIM

7.4 Extraction Procedure – Soil

Note: Samples being submitted under Regulation 153 will arrive at the lab in a 40mL vial containing approximately 10mL of methanol and an unknown amount of soil. The vials are pre-weighed by the supplier, so weighing the vial upon receipt allows the soil weight to be determined. Additional methanol may need to be added to ensure the 2:1 (volume of methanol: wet weight of soil) ratio dictated by CCME.

7.4.1 Thoroughly mix the sample while minimizing contact time in order to prevent the volatilization of gasoline range organics from the sample.

7.4.2 The results are reported in dry weight and the extraction is performed on a wet sample therefore % solids of the sample must be determined.

7.4.3 Transfer the equivalent of 5g of dried soil to a VOC vial. Add 10 mL of methanol (6.1). 7.4.4 Place the vial in the sonication bath for a minimum of 5 minutes, and then allow to settle.

If the extract remains cloudy place the vial in the refrigerator to settle out the particulate matter.

7.4.5 Transfer 10mL of organic free water and 50µL of the extract into a new VOC vial. Cap

and load on to the Atomx autosampler for analysis.

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7.4.6 The ATOMX autosampler then adds 5.0µL of the Working Internal Standard and

Surrogates Solution (6.5.3) and 5mL of organic free water. The sample is purged, desorbed, and injected into the GC/MS system.

7.4.7 Record all required soil extraction procedure information on EXTS-1 form.

7.5 Extraction Procedure - Water

7.5.1 Transfer 10mL of the sample into a new VOC vial. Cap and load the sample on to the

ATOMX autosampler.

7.5.2 The ATOMX autosampler then adds 5.0µL of the Working Internal Standards and Surrogates Solution (6.5.3). The sample is purged, desorbed, and injected into the GC/MS system.

7.6 Analysis Procedure

7.6.1 When maintenance is performed or when troubleshooting instrument issues load a Blank (6.8.2) onto the ATOMX autosampler. Analyze it to ensure it meets the tuning criteria listed in Table 3 (for reference only, individual instruments may vary slightly).

Table 3

M/Z Tuning Criteria

Mass Criteria

50 15-40% of m/z 95.

75 30-80% of m/z 95.

95 Base Peak

96 5-9% 0f m/z 95

173 less than 2% of m/z 174

174 greater than 50% of m/z 95

175 5-9% of mass 174

176 >95% and < 101% of m/z 174

177 5-9% of m/z 176

Reference EPA Methods 524 and 8260

7.6.2 Samples are analyzed by Purge & Trap GC/MS following the conditions listed in Sections 7.1 thru 7.3, above. A typical daily routine follows:

7.6.2.1 Check the previous days run for any suspected high level samples that may

have resulted in cross contamination of the purging system. If carry-over is detected repeat the samples as required.

7.6.2.2 Prepare samples and set up the following run sequence including all quality

control samples. Skip steps 7.6.2.2.2 and 7.6.2.2.3 if the current calibration is still valid (Section 7.7.3)

7.6.2.2.1 Blank

7.6.2.2.2 Blank

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7.6.2.2.3 Working Calibration Standards (S1-S9)

7.6.2.2.4 Blank

7.6.2.2.5 QC 2

7.6.2.2.6 QC 1

7.6.2.2.7 Method Spike

7.6.2.2.8 Matrix Spike of Sample 1

7.6.2.2.9 Method Blank

7.6.2.2.10 Samples 1 – 10

7.6.2.2.11 Duplicate of Sample 1

7.6.2.2.12 QC 1

7.6.2.2.13 Blank

7.6.2.2.14 Samples 11-20


7.6.2.2.16 QC 2

7.6.2.2.17 Blank

7.6.2.2.18 Samples 21-30


7.6.2.2.20 Matrix Spike of Sample 21

7.6.2.2.21 Blank

7.6.2.2.22 QC 1

7.6.2.2.23 This sequence from Step 7.6.2.2.10 is repeated until all samples have been processed

7.6.2.3 Refer to the QC logs for acceptable limits for the QC standards, duplicates and

spike samples. 7.7 Calibration Procedure

7.7.1 Calibrate the GC/MS with an initial 9 point external calibration using the Working Calibration standards run on the instrument (7.6.2.2.3).

7.7.1.1 Load the last calibration file. 7.7.1.2 Click on ‘File’ then ‘Save As’ with the filename YYMMDD_VOC.

7.7.1.3 Click on ‘Init’ then ‘Quick Update’ and choose the files of the Working

Calibration Standards run in 7.6.2.2.3.

7.7.2 A curve that is forced through zero shall be utilized for the determination of the concentrations of analytes present in the sample. Ensure the r2 value is >0.995.

7.7.2.1 If this is not met for any compounds prepare fresh working calibration standards

(6.6.9) and repeat the calibration process in 7.6.2.2. 7.7.2.2 If the second calibration fails repeat the calibration process again with freshly

prepared Intermediate and Working Calibration Standards (6.6).

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7.7.2.3 If the calibration still fails the instrument may require service. Inform the supervisor and consult the instrument manual for instructions.

7.7.2.4 Record all non-conformities and corrective actions performed on the non-

conformity log (as per SOP CP-032).

7.7.3 The instrument does not require a daily calibration. To verify that the calibration is valid, analyze the Working QC Standards (6.7.7) and compare the results for each compound with the accepted target value.

7.7.3.1 If all results are within the accepted range, the calibration is verified and

samples can be analyzed. 7.7.3.2 If any result is unacceptable, the calibration procedure is performed (7.6.2).

7.7.4 Document all equipment maintenance, comments and any changes in the instrument log

book. 7.8 Analytical Run Data Acceptance

7.8.1 The analytical run cannot be reported until the QC data has been verified and accepted. Record all QC data in the QC log and compare the results with current internal limits of acceptability.

7.8.2 If any of the QC standards fall outside of the acceptable internal and regulatory limits

(see appendix A of CP-032), re-analyze.

7.8.2.1 If the result is still unacceptable, prepare and analyze new QC Standards (6.7). If the results are acceptable then continue with the analytical run.

7.8.2.2 If the results are still unacceptable then re-calibrate the instrument (7.7). If this

does not solve the problem the instrument may require service. Inform the supervisor and consult the instrument manual for instructions.

7.8.2.3 Record all non-conformities and corrective actions performed on the non-

conformity log (as per SOP CP-032).

7.8.3 If a duplicate or matrix spike falls outside the acceptable limits the analyst shall determine which regulations the affected samples fall under. For all drinking water regulations if any one compound fails, prepare another aliquot of the sample or prepare a new spike for analysis. If these results are still unacceptable, select a different sample for duplicate and/or matrix spike analysis and analyze accordingly. For all other regulations 10% of the total number of analytes may fall outside the acceptable limits without requiring further verification.

7.8.3.1 If the results of the new analysis are acceptable continue with the analytical

run. 7.8.3.2 If acceptable results are still not achieved and the QC standards are

acceptable, the sample results may be reported with a qualifying statement.

7.8.3.3 Report all initial sample results (each result for the duplicate pair) for failed duplicate and matrix spike samples and qualify the data to indicate that the results are suspect due to possible matrix spike interferences.

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7.8.4 Each sample in the analytical run is examined to ensure that cross-contamination has not occurred. If any carry-over is detected all affected samples from that point on in the run are repeated after ensuring that the contamination has been removed from the system (7.6.2.1).

7.8.5 Any results above the calibration range (i.e. >200 µg/L) or surrogate recoveries outside of

acceptable limits (50%-140%) are diluted then repeated. If, after repeat analysis, surrogate recoveries are still outside of the acceptable limits, sample results may be reported with a qualifying statement.

8.0 Calculations 8.0 Internal standard calculations require that a response factor be calculated for each analyte of

interest. The response factor is calculated during the calibration of the mass spectrometer as follows:

Amount unknown x Area internal standard Amount internal standard x Area unknown

8.1 Water

8.1.1 Dilution Factor, DFw = Total volume purged (10mL) Volume of Sample (mL)

8.1.2 Final Concentration (µg/L) = Instrument Response (µg/L) x DF 8.2 Soils

8.2.1 Dry Weight of Soil and Dry Weight in g, WD = Ww x MC/100 Volume of Water in Sample in mL, Vw = Ww x (1 - MC/100)

Where Ww = Wet Weight of Soil (g) MC = Moisture content (%) Water: 1g = 1mL 8.2.2 Instrument Dilution Factor, DFs= VI / VF Where VI = Volume Injected by Instrument (mL) VF = Final Volume (10mL) 8.2.3 Concentration, µg/L = (VM + Vw) x DFs WD 1000 Where VM = Volume of Methanol, mL Vw = Volume of Water in Sample, mL DFs = dilution factor for soils WD = Dry Weight of Soil, g

uncontrolled

Caduceon Environmental Laboratories Page: 13 of 14 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB 8.2 Calculation of Total Xylenes

8.2.1 A = B + C Where A = Total Xylenes concentration B = concentration of m,p-Xylene C = concentration of o-Xylene Note: All values must be in the same units (mg/L or µg/L or µg/g)

8.3 Calculation of Total Dichloropropenes

8.3.1 A = B + C Where A = Total Dichloropropenes concentration B = concentration of cis-1,3-dichloropropene C = concentration of trans-1,3-dichloropropene Note: All values must be in the same units (mg/L or µg/L or µg/g)

8.4 Calculation of Total Trihalomethanes

8.4.1 A = B + C + D + E Where A = Total Trihalomethanes concentration B = concentration of Chloroform C = concentration of Bromoform D = concentration of Bromodichloromethane E = concentration of Chlorodibromomethane Note: All values must be in the same units (mg/L or µg/L or µg/g)

9.0 Method Validation & Method Performance 9.1 As a minimum, for each batch of samples, the following quality control samples shall be included:

Quality Control Standard Reagent Blank Duplicate Sample Matrix Spike (typically performed on the same sample chosen as the duplicate) In addition, the Lab Blank shall be monitored daily

9.2 A surrogate spike shall be added to all samples, QC samples and blanks. % Recoveries shall fall

within the ranges listed in Tables 4, 5, 6 and 7, below. If recoveries are outside established limits, verify calculations, dilutions and standard solutions. Verify instrument performance.

9.3 High recoveries may be due to co-eluting matrix interference; examine the sample

chromatogram. 9.4 Low recoveries may be due to the sample matrix. 9.5 Control charts are to be used for long term performance and how to interpret the charts can be

found in CP-031.

9.6 Method Uncertainty

9.6.1 The expanded uncertainty is determined as per CP-026. The data accumulated in the QC log is used to calculate the expanded uncertainty.

9.6.2 Expanded uncertainty is reported at 95% confidence interval (coverage factor k=2)

uncontrolled


Table 4 – Laboratory Control Samples (Water)

Compound

Low-level Laboratory Control Sample (LLCS)

Mid-level Laboratory Control Sample (MLCS)

TRUE (µg/L)

Mean (µg/L) Control Limits

(%Rec)

TRUE (µg/L)


(%Rec)

Dibromofluoromethane (S) - % 100 100.86 50-140 100 103.05 50-140

Toluene-d8 (S) - % 100 99.77 50-140 100 100.21 50-140

Bromofluorobenzene (S) - % 100 98.34 50-140 100 107.02 50-140

Dichlorodifluoromethane (Freon 12) 10 7.12 60-130 50 46.17 60-130

Difluorochloromethane (Freon 22) 10 8.67 60-130 50 50.3 60-130

1,2-Dichlorotetrafluoroethane (Freon 114) 10 6.94 60-130 50 47.88 60-130

2-Chloro-1,1,1-trifluoroethane (Freon 133a) 10 8.92 60-130 50 48.34 60-130

Trichlorofluoromethane (Freon 11) 10 8.73 60-130 50 47.26 60-130

Dichlorofluoromethane (Freon 21) 10 9.29 60-130 50 49.51 60-130

1,1,2-Trichlorotrifluoroethane (Freon 113) 10 8.81 60-130 50 45.94 60-130

2,2-Dichloro-1,1,1-trifluoroethane (Freon 123) 10 8.97 60-130 50 46.6 60-130

1,2-Difluorotetrachloroethane (Freon 112) 10 9.13 60-130 50 46.82 60-130

Vinyl Chloride 10 8.07 60-130 50 50.57 60-130

Chloromethane 10 9.01 60-130 50 45.90 60-130

Bromomethane 10 10.67 50-140 50 61.92 50-140

Chloroethane 10 10.59 60-130 50 53.72 60-130

Trichlorofluoromethane 10 8.52 60-130 50 47.34 60-130

1,1 – Dichloroethene 10 10.06 60-130 50 57.25 60-130

Acetone 10 10.23 60-130 50 50.84 60-130

Methylene Chloride 10 10.08 60-130 50 52.94 60-130

Methyl t-butyl ether (MTBE) 10 8.97 60-130 50 53.67 60-130

Trans – 1,2 – Dichloroethene 10 10.05 60-130 50 55.54 60-130

Hexane 10 9.22 60-130 50 49.92 60-130

1,1 – Dichloroethane 10 9.90 60-130 50 54.91 60-130

2,2-Dichloropropane 10 10.46 60-130 50 56.27 60-130

2 –Butanone (Methyl Ethyl Ketone) 10 9.26 50-140 50 53.98 50-140

cis – 1,2 – Dichloroethene 10 9.76 60-130 50 54.44 60-130

Bromochloromethane 10 10.22 60-130 50 54.14 60-130

Chloroform 10 9.59 60-130 50 52.74 60-130

1,1,1 – Trichloroethane 10 9.54 60-130 50 51.98 60-130

Carbon Tetrachloride 10 7.77 60-130 50 48.25 60-130

1,1-Dichloropropene 10 9.77 60-130 50 54.08 60-130

Benzene 10 9.03 60-130 50 51.84 60-130

1,2 – Dichloroethane 10 9.79 60-130 50 52.67 60-130

Trichloroethene 10 9.08 60-130 50 51.91 60-130

1,2 – Dichloropropane 10 9.23 60-130 50 52.59 60-130

Dibromomethane 10 9.01 60-130 50 50.08 60-130

Bromodichloromethane 10 8.73 60-130 50 51.93 60-130

cis – 1,3 – Dichloropropene 10 7.66 60-130 50 55.96 60-130

Methyl Isobutyl Ketone (MIBK) 10 7.69 60-130 50 54.49 60-130

uncontrolled


Compound



TRUE (µg/L)


(%Rec)

TRUE (µg/L)


(%Rec)

Toluene 10 8.88 60-130 50 53.62 60-130

1,4-Dioxane 200 197.93 50-140 1000 973.86 50-140

trans – 1,3 – Dichloropropene 10 8.26 60-130 50 56.56 60-130

1,1,2 – Trichloroethane 10 9.27 60-130 50 51.69 60-130

Tetrachloroethene 10 9.30 60-130 50 53.10 60-130


2-Hexanone (MBK) 10 7.07 60-130 50 54.55 60-130

Dibromochloromethane 10 8.50 60-130 50 51.83 60-130

1,2 – Dibromoethane (Ethylene Dibromide) 10 8.76 60-130 50 51.61 60-130

Chlorobenzene 10 9.03 60-130 50 51.83 60-130

1,1,1,2 – Tetrachloroethane 10 8.67 60-130 50 50.32 60-130

Ethylbenzene 10 8.63 60-130 50 54.87 60-130

m.p – Xylene 20 18.31 60-130 50 109.76 60-130

o – Xylene 10 8.42 60-130 50 58.25 60-130

Styrene 10 8.79 60-130 50 57.16 60-130

Bromoform 10 8.06 60-130 50 51.64 60-130

Isopropylbenzene 10 8.17 60-130 50 59.29 60-130

bromobenzene 10 9.03 60-130 50 55.44 60-130

1,1,2,2 – Tetrachloroethane 10 9.34 60-130 50 55.46 60-130

1,2,3-Trichloropropane 10 9.46 60-130 50 55.16 60-130

n-Propylbenzene 10 9.04 60-130 50 58.19 60-130

2-Chlorotoluene 10 8.52 60-130 50 56.59 60-130

4-Chlorotoluene 10 8.65 60-130 50 57.21 60-130

1,3,5-Trimethylbenzene 10 8.5 60-130 50 56.92 60-130

Tert-butylbenzene 10 8.21 60-130 50 59.46 60-130

1,2,4-trimethylbenzene 10 8.64 60-130 50 60.53 60-130

Sec-butylbenzene 10 9.24 60-130 50 58.88 60-130

1,3 – Dichlorobenzene 10 9.31 60-130 50 57.53 60-130


p-Isopropyltoluene 10 9.09 60-130 50 57.00 60-130


n-Butylbenzene 10 9.7 60-130 50 58.72 60-130

1,2-Dibromo-3-Chloropropane 10 8.15 60-130 50 52.14 60-130

1,2,4 – Trichlorobenzene 10 8.99 60-130 50 58.44 60-130

Hexachloro-1,3-butadiene 10 8.97 60-130 50 55.72 60-130

Naphthalene 10 9.05 60-130 50 55.34 60-130

1,2,3-Trichlorobenzene 10 8.45 60-130 50 58.98 60-130

NOTE: Data collected using a minimum of 10 points

uncontrolled


Table 5 - Extraction Spikes in Soil

Compound



TRUE (µg/g)

Mean (µg/g) Control Limits

(%Rec)

TRUE (µg/g)


(%Rec)

1,2 - Dichloroethane-d4 (S) - % 100 103.89 50-140 100 99.63 50-140

Toluene-d8 (S) - % 100 99.40 50-140 100 99.78 50-140


Dichlorodifluoromethane 4 3.66 50-140 20 16.40 50-140

Chloromethane 4 4.66 60-130 20 19.49 60-130

Vinyl Chloride 4 4.69 50-140 20 18.82 50-140

Bromomethane 4 4.9 50-140 20 17.92 50-140

Chloroethane 4 4.27 60-130 20 18.99 60-130

Trichlorofluoromethane 4 4.08 60-130 20 20.36 60-130

1,1 - Dichloroethene 4 4.89 60-130 20 22.98 60-130

Acetone 4 4.71 50-140 20 18.80 50-140


Methyl t-butyl ether (MTBE) 4 4.64 60-130 20 21.75 60-130

Trans - 1,2 - Dichloroethene 4 4.80 60-130 20 21.48 60-130

Hexane 4 4.86 60-130 20 18.56 60-130

1,1 - Dichloroethane 4 4.98 60-130 20 20.61 60-130

2,2 - Dichloropropane 4 4.41 60-130 20 20.77 60-130

2 - Butanone (Methyl Ethyl Ketone) 4 4.87 50-140 20 20.51 50-140

cis - 1,2 - Dichloroethene 4 4.94 60-130 20 20.33 60-130

Bromochloromethane 4 4.76 60-130 20 19.84 60-130

Chloroform 4 4.67 60-130 20 19.95 60-130

1,1,1 - Trichloroethane 4 4.45 60-130 20 20.15 60-130


1,1-Dichloropropene 4 4.54 60-130 20 20.98 60-130

Benzene 4 4.17 60-130 20 20.85 60-130

1,2 - Dichloroethane 4 4.56 60-130 20 19.99 60-130


1,2 - Dichloropropane 4 4.53 60-130 20 20.42 60-130

Dibromomethane 4 4.14 60-130 20 20.07 60-130

Bromodichloromethane 4 4.13 60-130 20 20.23 60-130

cis - 1,3 - Dichloropropene 4 3.73 60-130 20 20.94 60-130

Methyl Isobutyl Ketone (MIBK) 4 4.01 50-140 20 20.92 50-140

Toluene 4 4.08 60-130 20 21.39 60-130

Trans - 1,3 - Dichloropropene 4 3.89 60-130 20 21.24 60-130

1,1,2 - Trichloroethane 4 4.41 60-130 20 19.91 60-130



2-Hexanone (MBK) 4 3.82 60-130 20 20.95 60-130

Dibromochloromethane 4 3.96 60-130 20 20.18 60-130

1,2 – Dibromoethane (Ethylene dibromide) 4 4.18 60-130 20 19.95 60-130

Chlorobenzene 4 4.19 60-130 20 20.59 60-130

uncontrolled


Compound



TRUE (µg/g)


(%Rec)

TRUE (µg/g)


(%Rec)

1,1,1,2 - Tetrachloroethane 4 4.05 60-130 20 20.22 60-130

Ethylbenzene 4 4.03 60-130 20 21.95 60-130

m.p - Xylene 8 8.86 60-130 40 39.77 60-130

o - Xylene 4 4.03 60-130 20 21.82 60-130

Styrene 4 4.23 60-130 20 21.28 60-130

Bromoform 4 3.95 60-130 20 19.64 60-130

Isopropylbenzene 4 3.86 60-130 20 22.8 60-130

Bromobenzene 4 4.52 60-130 20 20.19 60-130

1,1,2,2 - Tetrachloroethane 4 4.75 60-130 20 19.79 60-130

1,2,3-Trichloropropane 4 4.78 60-130 20 19.95 60-130

n-Propylbenzene 4 4.42 60-130 20 20.08 60-130

2-Chlorotoluene 4 4.14 60-130 20 20.13 60-130

4-Chlorotoluene 4 4.23 60-130 20 20.07 60-130

1,3,5-Trimethylbenzene 4 4.09 60-130 20 19.82 60-130

Tert-butylbenzene 4 3.92 60-130 20 21.96 60-130

1,2,4-trimethylbenzene 4 4.22 60-130 20 21.97 60-130

Sec-butylbenzene 4 4.47 60-130 20 24.40 60-130

1,3 - Dichlorobenzene 4 4.61 60-130 20 20.08 60-130


p-Isopropyltoluene 4 4.33 60-130 20 25.03 60-130


n-Butylbenzene 4 4.52 60-130 20 20.46 60-130

1,2-Dibromo-3-Chloropropane 4 3.95 60-130 20 20.06 60-130

1,2,4 – Trichlorobenzene 4 4.1 60-130 20 21.66 60-130

Hexachloro-1,3-butadiene 4 3.92 60-130 20 19.54 60-130

Naphthalene 4 4.45 60-130 20 20.37 60-130

1,2,3-Trichlorobenzene 4 3.88 60-130 20 20.81 60-130

NOTE: Data collected using a minimum of 10 points

Table 6 - Extraction Spikes mSPLP

Compound


TRUE (µg/g) Mean (µg/g) Control Limits (%Rec)

1,2 - Dichloroethane-d4 (S) - % 100 101 50-140

Toluene-d8 (S) - % 100 104 50-140

Bromofluorobenzene (S) - % 100 101 50-140

Bromomethane 50 47.72 50-140

1,1-Dichloroethylene 50 44.60 60-130

Methylene Chloride 50 53.84 50-140

Trans-1,2-Dichloroethene 50 47.01 50-140

1,1-dichloroethane 50 53.20 60-130

Cis-1,2-Dichloroethene 50 49.04 60-130

Chloroform 50 53.72 60-130

uncontrolled


Compound


TRUE (µg/g) Mean (µg/g) Control Limits (%Rec)

Carbon Tetrachloride 50 44.81 50-140

1,1,1-Trichloroethane 50 48.82 60-130

1,2-Dichloroethane 50 55.14 60-130

Trichloroethylene 50 84.34 60-130

1,2-Dichloropropane 50 50.26 60-130

Cis-1,3-Dichloropropene 50 43.32 60-130

Tetrachloroethylene 50 47.09 60-130

Trans-1,3-Dichloropropene 50 48.85 50-140

1,1,2-Trichloroethane 50 57.57 60-130

Ethylene dibromide 50 59.03 60-130

1,4-Dioxane 200 234 60-130

1,1,1,2-Tetrachloroethane 50 48.27 60-130

1,1,2,2-Tetrachloroethane 50 1.32 60-130

1,4-Dichlorobenzene 50 45.28 60-130

1,2-Dichlorobenzene 50 51.63 60-130

Trichloroethylene + 1,1,2,2-Tetrachloroethane 100 85.66 60-130

Table 7 – TCLP Laboratory Control Samples

Compound



TRUE (µg/L)


(%Rec)

TRUE (µg/L)


(%Rec)

Dibromofluoromethane (S) - % 100 103.98 50-140 100 105 50-140

Toluene-d8 (S) - % 100 101.67 50-140 100 100.95 50-140


Vinyl Chloride 10 9.44 60-130 50 52.66 60-130

1,1 – Dichloroethene 10 8.97 60-130 50 46.71 60-130


2 –Butanone (Methyl Ethyl Ketone) 10 10.20 50-140 50 56.24 50-140

Chloroform 10 9.23 60-130 50 48.45 60-130


Benzene 10 10.33 60-130 50 54.87 60-130

1,2 – Dichloroethane 10 10.03 60-130 50 50.85 60-130



Chlorobenzene 10 8.10 60-130 50 43.00 60-130



uncontrolled


Table 8 - Method Detection Limits COMPOUND WATER & mSPLP SOIL TCLP

Calculated

MDL (µg/L)

Reporting MDL (µg/L)

Calculated MDL (µg/g)

Reporting MDL (µg/g)

Calculated MDL (µg/L)


Dichlorodifluoromethane (Freon 12) 0.09 2 0.03 0.05 N/A N/A

Difluorochloromethane (Freon 22) 0.14 3 N/A N/A N/A N/A

1,2-Dichlorotetrafluoroethane (Freon 114) 0.08 3 N/A N/A N/A N/A

2-Chloro-1,1,1-trifluoroethane (Freon 133a) 0.17 3 N/A N/A N/A N/A

Trichlorofluoromethane (Freon 11) 0.11 0.5 N/A N/A N/A N/A

Dichlorofluoromethane (Freon 21) 0.10 4 N/A N/A N/A N/A

1,1,2-Trichlorotrifluoroethane (Freon 113) 0.15 3 N/A N/A N/A N/A

2,2-Dichloro-1,1,1-trifluoroethane (Freon 123) 0.12 4 N/A N/A N/A N/A

1,2-Difluorotetrachloroethane (Freon 112) 0.07 3 N/A N/A N/A N/A

Chloromethane 0.06 2 0.06 2 N/A N/A

Vinyl Chloride 0.09 0.2 0.02 0.02 0.18 20

Bromomethane 0.14 0.5 0.25 3 N/A N/A

Chloroethane 0.08 3 0.04 3 N/A N/A

Trichlorofluoromethane 0.10 5 0.03 0.2 N/A N/A

1,1 - Dichloroethene 0.08 0.5 0.03 0.2 0.12 20

Acetone 1.45 30 0.52 5 N/A N/A

Methylene Chloride 0.65 5 0.02 0.05 0.09 20

Methyl t-butyl ether (MTBE) 0.10 2 0.02 0.05 N/A N/A

Trans - 1,2 - Dichloroethene 0.06 0.5 0.03 0.05 N/A N/A

Hexane 0.04 5 0.02 0.05 N/A N/A

1,1 - Dichloroethane 0.06 0.5 0.04 0.05 N/A N/A

2,2-Dichloropropane 0.10 0.2 0.05 0.05 N/A N/A

2 -Butanone (Methyl Ethyl Ketone) 0.90 20 0.04 0.5 0.23 20

cis - 1,2 - Dichloroethene 0.06 0.5 0.03 0.05 N/A N/A

Bromochloromethane 0.16 0.2 0.04 0.05 N/A N/A

Chloroform* 0.20 1 0.03 0.05 0.13 20

1,1,1 - Trichloroethane 0.13 0.5 0.03 0.05 N/A N/A

Carbon Tetrachloride 0.16 0.2 0.03 0.50 0.15 20

1,1-Dichloropropene 0.14 0.2 0.04 0.2 N/A N/A

Benzene 0.07 0.5 0.05 0.05 0.14 20

1,2 – Dichloroethane 0.11 0.5 0.02 0.05 0.15 20

Trichloroethene 0.07 0.5 0.02 0.05 0.22 20

1,2 – Dichloropropane 0.13 0.5 0.02 0.05 N/A N/A

Dibromomethane 0.06 0.5 0.03 0.05 N/A N/A

Bromodichloromethane* 0.14 2 0.02 0.2 N/A N/A

cis - 1,3 – Dichloropropene** 0.06 0.5 0.04 0.05 N/A N/A

Methyl Isobutyl Ketone (MIBK) 0.17 20 0.02 0.5 N/A N/A

Toluene 0.22 0.5 0.04 0.2 N/A N/A

1,4 – Dioxane 3.13 20 N/A N/A N/A N/A

Trans - 1,3 – Dichloropropene** 0.08 0.5 0.05 0.05 N/A N/A

1,1,2 – Trichloroethane 0.04 0.5 0.03 0.05 N/A N/A

uncontrolled


COMPOUND WATER & mSPLP SOIL TCLP

Calculated

MDL (µg/L)


Calculated MDL (µg/g)

Reporting MDL (µg/g)

Calculated MDL (µg/L)


Tetrachloroethene 0.08 0.5 0.02 0.05 0.10 20

1,3-Dichloropropane 0.11 0.2 0.04 0.05 N/A N/A

2-Hexanone (MBK) 0.09 5 0.04 0.5 N/A N/A

Dibromochloromethane* 0.03 2 0.04 0.05 N/A N/A

1,2 – Dibromoethane (Ethylene Dibromide) 0.03 0.2 0.05 0.5 N/A N/A

Chlorobenzene 0.08 0.5 0.02 0.05 0.06 20

1,1,1,2 – Tetrachloroethane 0.15 0.5 0.03 0.05 N/A N/A

Ethylbenzene 0.20 0.5 0.03 0.05 N/A N/A

m.p – Xylene*** 0.14 1.0 0.05 0.05 N/A N/A

o – Xylene*** 0.14 0.5 0.02 0.05 N/A N/A

Styrene 0.04 0.5 0.08 0.3 N/A N/A

Bromoform* 0.05 5 0.03 0.05 N/A N/A

Isopropylbenzene 0.04 0.2 0.2 0.3 N/A N/A

Bromobenzene 0.15 0.4 0.03 0.05 N/A N/A

1,1,2,2 - Tetrachloroethane 0.03 0.5 0.03 0.05 N/A N/A

1,2,3-Trichloropropane 0.07 0.5 0.04 0.05 N/A N/A

n-Propylbenzene 0.03 0.1 0.03 0.05 N/A N/A

2-Chlorotoluene 0.06 0.2 0.04 0.05 N/A N/A

4-Chlorotoluene 0.08 0.2 0.04 0.05 N/A N/A

1,3,5-Trimethylbenzene 0.06 0.1 0.09 0.2 N/A N/A

Tert-Butylbenzene 0.03 0.1 0.14 0.2 N/A N/A

1,2,4-Trimethylbenzene 0.03 1 0.22 0.7 N/A N/A

Sec-ButylBenzene 0.06 0.1 0.03 0.3 N/A N/A

1,3 - Dichlorobenzene 0.05 0.5 0.04 0.05 N/A N/A

1,4 - Dichlorobenzene 0.04 0.5 0.02 0.05 0.06 20

p-Isopropyltoluene 0.05 0.2 0.03 0.05 N/A N/A

1,2 - Dichlorobenzene 0.04 0.5 0.04 0.05 0.04 20

n-ButylBenzene 0.14 0.4 0.03 0.5 N/A N/A

1,2-Dibromo-3-Chloropropane 0.07 0.6 0.04 0.3 N/A N/A

1,2,4 - Trichlorobenzene 0.05 0.5 0.04 0.05 N/A N/A

Hexachloro-1,3-butadiene 0.06 0.6 0.04 0.5 N/A N/A

Naphthalene 0.04 0.4 0.22 0.4 N/A N/A

1,2,3-Trichlorobenzene 0.10 0.5 0.04 1.0 N/A N/A

*** Total Xylenes 0.058 1.1 0.036 0.04 N/A N/A

** Total Dichloropropenes 0.054 0.5 0.014 0.03 N/A N/A

* Total Trihalomethanes 0.078 6 0.02 0.05 N/A N/A

uncontrolled


Table 9 - List of Compounds and Quantitation Masses.

Compound Primary Quantitation Mass Secondary Quantitation Mass

Acetone 58 43

Benzene 78 -

Bromobenzene 156 77, 158

Bromochloromethane 128 49, 130

Bromodichloromethane 83 85, 127

Bromoform 173 175, 254

Bromomethane 94 96

2-Butanone (Methyl ethyl ketone) 72 43

n-Butylbenzene 91 92, 134

sec-Butylbenzene 105 134

tert-Butylbenzene 119 91, 134

Carbon tetrachloride 117 119

Chlorobenzene 112 77, 114

Chloroethane 64 (49*) 66 (51*)

Chloroform 83 85

Chloromethane 50 (49*) 52 (51*)

2-Chlorotoluene 91 43

4-Chlorotoluene 91 -

2-Chloro-1,1,1-trifluoroethane 118 83,120

1,2-Dibromo-3-chloropropane (DBCP) 75 155, 157

Dibromochloromethane 129 127, 131

1,2-Dibromoethane (Ethylene dibromide)

107 109, 188

Dibromomethane 93 95, 174

1,2-Dichlorobenzene 146 111, 148



Difluorochloromethane 51 87

Dichlorodifluoromethane 85 87

Dichlorofluoromethane 67 69

2,2-Dichloro-1,1,1-trifluoroethane 83 85, 69

1,1-Dichloroethane 63 65, 83

1,2-Dichloroethane 62 98

1,1-Dichloroethene (Vinylidene chloride) 96 61, 63

cis-1,2-Dichloroethene 96 61, 98

trans-1,2-Dichloroethene 96 61, 98

1,2-Dichloropropane 63 112



1,1-Dichloropropene 75 110, 77

cis-1,3-Dichloropropene 75 77, 39

uncontrolled


Compound Primary Quantitation Mass Secondary Quantitation Mass

trans-1,3-Dichloropropene 75 77, 39

1,2-Difluorotetrachloroethane 101 167, 169

1,2-Dichlorotetrafluoroethane 85 135, 87

1,4-Dioxane 88 58, 43, 57

Ethylbenzene 91 106

Hexane 57 41, 43

Hexachloro-1,3-butadiene 225 223, 227

2-Hexanone (MBK) 43 58, 57, 100

Isopropylbenzene 105 120

p-Isopropyltoluene 119 134, 91

Methyl-t-butyl ether 73 57

4-Methyl-2-pentanone (MIBK) 100 43, 58, 85

Methylene chloride 84 86, 49

Naphthalene 128 127

n-Propylbenzene 91 120

Styrene 104 78

1,1,1,2-Tetrachloroethane 131 133, 119

1,1,2,2-Tetrachloroethane 83 131, 85

Tetrachloroethene 164 129, 131, 166

Toluene 92 91

1,2,3-Trichlorobenzene 180 182, 145

1,2,4-Trichlorobenzene 180 182, 145

1,1,1-Trichloroethane 97 99, 61

1,1,2-Trichloroethane 83 97, 85

Trichlororethene 95 97, 130, 132

Trichlorofluoromethane 101 103

1,2,3-Trichloropropane 75 77

1,1,2-Trichlorotrifluoroethane 101 151,103

1,2,4-Trimethylbenzene 105 120

1,3,5-Trimethylbenzene 105 120

Vinyl chloride 62 64

o-Xylene 106 91

m-Xylene 106 91

p-Xylene 106 91

9.7 Based on method performance and based on validation data this method is fit for intended use. 9.8 Unless otherwise indicated, all tables found in section 9 of this method contain original validation

data and are present to support the statements made in section 9.7. All analysts must refer to the relevant QAQC logs for the current limits when verifying data is acceptable for reporting.

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Caduceon Environmental Laboratories Page: 23 of 24 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB 10.0 References 10.1 Methods Documents

10.1.1 USEPA "SW-846 Tests Methods for Evaluating Solid Waste," 3rd Ed.; Methods 5030, 5035 and 8260. Current Version.

10.1.2 Organic Extraction and Sample Preparation, EPA Method 3500, Current Version. 10.1.3 Caduceon Method % Solids Method %SOLIDS-001. 10.1.4 Caduceon TCLP/SPLP-001 Toxicity Characteristic and Synthetic Precipitation Leaching

Procedure

10.2 Caduceon Procedures

10.2.1 Caduceon CP-021 Balance Calibration and Verification. 10.2.2 Caduceon CP-022 Volumetric Calibration and Verification. 10.2.3 Caduceon CP-029 Method Detection Limits. 10.2.4 Caduceon CP-030 Method Validation. 10.2.5 Caduceon CP-031 Control Charting. 10.2.6 Caduceon CP-032 Non-Conformity Logs. 10.2.7 Caduceon SOP-025 Receiving of Chemicals, Essential Parts and Equipment.

10.3 Other Supporting Documents

10.3.1 ATOMX Teledyne Tekmar User Manual. 10.3.2 HP Instrument and Software Manual

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Caduceon Environmental Laboratories Page: 24 of 24 Volatile Organic Compounds in Water, Soil and Solids P&T GC/MS Revision Date: 03-June-2021 Method C-VOC-02 Revision #: 2.3 Management Review: CB Quality Review: SB Log of Revisions

Date Rev Description Author

20-Apr-2017

1.4 Section 6.5 updated to include storage conditions Section 7.2 updated to reflect current settings Section 9.9 added statement about method validation data

SB

28-Aug-2018 2.0 Multiple sections updated to add additional compounds and TCLP analysis. Validation data for new compounds has been added to current tables.

JE

03-May-2019 2.1 Section 4.2, 4.4 – Updated holding times Section 6.6- 6.9 – Updated standards, preparations storage conditions and forms used to reflect current practice Section 7.4 - Updated to correct some conditions and add form Section 7.6.1 updated to qualify tuning criteria Section 7.8.3 updated analytical run acceptance Section 9.7 – Corrected compound names throughout all Tables Added Table 7 – List of Compounds and Quantitation Masses Appendix A removed from method Corrected numbering throughout document

JE/CB

25-Jan-2021 2.2 Updated multiple sections to include SPLP Section 3.2 changed MSDS to SDS Sections 5.9.2 and 7.2.1 updated to correct column name Sections 6.6 and 6.7 updated standard/QC names Section 7.4.4 updated extraction section to reflect current practice. Section 7.6.1 updated to note instrument conditions. Section 7.6.2.2 updated sample sequence. Section 7.8.2 updated to clarify data acceptance. Sections 7.8.5 and 9.6 updated to include surrogate limits

CB/SKB

03-Jun-2021 2.3 Section 1.1 updated to include mSPLP Section 6.6.7 updated to correct calibration standards. Section 9.2 update to include additional tables. Section 9.6 updated to include validation data for mSPLP

CB/SB

Document Review This document was last reviewed and authorized by: Laboratory Branch Manager Date Laboratory Branch Manager Date Laboratory Branch Manager Date Laboratory Branch Manager Date

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