Appendix A Laboratory Standard Operating Procedures *** Laboratory SOPs are proprietary business information to be shared for review among Pepco, AECOM, and DDOE only *** Benning Road Facility DRAFT June 2012 Sampling and Analysis Plan – Quality Assurance Project Plan This is a controlled document. When printed it becomes uncontrolled. TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 17 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 1 of 1 Title: DETERMINATION OF VOLATILE ORGANICS BY GC/MS Methods: SW-846 8260B AND EPA 624 Approvals (Signature/Date): __________________________7/20/2011 _ ________________ 7/26/2011 Kathy Gordon Date Steve Jackson Date Technical Specialist Health & Safety Manager __________________________7/25/2011 ________________________8/16/2011 Nasreen DeRubeis Date Debbie Lowe Date Quality Assurance Manager Laboratory Director Copyright Information: This documentation has been prepared by TestAmerica Analytical Testing Corp. and its affiliates (“TestAmerica”), solely for their own use and the use of their customers in evaluating their qualifications and capabilities in connection with a particular project. The user of this document agrees by its acceptance to return it to TestAmerica upon request and not to reproduce, copy, lend, or otherwise disclose its contents, directly or indirectly, and not to use if for any other purpose other than that for which it was specifically provided. The user also agrees that where consultants or other outside parties are involved in the evaluation process, access to these documents shall not be given to said parties unless those parties also specifically agree to these conditions. THIS DOCUMENT CONTAINS VALUABLE CONFIDENTIAL AND PROPRIETARY INFORMATION. DISCLOSURE, USE OR REPRODUCTION OF THESE MATERIALS WITHOUT THE WRITTEN AUTHORIZATION OF TESTAMERICA IS STRICTLY PROHIBITED. THIS UNPUBLISHED WORK BY TESTAMERICA IS PROTECTED BY STATE AND FEDERAL LAW OF THE UNITED STATES. IF PUBLICATION OF THIS WORK SHOULD OCCUR THE FOLLOWING NOTICE SHALL APPLY: ©COPYRIGHT 2011 TESTAMERICA ANALYTICAL TESTING CORP. ALL RIGHTS RESERVED. Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 2 of 2 1. SCOPE AND APPLICATION 1.1. This method is applicable to the determination of Volatile Organic Compounds in waters, wastewater, soils, sludges and other solid matrices. Standard analytes are listed in Tables 1, 2, and A-1. For DoD current version refer to SOP PT-QA-029. 1.2. This SOP is applicable to method 8260B and 624. Appendix A present modifications to the procedures in the main SOP that are necessary for analysis of water samples by method 624. For DoD QSM 3.0 requirements refer to SOP PT-QA-025, Implementation of DoD QSM Version 3, January 2006. For DoD QSM current version requirements refer to SOP PT-QA-029. 1.3. This method can be used to quantify most volatile organic compounds that have boiling points below 200°C and are insoluble or slightly soluble in water. Volatile water soluble compounds can be included in this analytical technique; however, for more soluble compounds, quantitation limits are approximately ten times higher because of poor purging efficiency. 1.4. The method is based upon a purge and trap, gas chromatograph/mass spectrometric (GC/MS) procedure. The approximate working range is 5 to 250 µg/L for 5 mL standard level waters, 1 to 40 µg/L for low level waters, 5 to 250 µg/kg for low-level soils, and 250 to 25,000 µg/kg for medium-level soils. Reporting limits are listed in Tables 1, 2, and A-1. 1.5. Method performance is monitored through the use of surrogate compounds, matrix spike/matrix spike duplicates, and laboratory control spike samples. 2. SUMMARY OF METHOD 2.1. Volatile compounds are introduced into the gas chromatograph by the purge and trap method. The components are separated via the chromatograph and detected using a mass spectrometer, which is used to provide both qualitative and quantitative information. 2.2. Aqueous samples are purged directly. Generally, soils are preserved by extracting the volatile analytes into methanol. If especially low detection limits are required, soil samples may be frozen and purged directly. 2.3. In the purge and trap process, an inert gas is bubbled through the solution at ambient temperature or at 40oC (40oC required for low level soils) and the volatile components are efficiently transferred from the aqueous phase to the vapor phase. The vapor is swept through a sorbant column where the volatile components are Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 3 of 3 trapped. After purging is completed, the sorbant column (trap) is heated and back flushed with inert gas to desorb the components onto a gas chromatographic column. The gas chromatographic column is then heated to elute the components, which are detected with a mass spectrometer. 2.4. Qualitative identifications are confirmed by analyzing standards under the same conditions used for samples, and comparing the resultant mass spectra and GC retention times. Each identified component is quantified by relating the MS response for an appropriate selected ion produced by that compound to the MS response for another ion produced by an internal standard. 3. DEFINITIONS 3.1. Batch: The batch is a set of up to 20 samples of the same matrix processed using the same procedures and reagents within the same time period. Using this method, each BFB analysis will normally start a new batch. Batches for medium level soils are defined at the sample preparation stage and may be analyzed on multiple instruments over multiple days, although reasonable effort should be made to keep the samples together. 6.8.1 The Quality Control batch must contain a matrix spike/spike duplicate (MS/MSD), a Laboratory Control Sample (LCS), and a method blank. In some cases, at client request, the MS/MSD may be replaced with a matrix spike and sample duplicate. If insufficient sample is received, an LCS/LCSD will be used in the place of an MS/MSD. Refer to the TestAmerica Pittsburgh QC Program document (PT-QA-021) for further details of the batch definition. 3.2. Method Blank A method blank consisting of all reagents added to the samples must be analyzed with each batch of samples. The method blank is used to identify any background interference or contamination of the analytical system, which may lead to the reporting of elevated concentration levels or false positive data. 3.3. Laboratory Control Sample (LCS) Laboratory Control Samples are well characterized, laboratory generated samples used to monitor the laboratory's day-to-day performance of routine analytical methods. The LCS, spiked with a group of target compounds representative of the method analytes, is used to monitor the accuracy of the analytical process, independent of matrix effects. Ongoing monitoring of the LCS results provides evidence that the Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 4 of 4 laboratory is performing the method within accepted QC guidelines for accuracy and precision. 3.4. Surrogates Surrogates are organic compounds which are similar to the target analyte(s) in chemical composition and behavior in the analytical process, but which are not normally found in environmental samples. Each sample, blank, LCS, and MS/MSD is spiked with surrogate standards. Surrogate spike recoveries must be evaluated by determining whether the concentration (measured as percent recovery) falls within the required recovery limits. 3.5. Matrix Spike/Matrix Spike Duplicate (MS/MSD) A matrix spike is an environmental sample to which known concentrations of target analytes have been added. A matrix spike duplicate is a second aliquot of the same sample, which is prepared and analyzed along with the sample and matrix spike. Matrix spikes and duplicates are used to evaluate accuracy and precision in the actual sample matrix. 3.6. Calibration Check Compound (CCC) CCCs are a representative group of compounds, which are used to evaluate initial calibrations and continuing calibrations. Relative standard deviation (%RSD) for the initial calibration and % drift or % deviation (%D) for the continuing calibration response factors are calculated and compared to the specified method criteria. 3.7. System Performance Check Compounds (SPCC) SPCCs are compounds, which are sensitive to system performance problems and are used to evaluate system performance and sensitivity. Response factors from the initial and continuing calibrations are calculated for the SPCC compounds and compared to the specified method criteria. 4. INTERFERENCES 4.1. Method interferences may be caused by contaminants in solvents, reagents, glassware, and other processing apparatus that lead to discrete artifacts. All of these materials must be routinely demonstrated to be free from interferences under conditions of the analysis by running laboratory method blanks as described in the Quality Control section. The use of ultra high purity gases, pre-purged purified reagent water, and approved lots of purge and trap grade methanol will greatly reduce introduction of contaminants. In extreme cases the purging vessels may be pre-purged Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 5 of 5 to isolate the instrument from laboratory air contaminated by solvents used in other parts of the laboratory. 4.2. Samples can be contaminated by diffusion of volatile organics (particularly methylene chloride and fluorocarbons) into the sample through the septum seal during shipment and storage. A field blank prepared from reagent water and carried through the sampling and handling protocol can serve as a check on such contamination. 4.3. Matrix interferences may be caused by non-target contaminants that are coextracted from the sample. The extent of matrix interferences will vary considerably from source to source depending upon the nature and diversity of the site being sampled. 4.4. Cross-contamination can occur whenever high-level and low-level samples are analyzed sequentially or in the same purge position on an autosampler. Whenever an unusually concentrated sample is analyzed, it should be followed by one or more blanks to check for cross-contamination. The purge and trap system may require extensive bake-out and cleaning after a high-level sample. 4.5. Some samples may foam when purged due to surfactants present in the sample. When this kind of sample is encountered an antifoaming agent (Dow Corning Antifoam C) can be used. A blank spiked with this agent must be analyzed with the sample to show there is no target interferences induced by this agent. The antifoaming agent is not used routinely. If it needs to be used, approval from Project Manager is obtained, unless prior client approval has been obtained. 5. SAFETY 5.1. Employees must abide by the policies and procedures in the Corporate Environmental Health and Safety Manual (CW-E-M-001), Radiation Safety Manual and this document. This procedure may involve hazardous material, operations and equipment. This SOP does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of the method to follow appropriate safety, waste disposal and health practices under the assumption that all samples and reagents are potentially hazardous. Safety glasses, gloves, lab coats and closed-toe, nonabsorbent shoes are a minimum. 5.2. The gas chromatograph contains zones that have elevated temperatures. The analyst needs to be aware of the locations of those zones, and must cool them to room temperature prior to working on them. 5.3. There are areas of high voltage in the gas chromatograph. Depending on the type of work involved, either turn the power to the instrument off, or disconnect it from its source of power. Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 6 of 6 5.4. The mass spectrometer is under deep vacuum. The mass spectrometer must be brought to atmospheric pressure prior to working on the source. 5.5. The following is a list of the materials used in this method, which have a serious or significant hazard rating. NOTE: This list does not include all materials used in the method. The table contains a summary of the primary hazards listed in the MSDS for each of the materials listed in the table. A complete list of materials used in the method can be found in the reagents and materials section. Employees must review the information in the MSDS for each material before using it for the first time or when there are major changes to the MSDS. Material (1) Hazards Exposure Signs and symptoms of exposure Limit (2) Methanol Flammable 200 ppm- A slight irritant to the mucous membranes. Poison TWA Toxic effects exerted upon nervous system, Irritant particularly the optic nerve. Symptoms of overexposure may include headache, drowsiness and dizziness. Methyl alcohol is a defatting agent and may cause skin to become dry and cracked. Skin absorption can occur; symptoms may parallel inhalation exposure. Irritant to the eyes. 1 – Always add acid to water to prevent violent reactions. 2 – Exposure limit refers to the OSHA regulatory exposure limit. 5.6. Eye protection that protects against splash, laboratory coat, and appropriate gloves must be worn while samples, standards, solvents, and reagents are being handled. Cut resistant gloves must be worn doing any other task that presents a strong possibility of getting cut. Disposable gloves that have become contaminated will be removed and discarded, other gloves will be cleaned immediately. 5.7. Exposure to chemicals must be maintained as low as reasonably achievable, therefore, unless they are known to be non-hazardous, all samples should be opened, transferred, and prepared in a fume hood, or under other means of mechanical ventilation. Solvent and waste containers will be kept closed unless transfers are being made. 5.8. The preparation of standards and reagents will be conducted in a fume hood with the sash closed as far as the operations will permit. 5.9. All work must be stopped in the event of a known or potential compromise to the health and safety of a TestAmerica associate. The situation must be reported immediately to a laboratory supervisor or EH&S coordinator. Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 7 of 7 6. EQUIPMENT AND SUPPLIES 6.1. Microsyringes: 10 uL and larger, 0.006 inch ID needle. 6.2 Syringe: 5 or 25 mL glass with luerlok tip, if applicable to the purging device. 6.2. Balance: Top-loading balance capable of weighing 0.01 g 6.3. Glassware: 6.8.1 Vials: 40 mL with screw caps and Teflon liners. 6.8.2 Volumetric flasks: 10 mL, 50 mL and 100 mL, class A with ground-glass stoppers. 6.4. Spatula: Stainless steel. 6.5. Disposable pipettes: Pasteur. 6.6. pH paper: Narrow range. 6.7. Gases: Helium: Ultra high purity, gr. 99.999%. 6.8. Purge and Trap Device: The purge and trap device consists of the sample purger, the trap, and the desorber. 6.8.1 Sample Purger: The recommended purging chamber is designed to accept 5 mL samples with a water column at least 3 cm deep. The purge gas must pass through the water column as finely divided bubbles, each with a diameter of less than 3 mm at the origin. The purge gas must be introduced no more than 5 mm from the base of the water column. Alternative sample purge devices may be used provided equivalent performance is demonstrated. Low level soils are purged directly from a VOA vial. 6.8.2 Trap: OI # 10 6.8.3 Desorber: The desorber should be capable of rapidly heating the trap to at least 180(cid:176) C. Many such devices are commercially available. 6.8.4 Sample Heater: A heater capable of maintaining the purge device at 40(cid:176) C is necessary for low level soil analysis. Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 8 of 8 6.9 Gas Chromatograph/Mass Spectrometer System: 6.9.1 Gas Chromatograph: The gas chromatograph (GC) system must be capable of temperature programming. 6.9.2 Gas Chromatographic Columns: Capillary columns are used. Some typical columns are listed below: 6.9.2.1 Column 1: 20m x 0.18 ID J&W DB-624 or Restek 502.2 with 1 µm film thickness. 6.9.3 Mass Spectrometer: The mass spectrometer must be capable of scanning 35- 300 AMU every two seconds or less, using 70 volts electron energy in the electron impact mode and capable of producing a mass spectrum that meets the required criteria when 50 ng or 25 ng of 4-Bromofluorobenzene (BFB) are injected onto the gas chromatograph column inlet. 6.9.4 Data System: A computer system that allows the continuous acquisition and storage on machine-readable media of all mass spectra obtained throughout the duration of the chromatographic program. The computer must have software that allows searching any GC/MS data file for ions of a specified mass and plotting such ion abundances versus time or scan number. This type of plot is defined as an Extracted Ion Current Profile (EICP). Software must also be available that allows integrating the abundances in any EICP between the specified time or scan- number limits. Also, for the non-target compounds, software must be available that allows for the comparison of sample spectra against reference library spectra. The most recent release of the NIST/EPA mass spectral library should be used as the reference library. The computer system must also be capable of backing up data for long-term off-line storage. 7. REAGENTS AND STANDARDS 7.1 Reagents 7.1.1 Methanol: Purge and Trap Grade, High Purity 7.1.2 Reagent Water: High purity water that meets the requirements for a method blank when analyzed. (See section 9.5) Reagent water is obtained from Millipore system. Other methods of preparing reagent water are acceptable. 7.1.3 1:1 HCl Distributed To: QA Web Page: Company Confidential & Proprietary This is a controlled document. When printed it becomes uncontrolled. TestAmerica TestAmerica Pittsburgh SOP No. PT-MS-002, Rev. 16 Effective Date: 08/16/2011 THE LEADER IN ENVIRONMENTAL TESTING Page No.: 9 of 9 7.2 Standards 7.2.1 Calibration Standard 7.2.1.1 Stock Solutions: Stock solutions may be purchased as certified solutions from commercial sources or prepared from pure standard materials as appropriate. These standards are prepared in methanol and stored in Teflon-sealed screw-cap bottles with minimal headspace at -10(cid:1) to - 20(cid:1)C. 7.2.1.2 Working standards: A working solution containing the compounds of interest is prepared from the stock solution(s) in methanol. The working standard solutions will be prepared monthly with the exceptions of the gases and 2-chloroethylvinyl ether solutions, which will be prepared on a weekly basis. These standards are stored in the freezer or as recommended by the manufacturer. Working standards are monitored by comparison to the initial calibration curve. If any of the calibration check compounds drift in response from the initial calibration by more than 20% then corrective action is necessary. This may include steps such as instrument maintenance, preparing a new calibration verification standard or tuning the instrument. If the corrective actions do not correct the problem then a new initial calibration must be performed. 7.2.1.3 Aqueous Calibration Standards are prepared in reagent water using the secondary dilution standards. These aqueous standards must be prepared daily. 7.2.1.4 If stock or secondary dilution standards are purchased in sealed ampoules they may be used up to the manufacturers expiration date. 7.2.2 Internal Standards: Internal standards are added to all samples, standards, and blank analyses. Refer to Table 6 for internal standard components. 7.2.3 Surrogate Standards: Refer to Table 7 for surrogate standard components and spiking levels. 7.2.4 Laboratory Control Sample Spiking Solutions: Refer to Table 8 for the normal control LCS components and spiking levels. 7.2.5 Matrix Spiking Solutions: The matrix spike contains the same control components as the LCS. Refer to Table 8. Distributed To: QA Web Page: Company Confidential & Proprietary