United States Environmental Protection Agency Office of Solid Waste and Publication 9240.0-09FSA Emergency Response November 1996 vvEPA Multi-Media, Multi-Concentration, Organic Analytical Service for Superfund Office of Emergency and Remedial Response Analytical OperationsNData Quality Center (5204G) Quick Reference Fact Sheet Under the legislative authority granted to the U.S. Environmental Protection Agency (EPA) under the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) and the Superfund Amendments and Reauthorization Act of 1986 (SARA), EPA develops standardized analytical methods for the measurement of various pollutants in environmental samples from known or suspected hazardous waste sites. Among the pollutants that are of concern to EPA at such sites are a series of volatile, semivolatile, pesticide, and Aroclor compounds that are analyzed using gas chromatography coupled with mass spectrometry (GC/MS) and gas chromatography with an electron capture detector (GC/EC). The Analytical OperationsXData Quality Center (AOC) of the Office of Emergency and Remedial Response (OERR) offers an analytical service that provides data from the analysis of water, soil/sediment, and waste samples for organic compounds for use in the Superfund decision-making process. Through a series of standardized procedures and strict chain-of-custody, the organic analytical service produces data of known and documented quality. This service is available through the Superfund Contract Laboratory Program (CLP). DESCRIPTION OF SERVICES The organic analytical service provides a technical and contractual framework for laboratories to apply EPA/CLP analytical methods for the isolation, detection and quantitative measurement of 33 volatile, 64 semivolatile, and 28 pesticide/Aroclor target compounds in water and soil/sediment environmental samples. The analytical service provides the methods to be used and the specific technical and contractual requirements, including quality assurance, quality control, and standard operating procedures, by which EPA will evaluate the data This service uses GC/MS and GC/EC methods to analyze the target compounds. Two data delivery turnarounds are available to the Regional EPA offices: 35 day turnaround and 14 day turnaround after laboratory receipt of the last sample in the set. DATA USES This analytical service provides data which EPA uses for a variety of purposes, such as determining the nature and extent of contamination at a hazardous waste site, assessing priorities for response based on risks to human health and the environment, determining appropriate cleanup actions, and determining when remedial actions are complete. The data may be used in all stages in the investigation of a hazardous waste site including site inspections, Hazard Ranking System scoring, remedial investigations/feasibility studies, remedial design, treatability studies, and removal actions. In addition, this service provides data that are available for use in Superfund enforcement/litigation activities. ANALYTES The analytes for which this service is applicable and the corresponding baseline quantitation limits are listed in Table 1. For water samples, the lowest quantitation limits reportable are 10 ppb for the volatile analytes, 10 ppb for the semivolatile analytes, and 0.05 ppb for the pesticide analytes. For soil samples, the lowest quantitation limits reportable are 10 ppb for the volatile analytes, 330 ppb for the semivolatile analytes, and 1.7 ppb for the pesticide analytes. ------- Table 1. Target Compound List and Contract Required Quantitation Limits* Quantitation Limits Water Low Soil ug/L ug/Kg Quantitation Limits Water Low Soil ug/L ug/Kg VOLATILES 1. Chloromethane 10 10 2. Bromomethane 10 10 3. Vinyl Chloride 10 10 4. Chloroethane 10 10 5. Methylene Chloride 10 10 6. Acetone 10 10 7. Carbon Disulfide 10 10 8.1,1-Dichloroethene 10 10 9.1,1-Dichloroethane 10 10 10.1,2-Dichloroethene (total) 10 10 11. Chloroform 10 10 12.1,2-Dichloroethane 10 10 13. 2-Butanone 10 10 14.1,1,1-Trichloroethane 10 10 15. Carbon Tetrachloride 10 10 16. Bromodichloromethane 10 10 17.1,2-Dichloropropane 10 10 18. cis-1,3-Dichloropropene 10 10 19. Trichloroethene 10 10 20. Dibromochloromethane 10 10 21.1,1,2-Trichloroethane 10 10 22. Benzene 10 10 23. trans-1,3-Dichloropropene 10 10 24. Bromoform 10 10 25. 4-Methyl-2-pentanone 10 10 26. 2-Hexanone 10 10 27. Tetrachloroethene 10 10 28. Toluene 10 10 29.1,1,2,2-Tetrachloroethane 10 10 30. Chlorobenzene 10 10 31. Ethylbenzene 10 10 32. Styrene 10 10 33. Xylenes (Total) 10 10 SEMIVOLATILES 34. Phenol 10 330 35. bis(2-Chloroethyl) ether 10 330 36.2-Chlorophenol 10 330 37.1,3-Dichlorobenzene 10 330 38.1,4-Dichlorobenzene 10 330 39.1,2-Dichlorobenzene 10 330 40. 2-Methylphenol 10 330 41. 2,2'-oxybis(1-Chloropropane) 10 330 42. 4-Methylphenol 10 330 43. N-Nitroso-di-n-propylamine 10 330 44. Hexachloroethane 10 330 45. Nitrobenzene 10 330 46. Isophorone 10 330 47. 2-Nitrophenol 10 330 48. 2,4-Dimethylphenol 10 330 49. bis(2-Chloroethoxy) methane 10 330 50. 2,4-Dichlorophenol 10 330 51.1,2,4-Trichlorobenzene 10 330 52. Naphthalene 10 330 53. 4-Chloroaniline 10 330 54. Hexachlorobutadiene 10 330 55. 4-Chloro-3-methylphenol 10 330 56.2-Methylnaphthalene 10 330 57. Hexachlorocyclopentadiene 10 330 58. 2,4,6-Trichlorophenol 10 330 59. 2,4,5-Trichlorophenol 25 800 60.2-Chloronaphthalene 10 330 61. 2-Nitroaniline 25 800 62. Dimethylphthalate 10 330 63. Acenaphthylene 10 . 64. 2,6-Dinitrotoluene 10 . 65. 3-Nitroaniline 25 . 66. Acenaphthene 10 . 67. 2,4-Dinitrophenol 25 . 68. 4-Nitrophenol 25 . 69. Dibenzofuran 10 . 70.2,4-Dinitrotoluene 10 . 71. Diethylphthalate 10 . .330 .330 .800 .330 .800 .800 .330 .330 .330 72. 4-Chlorophenyl phenyl ether 10 330 73. Fluorene 10 330 74.4-Nitroaniline 25 800 75.4,6-Dinitro-2-methylphenol 25 800 76. N-nitrosodiphenylamine 10 330 77.4-Bromophenyl phenyl ether 10 330 78. Hexachlorobenzene 10 330 79. Pentachlorophenol 25 800 80. Phenanthrene 10 330 81. Anthracene 10 330 82. Carbazole 10 330 83. Di-n-butylphthalate 10 330 84. Fluoranthene 10 330 85. Pyrene 10 330 86. Butylbenzylphthalate 10 330 87. 3,3'-Dichlorobenzidine 10 330 88. Benzo(a)anthracene 10 330 89. Chrysene 10 330 90. bis(2-Ethylhexyl)phthalate 10 330 91. Di-n-octylphthalate 10 330 92. Benzo(b)fluoranthene 10 330 93. Benzo(k)fluoranthene 10 330 94. Benzo(a)pyrene 10 330 95. lndeno(1,2,3-cd)pyrene 10 330 96. Dibenz(a,h)anthracene 10 330 97. Benzo(g,h,i)perylene 10 330 Water Soil PESTICIDES/AROCLORS ug/L ug/L 98. alpha-BHC 0.05 1.7 99. beta-BHC 0.05 1.7 100. delta-BHC 0.05 1.7 101. gamma-BHC (Lindane) 0.05 1.7 102. Heptachlor 0.05 1.7 103. Aldrin 0.05 1.7 104. Heptachlor epoxide 0.05 1.7 105. Endosulfan I 0.05 1.7 106. Oieldrin 0.10 3.3 107.4,4'-DDE 0.10 3.3 108. Endrin 0.10 3.3 109. Endosulfan II 0.10 3.3 110. 4,4'-DDD 0.10 3.3 111. Endosulfan sulfate 0.10 3.3 112. 4,4'-DDT 0.10 3.3 113. Methoxychlor 0.50 17.0 114. Endrin ketone 0.10 3.3 115. Endrin aldehyde 0.10 3.3 116. alpha-Chlordane 0.05 1.7 117. gamma-Chlordane 0.05 1.7 118. Toxaphene 5.0 170.0 119. Aroclor-1016 1.0 33.0 120. Aroclor-1221 2.0 67.0 121. Aroclor-1232 1.0 33.0 122. Aroclor-1242 1.0 33.0 123. Aroclor-1248 1.0 33.0 124. Aroclor-1254 1.0 33.0 125. Aroclor-1260 1.0 33.0 * For volatiles, quantitation limits for medium soils are approximately 120 times the quantltatlon limits for low soils. For semivolatlle medium soils, quanlitatlon limits are approximately 30 times the quanlllatlon limits for low soils. ------- Specific sample quantitation limits are highly matrix dependent. The list of target compounds for this service was originally derived from the EPA Priority Pollutant List of 129 compounds. In the years since the inception of the CLP, compounds have been added to and deleted from the Target Compound List, based on advances in analytical methods, evaluation of method performance data, and the needs of the Superfund program. For drinking water/groundwater type samples, use of the low concentration organic analytical service (water matrix) is recommended. For high hazard organic samples (e.g., drum samples), use of the high concentration organic analytical service is recommended. METHODS AND INSTRUMENTATION For semivolatile and pesticide/Aroclor samples, a 1-L water sample is extracted with methylene chloride. For low level semivolatile soil and pesticide/Aroclor soil samples, a 30-g soil sample is extracted with methylene chloride/acetone. For medium level semivolatile soil samples, a 1-g soil sample is extracted with methylene chloride/acetone. For both water and soil samples, the extract is concentrated, subjected to fraction-specific cleanup procedures, and analyzed by GC/MS for semivolatiles or GC/EC for pesticides/Aroclors. For voltile water samples, 5 mL of water is added to a purge and trap device and purged with an inert gas at room temperature. For volatile low level soil samples, a 5-g aliquot of soil is added to a purge and trap device with 5 mL of reagent water and purged with an inert gas at 40 °C. For volatile medium level soil samples, 4 g are extracted with methanol and an aliquot is added to a purge and trap device. For both water and soil samples, the volatiles purged from the sample are trapped on a solid sorbent. They are subsequently desorbed by rapidly heating the sorbent and then introduced into a GC/MS system. Table 2 summarizes the instruments and methods used in this analytical service. DATA DELIVERABLES Data deliverables for this service include hardcopy data reporting forms and supporting raw data. In addition to the hardcopy deliverable, contract laboratories must submit the same data on diskette. The diskette data are used by EPA to rapidly assess the contractual and technical performance of the laboratory. The laboratory must submit data to EPA within 35 days (or 14 days for 14-day contracts) of sample receipt. EPA then checks the data for compliance with contract requirements within 10 days and adds the data to a comprehensive database of CLP analytical results. A report of instances of noncompliance is distributed to the laboratory and the Region. The laboratory has 10 days to reconcile defective data and resubmit the data to EPA. EPA then screens the data within 10 days and sends a final report to the laboratory and the Region. QUALITY ASSURANCE The quality assurance (QA) process consists of management review and oversight at the planning, implementation, and completion stages of the environmental data collection activity. This process ensures that the data provided are of the quality required. Table!. Instruments and Methods Fraction Volatiles Semivolatiles Pesticides/Arodors Instrument GC/MS with purge and trap device GC/MS GC/EC with dual column Method Purge and trap concentration followed by GC/MS analysis Liquid-liquid extraction followed by capillary GC/MS analysis Liquid-liquid extraction followed by capillary GC/EC analysis ------- During the implementation of the data collection effort, QA activities ensure that the quality control (QC) system is functioning effectively, and that the deficiencies uncovered by the QC system are corrected. After environmental data are collected, QA activities focus on assessing the quality of data to determine its suitability to support enforcement or remedial decisions Each contract laboratory prepares a quality assurance plan (QAP) with the objective of providing sound analytical chemical measurements. The QAP must specify the policies, organization, objectives, and functional guidelines, as well as the QA and QC activities designed to achieve the data quality requirements for this analytical service. QUALITY CONTROL The analytical data acquired from QC procedures are used to estimate and evaluate the analytical results and to determine the necessity for or the effect of corrective action procedures. The QC process includes those activities required during analytical data collection to produce the desired data quality and to document the quality of the collected data The QC operations required for this analytical service are shown in Table 3. PERFORMANCE MONITORING ACTIVITIES Laboratory performance monitoring activities are provided primarily by AOC and the Regions to ensure that contract laboratories are producing data of the appropriate quality. EPA performs on-site laboratory audits, data package audits and GC/MS tape audits, and evaluates laboratory performance through the use of blind performance evaluation samples. For more information on this analytical service, contact: Howard Fribush Organic Program Manager USEPA/AODQC 401 M Street, SW (5204G) Washington, DC 20460 703603-8831 FAX: 703 603-9112 Table3. Frequency of QC Operations QC Operation Surrogates (for semivolatiles and pesticides) System monitoring compounds (volatiles) Method blanks (volatiles) Method blanks (semivolatiles and pesticides) Storage blanks (volatiles) GC/MS mass calibration and ion abundance patterns (volatiles and semivolatiles) Frequency Added to each sample, standard, and blank Added to each sample, standard, and blank Prepared each 20 samples for each matrix and level Prepared with each group of samples of same matrix and level, each time samples are extracted Prepared and stored with each group of samples received from the field Every 12 hours, for each instrument used for analysis QC Operation GC resolution check (pesticides) Initial calibration Continuing calibration Stability of internal standard responses (volatiles and semivolatiles) Retention time stability Matrix spike and matrix spike duplicate Frequency Prior to initial calibration, on each instrument used for analysis Upon initial set up of each instrument, and each time continuing calibration fails to meet the acceptance criteria Every 12 hours, for each instrument used for analysis Every analysis Every analysis Once every 20 or fewer samples of same fraction, matrix, and level ------- Attachment A: Pilot Case Studies Albion-Sheridan Landfill Anecdotal evidence indicated that some quantity of industrial wastes were disposed of at the 30-acre Albion- Sheridan Landfill, but the location, volume and identity of wastes were unknown. No data were available for the site at the beginning of the RI/FS. EPA implemented the streamlining principles of the 1991 MLF RI/FS guidance, and scoped a phased approach to characterization of the Albion-Sheridan site with the goal of implementing the containment remedy. The draft work plan was revised to incorporate the phased investigation, focusing first on ground-water contamination to establish whether there was a basis for a response action. Ground-water contamination did support the need for action at the site, so it was not necessary to quantify additional exposure pathways for this purpose. The remainder of the risk assessment was streamlined by using a conceptual site model to demonstrate that the other potential pathways of concern (e.g. direct contact) would be addressed by the components of the presumptive remedy (e.g. landfill cap). EPA conducted a geophysical survey of the site to identify potential drum storage areas. Based on the results of the geophysics, EPA concluded that while there were anomalies in the results, there were no areas that appeared to consist of large numbers of drummed waste, thereby warranting further investigation. Because the State had remaining concerns with EPA's approach to hot spots, the State conducted its own geophysical survey and dug test pits at 12 locations. At one location approximately 300- 400 drums were uncovered, and EPA reiterated its agreement to send any drums of hazardous waste off-site for disposal. Of the 300-400 drums, the number containing hazardous waste is unknown at this time. Lexington County Landfill Ground-water data were available for this 70-acre landfill prior to initiation of the RI, which indicated exceedences of MCLs, and therefore a basis for a response action. The strategy for the Lexington County Landfill RI was similar to the Albion-Sheridan Landfill, in that a phased approach was implemented. Sampling focused on further characterization of ground-water contamination, and the risk assessment was streamlined, focusing also on the ground-water pathway. Planned soil sampling and analysis to estimate direct contact threats was eliminated, and it was demonstrated (using a conceptual site model) that other potential pathways of concern would be addressed by components of the presumptive remedy. A planned drum search of the 70-acre landfill was eliminated based on the guidelines for hot spot characterization contained in the 1991 MLF RI/FS guidance. At Lexington County Landfill, as at Albion Sheridan Landfill, it is likely that some industrial waste was disposed of at the site, but the location, quantity and identity of the wastes were unknown. Because there was no evidence to guide such a search, EPA decided that the best approach was to contain the landfill, accounting for uncertainties in the nature of the wastes during the design. The selected remedy includes consolidation and capping of the waste areas, landfill gas collection and venting; extraction of contaminated groundwater/leachate with discharge to POTW; additional sampling of surface water and sediment to characterize any off-site contamination; and monitoring of ground water, surface water, sediment and landfill gas. Additionally, to address a plume, a ground-water pump and treat remedy was put in place. BFI/Rockingham Extensive ground-water data were available for this site at the initiation of the RI, and the first step in implementation of the presumptive remedy was to evaluate the potential for using the data. The data were found to be useable to establish an initial basis for action, which allowed streamlining of the risk assessment and RI. Only confirmational ground-water sampling was conducted during the RI; characterization of the landfill surface soil and debris mass did not occur. Geotechnical information regarding settlement, cover quality, and stability was also collected. The knowledge that containment was the likely remedy allowed the RI to become primarily a design- related investigation. In addition, based on historical information, hot spots were not of concern at this site. Levels of volatile organic compounds (VOCs) and certain metals clearly indicated that a ground-water risk was present. The existence of ground-water risk confirmed that a "No Action" decision was unlikely, and that a landfill cap would be a component of the source control action. The risk assessment was streamlined by quantifying the ground- water risk and qualitatively discussing the other pathways that would be addressed by the source control action. All pathways outside the landfill, which included off-site ground water and off-site soils, were fully quantified. An early action was conducted as a non-time-critical removal at this site in order to begin construction of the landfill cap. The combination of the presumptive remedy with the early action resulted in a significant time savings in the remedy selection and construction processes. ------- leachate, and/or landfill gas). The exposure pathways are then compared to those addressed by the containment remedy, as .follows: "' • direct contact with soil and/or debris prevented by landfill cap; • exposure to contaminated ground water prevented by ground- water control; • exposure to contaminated leachate prevented by leachate collection and treatment; and • exposure to landfill gas addressed by gas collection and treatment, as appropriate. This comparison reveals that the containment remedy addresses all pathways associated with the landfill source. The phased approach can be implemented at landfill sites using the conceptual site model because it demonstrates that all exposure pathways are addressed by the containment remedy, and field sampling is therefore not required to characterize the nature and extent of contamination once it has been demonstrated that the site presents a risk and warrants action. A streamlined risk evaluation was successfully conducted at the three pilot sites, with contaminated ground water presenting the justification for a response action. Sampling, analysis, and a conventional risk assessment were required to characterize contamination, if any, that had migrated away from the source areas. Quantitative Results is illustrated in Highlight 2, the RI/FS durations for the pilot sites ranged from 23 to 32 months, compared to 44 to 72 months for the control sites. The average pilot RI/FS duration was 28 months, as compared to the national average of 51 months. The RI/FS durations for the pilot sites represent a time savings ranging from 16 to 40 months when compared to the control sites, and 23 months when compared to the national average. These results translate into an estimated time savings ranging from 36-56 percent when comparing the pilots to the control sites, and an estimated 45 percent when comparing the average pilot duration to the national average. The figures for the BFI/Rockingham site include completion of an Engineering Evaluation/Cost Analysis (EE/CA) to support implementation of source control (i.e., cap, leachate and gas collection) as a non-time-critical removal action. The EE/CA was completed in 12 months, which is a subset of the 23 months indicated in Highlight 2. The 23 months was the time required to complete the RI/FS for the entire site, including ground-water contamination. The pilot results for the BFI/Rockingham site are particularly noteworthy because the source control action was initiated just 12 months after the RI/FS start, and construction of the cap was completed in July 1995, just three years after the RI/FS start. A savings in time was also realized as a result of the streamlined isk evaluations conducted at the pilot sites, as illustrated in Highlight 3. The time required to complete the risk assessments at the pilot sites ranged from 7 to 10 months, as compared to 9 to 22 months for the controls, which represents a savings ranging from 17 to 68 percent when compared to the control sites. Highlight 2 RI/FS Durations (Months) for Pilot/Control Site and National Averages 20 23 47 32 72 28 44 28 51 BH pater Albion- West L<=*9- Cedar- f** NafanaJ — SheHdan KL *"Ca town Average Average LF Highlights Risk Assessment Durations (Months) for Pilot/Control Sites 22 10 12 Albion- West Sheridan - KL Lexington Co. town _LF_ Cost savings were estimated in one of two ways for the pilot sites. ------- The RI/FS costs for Albion-Sheridan Landfill and Lexington County were compared to the national average RI/FS cost of $1 •million, resulting in an estimated 10 percent and 1 percent savings, sspectively, for those sites. The cost savings estimate for the BFI/Rockingham site was developed by the PRP, and was based upon a comparison with their costs for RI/FSs conducted at other similar sites. A savings of 60 percent was estimated for the RI/FS, which included the source area and areas of migration, and an engineering evaluation/cost analysis (EE/CA) to support the non- time-critical removal action on the landfill cap. Conclusion EPA found that the containment presumptive remedy resulted in a savings of time and costs at each of the pilot sites. The savings were the result of implementing a phased approach to site characterization and streamlining the risk assessment, both of which were possible because the landfill contents were contained. The savings in time and costs were most significant at the BFI/Rockingham site, where the cap was completed three years after initiation of the RI/FS, and an estimated $3 million was saved. This significant savings was the result of combining the containment presumptive remedy with an early action accomplished as a non-time-critical removal action. Based on these results, municipal landfill sites appear to be well suited to the combined application of these streamlining and acceleration tools. Next Steps Since establishment of the presumptive remedy, EPA has tracked implementation at two additional landfill sites (demonstration sites): (1) Bennington Landfill, Vermont, and (2) Tomah Municipal Landfill, Wisconsin. EPA will summarize findings from the demonstration sites upon signature of their respective Records of Decision (RODs). Presumptive Remedy Directives To date, EPA has issued the following presumptive remedy directives: (1) "Presumptive Remedies: Policy and Procedures," September 1993, Directive No. 9355.0-47FS; (2) "Conducting Remedial Investigations/Feasibilities Studies for CERCLA Municipal Landfill Sites," EPA/540/P- 91/00 I.February 1991. (3) "Presumptive Remedy for CERCLA Municipal Landfill Sites," September 1993, Directive No. 9355.0-49FS; (4) "CERCLA Landfill Caps RI/FS Data Collection Guide," August 1995, Directive No. 9355.3-18FS; (5) "Site Characterization and Technology Selection for Volatile Organic Compounds in Soil/Sludge," September 1993, Directive No. 9355.4-048FS; (6) "Presumptive Remedies for Soils, Sediments, and Sludges at Wood Treater Sites," December 1995, Directive No. 9200.5-162. (7) "Presumptive Response Strategy and Ex-Situ Treatment Technologies for Contaminated Ground Water at CERCLA Sites," EPA/540/R-96/023, October 1996. In addition, presumptive remedies directives for the following types of sites or contaminants are forthcoming: (1) PCBs (2) Manufactured gas plants (3) Grain storage sites (4) Metals in soils (in cooperation with the U.S. Department of Energy). Additional Information For additional information on the pilot sites or the presumptive remedy for municipal landfills, please call Andrea McLaughlin, Office of Emergency and Remedial Response, 703-603-8793. ------- |