U.S. EPA Region 4 Technical Services Section Issue Paper for Polychlorinated Biphenyl Characterization at Region 4 Superfund and RCRA Sites H

Technical Services Section Issue

U.S. EPA Region 4 Technical Services Section Issue Paper for Polychlorinated Biphenyl Characterization at Region 4 Superfund and RCRA Sites H. Kay Wischkaemper1, Andrew F. Beliveau2, Russell W. Henderson3

Contents PURPOSE Purpose 1 EXECUTIVE SUMMARY 2 This document is written for Region 4 Project Managers, Region 4 Technical Services Section Issue Paper for On-Scene Coordinators, and technical staff and provides a Polychlorinated Biphenyl Characterization at Region 4 recommended approach for the evaluation and characterization Superfund and RCRA Sites 9 of polychlorinated biphenyls (PCBs) in groundwater, soil, and Introduction 9 sediment in order to support defensible and protective remedy PCB Chemistry and Characteristics 9 PCB Physical Properties That Control Fate and selection at PCB contaminated sites. PCB contamination Transport 13 typically results from the release of PCB manufactured fluids PCB Environmental Weathering 14 that were used in high voltage capacitors, transformers, Environmental Fate Due to Use 15 hydraulic oils, switches and other fire resistant products as well Associated Contaminants 16 Sediment Conditions Affecting PCBs 16 as the reuse of PCB waste streams in products such as dust PCB Transport and Ecological pathways 16 suppression oils and foundry casting sands. Characterization Determining the presence of Colloidal Transport 17 of groundwater, soil and sediment for PCBs is unique because PCB Production and Uses 17 of the varied site conceptual models for PCB and PCB mixture PCB Analytical Issues 19 migration and the specific analytical requirements to evaluate Sampling Recommendations 21 Sediment Sampling 23 the presence and extent of PCB contamination. At sites where Developing a PCB Soil and Water Work Plan 24 PCB groundwater contamination is present, a high percentage Assemble The Site Team 25 of those cases found PCB groundwater contamination that is the Develop a Conceptual Site Model (CSM) 25 result of facilitated transport associated with solvents, colloids, Develop the Field Sampling Plan and QAPP for the site work. 26 or emulsions. Because of the facilitated transport mechanism, Analytical data requirements for full an evaluation is necessary that considers issues such as characterization 27 sampling techniques, turbidity, the presence of elevated carbon, Example of Data Evaluation 30 etc. Determining site clean-up strategies and risk can require Frequently Asked Questions 32 individual solutions depending on what processes, material Definitions, Acronyms, and Abbreviations 35 References 37 types, and site hydrogeologic settings are present at the site. Appendices 40 This document helps the site project manager begin the process Appendix A: Groundwater Sampling 40 of planning the site characterization using appropriate analytical Appendix B: Table of the Dioxin-like Congeners in procedures on adequate samples with the endpoint being that Aroclors 42 Appendix C: PCB Aroclor/Homolog Properties 43 defensible data are available to support sound decision making Appendix D: Flow Diagram for Evaluating at the often very complicated PCB contaminated sites. Facilitated Transport 44 Region 4 has a number of PCB sites that have already provided Appendix E: Solubility’s of Aroclors, Homologs and Congeners 49 valuable lessons and aided in the development of this approach Appendix F: PCB Field Detection and Immunoassay so that a practical and technically defensible site management Methods for PCB Screening 52 strategy can be applied systematically for sampling and analysis Appendix G: Data Quality requirements for analysis of PCB contamination for impacts to groundwater, human of soils and groundwater 58 Appendix H: Table of PCB Congener and Aroclor health risk assessment, and ecological risk assessment. This Properties Calculated by EPA Kerr Lab 68 issue paper was developed to aid site project managers, risk assessors, and hydrogeologists in characterizing PCB 1U.S. EPA Region 4/Technical Services Section contaminated Superfund and RCRA sites. 2Retired U.S. EPA Region 1 3 Oneida Total Integrated Enterprises (OTIE) Issue Date: 2/28/2013 EXECUTIVE SUMMARY Project Manager, Hydrogeologist, Ecological Risk The following information summarizes the process Assessor, Human Health Risk Assessor, Region 4 of developing and implementing a successful PCB Analytical Coordinator, and Field Implementation site characterization Plan. Personnel (from here on out the paper will call this “The Site Team”). Discuss the conceptual site model and how the field sampling plan needs to be written 1 in order to be used in the field to characterize the Assemble The Site Team composed of the PCB contaminant distribution.

Flow Diagram for Developing a PCB Site Characterization Plan

Assemble the Site Team which includes Project Manager, Hydrogeologist, Ecological Risk Assessor, Human Health Risk Assessor, Region 4 Analytical Coordinator, and Field Implementation Personnel

Develop a Conceptual Site Model with Existing Data So that all Members of the Site Team are in agreement on the Data Quality Objectives Moving Forward

Develop a Field Sampling Plan and QAPP for Site Characterization of Groundwater, Surface Water, Soil and Sediment

Implement the Field Sampling Plan and send the samples to the Laboratory (for soil and sediment - either to be processed or held frozen)

Submit the soil, sediment, groundwater, and surface water location and depth data to the R4DARTCoordinator for upload into DART

Submit the analytical data to the R4DARTCoordinator for upload into DART

Re-assemble The Site Team to determine if analysis of held frozen samples should occur and if additional sampling needs to take place

Figure ES-1: Flow Diagram for Project Planning

2 Ground Water Issue Polychlorinated Biphenyl Characterization • through plumbing features to subsurface 2 Develop a Conceptual Site Model (CSM). This piping/trenches initial CSM will allow all the parties on the Team to • through plumbing features to ground surface have a common understanding of the • Overland flow to surface water features characterization concerns and solutions for field • Deposition by conditions that may pose difficulties during the • particles blown onto the ground surface sampling event. The CSM will also inform the type • Particles carried down to the ground surface of sampling, the nature of the Field Sampling Plan during rainfall events (FSAP), and the budget for performing the In looking at the CSM and Example Pathways characterization – an example is shown in the above, several issues may need to be addressed: Figure below and the supporting text for the Figure. • Aroclor (plus Aroclors 1262 and 1268) and Example Pathways: congener analysis may be necessary in order to evaluate the weathering that may have occurred. • Leaching through • If PCB NAPL is suspected then the lab should be • subsurface soil to groundwater notified so they can prepare to handle a highly • waste disposal units to subsurface soil contaminated sample. • Migration • For characterization of subsurface soil • from ground water to surface water features and groundwater nature and extent, the • from plumbing features to surface recommended procedure is for a percentage impoundments and surface water features (10% or no less than 5) of samples be subjected to congener analysis

Plumbing

Landfill Rivers/ Water PCB/Solvent Lagoon Streams Table NAPL PCB Plume

PCB Plume

Example General Conceptual Site Model Schematic

Figure ES-2: Example of a General Conceptual SiteModel Schematic

Polychlorinated Biphenyl Characterization Ground Water Issue 3 • For the Risk Assessment 10% of the surface soil suggests that soil samples be obtained in suspected samples (but no less than 5) should be analyzed source (highly contaminated) areas, moderately for congeners contaminated areas and suspected clean areas • On a site specific or case by case basis, for the and analyzed for both Aroclors and congeners so Ecological Risk Evaluation surface water and that the representativeness of the Aroclor data can sediment samples may need to be analyzed for be adequately evaluated. A curve produced by congeners 77, 123, 118, 114,1 05, 126, 153,167, plotting congener total PCBs versus Aroclor total 156, 157, 169, 189 PCB data, can be used to provide correlation for the soil sampling data so that site managers can • If a groundwater plume is known to be present, determine whether or not Aroclor data alone can be an evaluation for facilitated transport is highly trusted at other locations to represent the total PCB recommended concentrations in soil and water. Congener analysis 3 may be necessary for surface soil and sediment so Develop the Field Sampling Plan and QAPP that the information can be incorporated into the for the site work. ecological risk evaluations. The sections provided In order to get the proper data for remedy selection below include information that will inform the Field several analyses need to be performed for various Sampling Plan and QAPP. environmental media. Aroclor analysis is the least Soil and Sediment expensive method for analyzing samples for PCBs, • For subsurface soil leaching to groundwater so Aroclor data will generally be gathered for all and for nature and extent, Aroclor and congener media. In order to correlate the Aroclor data and analysis are recommended. A percentage (10% determine where it is representative, congener or no less than 5) of samples should be analyzed data also should be obtained for nature and extent. by congener analysis. There are exceptions to this suggestion. For example, in the instance where the site is an old • For soil and sediment, it is recommended that landfill and removal has been called in to do a final if little is known about PCB distribution at the action and no additional federal or state actions will site, soil and/or sediment samples should be take place, consideration should be given to what is run using Aroclor analysis and then a subset of known about the site at the time removal authority samples can be selected for congener analysis, is in the execution planning stage. If one portion once the Aroclor data are reviewed. For PRP of the site is highly contaminated and aroclor data lead sites, taking a greater number of samples already indicate an action, then congener analysis during the initial field work and holding them in may only be necessary for verifying the nature and a frozen state should be considered so that if extent of that portion of the site. If another portion there is poor correlation between the Aroclor and of the site is contaminated but concentration data congener analysis, the archived samples can be is borderline actionable, then congener analysis used to fill data gaps, as necessary. Note that may be necessary to verify the definition of the soil and sediment samples can be held frozen for actionable extent. The most important thing to do up to one year for congener analysis. If the site is CONSULT WITH THE SITE TEAM in order to is Fund Lead and samples are being collected for develop a practical removal execution plan. the EPA Lab in Athens, or for an EPA contracted Non Routine Analytical Services, the labs may Though Aroclor was the original product, it weathers not be able to hold frozen samples (See Figure as it moves through the soil column or as it resides ES-1 on page ix for freezing requirements for in sediment or sludges. The curve matching samples). process used for Aroclor analysis can underestimate the total PCBs, if weathering has occurred. An • Typically for Ecological Risk evaluations evaluation of the correlation between the congener congeners 81-TeCB, 77-TeCB, 123-PeCB, 118- and Aroclor data is necessary so that total PCBs PeCB, 114-PeCB, 105-PeCB, 126-PeCB, 153- can be extrapolated over the entire site and for HxCB, 167-HxCB, 156-HxCB, 157-HxCB, 169- various environmental media. Region 4 TSS HxCB, 189-HpCB are the most significant. Ten

4 Ground Water Issue Polychlorinated Biphenyl Characterization Table ES-1: Analytical Details for Sample Handling

Recommended reporting Analysis Recommended Site Lead Media limits based on MCLs, Holding Times Objective Analytical Method RSLs and AWQC

0.014 ug/L for Groundwater/surface 7 days until extraction and Extracts EPA Method 8082A water issues; 0.5 ug/L should be stored under refrigeration in Aroclor (be sure and include for groundwater not the dark and should be analyzed within 1262 and 1268) Ground influencing surface 40 days of extraction. Water/ water Surface Water For Athens - run EPA Method 1668B or If stored in the dark at less than 6 °C, Method Reporting Congener Non-Routine aqueous samples may be stored for up Limit EPA Analytical Services for to one year. Region 4 1668A or B Fund Lead 7 days until extraction and Extracts EPA Method 8082A 33 ug/kg: 330 ug/kg should be stored under refrigeration in Aroclor (be sure and include max the dark and should be analyzed within 1262 and 1268) 40 days of extraction. Soil/ Sediment For Athens - run EPA Method 1668B or Method Reporting Up to 1 year frozen - Store in in the dark Congener Non-Routine Limit at less than -10 °C Analytical Services for 1668A or B 0.014 ug/L for Groundwater/surface 7 days until extraction and Extracts EPA Method 8082A water issues; 0.5 ug/L should be stored under refrigeration in Aroclor (be sure and include Ground for groundwater not the dark and should be analyzed within 1262 and 1268) Water/ influencing surface 40 days of extraction. Surface water Water If stored in the dark at less than 6 °C, Method Reporting Congener EPA Method 1668B aqueous samples may be stored for up PRP Limit to one year. 7 days until extraction and Extracts 33 ug/kg: should be stored under refrigeration in Aroclor EPA Method 8082A Soil/ 330 ug/kg max the dark and should be analyzed within Sediment 40 days of extraction. Method Reporting Up to 1 year frozen - Store in in the dark Congener EPA Method 1668B Limit at less than -10 °C Note: consultation between the Region 4 Analytical Coordinator, the RPM/OSC, Human Health Risk Assessor, Hydrogeologist, and Ecological Risk Assessor are paramount since labs and analytical method details require clear direction Regional Screening levels (RSL’s) - http://www.epa.gov/region9/superfund/prg/ Maximum Contaminant LeveL (MCL’s) Ambient Water Quality Criteria (AWQC) NOTE: Reporting levels can be customized to specific site needs to some extent for both the Regional laboratory and the CLP. In the absence of special requests, the routine approach for the Regional laboratory is to lower reporting levels to Maximum Contaminant Limits (MCLs) for only those contaminants which have an MCL. In the absence of special requests, the routine approach for the CLP, when the lowest reporting levels available from the contract are requested, provides the following results: Polychlorinated Biphenyls analyzed as Aroclor mixtures do not meet MCLs. Reporting Limit: Region 4 normally uses this term for the Sample-Specific Quantitation Limit, which has been adjusted for dilutions, moisture content, or other sample-specific factors. This value is the quantitation limit actually achieved in the analysis, and may be the same as the Quantitation Limit that was set as the goal for project planning. However, often, this value will be higher than the Quantitation Limit, since the goal of this Minimum Reporting Limit can only be achieved for relatively clean samples. This is the value that normally appears on the data sheet for data reporting. This is a data reporting value and will vary according to sample matrix of the specific sample.

Polychlorinated Biphenyl Characterization Ground Water Issue 5 percent of the sediment samples (no less than The Site Team for the detection limits and 5) should be analyzed for this list of congeners. congeners to be analyzed for is necessary. Details of the ecological sampling strategy should be based on consultation with The Site Aroclor Analysis for soil and groundwater – EPA Team. Method 8082A (http://www.epa.gov/osw/hazard/ Groundwater and Surface Water testmethods/sw846/pdfs/8082a.pdf). Be sure and note that in addition to Method 8082A for Aroclors, • Groundwater samples should be collected analysis must also include Aroclors 1262 and 1268. using the low flow/low stress technique (See Yeskis and Zavala, 2002 - http://www.epa.gov/ Congener Analysis for soil and groundwater – tio/tsp/download/gw_sampling_guide.pdf and EPA Method 1668B (http://water.epa.gov/scitech/ the Appendix A). This technique (versus the methods/cwa/bioindicators/upload/2009_01_07_ conventional low flow sampling) purges the well methods_method_1668.pdf ) or if the Region 4 Lab at the approximate rate that water enters the well in Athens is used, Method 1668A is sufficient. so that if the well is productive, sampling can Congener Analysis for Dioxin like PCBs and progress at a reasonable rate without invoking Ecological PCBs – Use the same statement of turbulent flow and turbidity. This also reduces work (SOW) as employed for the regular congener the possibility of getting only stagnant water analysis and specify the individual congeners to be in the well casing. Both Aroclor and congener reported. There are 12 PCB congeners that have analyses are recommended for water samples. been designated by the World Health Organization A percentage (10% or no less than 5) of samples (WHO) (Van-den Berg et al, 1998) as having should be run using congener analysis. A “dioxin-like” (or non-ortho-substituted) toxicity. correlation analysis of the Aroclor and congener They are as follows: 77, 81, 105, 114, 118, 123, data is recommended. 126, 156, 157, 167, 169, and 189. There are 18 • If turbidity is an issue, and in Region 4 that is PCB congeners that have been designated by the > 10 Nephelometric Turbidity Units (NTU’s), National Oceanic and Atmospheric Administration redevelop the well and resample. If turbidity (NOAA) as always appearing in sediment and fish remains an issue and is inherent in a low yield tissue and that do not readily degrade. This NOAA well, filtration with a 2 micron filter can be Congener List includes congener number: 8, 18, 28, considered, NOT a 0.45 micron filter. Colloidal 44, 52, 66, 77, 101, 105, 118, 128, 138, 153, 170, material can transport PCBs and removal of that 180, 187, 195, and 206. material through filtration can provide a false Initially homolog analyses was proposed by negative sample result. Region 4 because the analysis cost has typically • Analysis for dissolved organic carbon (DOC) been less than congener analysis, but because should be performed if facilitated transport is Method 680 is not an EPA promulgated method suspected (see FAQ). and because complications in executing Method 680 have emerged, the Region has reconsidered • Surface water samples, obtained using advocating a wholesale recommendation for the conventional sample gathering methods for homolog analysis. Region 4 has become aware ecological assessments, may require sample that private sites have been running the congener analysis for Aroclor and congener’s 81-TeCB, analysis using EPA Method 1668B (the Congener 77-TeCB, 123-PeCB, 118-PeCB, 114-PeCB, Analysis method) and then summing the congeners 105-PeCB, 126-PeCB, 153-HxCB, 167-HxCB, into the homolog groups and presenting the data 156-HxCB, 157-HxCB, 169-HxCB, 189-HpCB. as a homolog analysis. This is fine, but the cost If ground water discharge to surface water is of the analysis is the same or higher than running a pathway of interest, the detection limit of the samples for congeners, so Region 4 is now 0.014 ug/L should be used for surface water simplifying our process approach to consider only and groundwater analysis. Consultation with Aroclor and congener analysis.

6 Ground Water Issue Polychlorinated Biphenyl Characterization Perform Aroclor analysis: Administration (NOAA) 18 congeners are to be • For Region 4, Aroclor analysis should be run analyzed and also needed to determine total PCB. for all samples.1 • When the data user desires to determine what • When the Gas Chromatography/Electron congeners are present and which congeners Capture Detector (GC/ECD) pattern is unaltered have been lost due to weathering. and matches the standard pattern. For example the chromatogram represents peaks that are • GC/LRMS may not be sensitive enough to easily assigned to an Aroclor and there are a few quantitate congeners #77, #81, #126, and “renegade” peaks, making the chromatogram #169 the most toxic of the World Health noisy. Organization (WHO) high risk congeners due to their very low concentrations in • When high concentrations of PCB is present in manufactured Aroclors. the soils due to DNAPL presence. • Gas Chromatography/High Resolution • When only one Aroclor is found or the Aroclor Mass Spectrometry (GC/HRMS) is used to mixture has widely different chlorination levels. determine the concentrations for the 12 WHO For example, a site where only 1016 or 1260 dioxin like congeners were disposed, the chlorination level between • Congener analysis is used over homolog these Aroclors is significant so the chromatogram analysis because there is a promulgated will clearly discern the peaks assigned to each of EPA Method, it is more sensitive, more the Aroclors. selective, and more suited for risk assessment • When objectives include assignment of a specific purposes. GC/ECD is acceptable to analyze responsible party to a specific Aroclor release. the NOAA 18 congeners, however, it cannot be used to determine all 209 congeners. Perform Congener analysis: Congener analysis can be performed using Use in Risk Assessment: The use of congener data High Resolution long column/long run time Gas for risk assessment is different than with Aroclors. Chromatography/Electron Capture Detection Slope factors for 4 PCB Aroclors (1016, 1242, (HRGC/ECD), Gas Chromatography/Low 1254, 1260) have been developed but not for all Resolution Mass Spectrometry (GC/LRMS), or High Aroclors or all congeners. The Risk Assessor may Resolution Gas Chromatography/High Resolution use the total PCBs (sum of congeners) to calculate Mass Spectrometry (HRGC/HRMS). Pesticide a total PCB risk and hazard. The dioxin-like PCB interferences can occur (Toxaphene) when using congeners will be assessed separately. GC/ECD Analysis, whereas they do not occur with Note that when risk is calculated the provision for HRGC/ECD. Congener analysis using GC/ECD has preventing double counting should be employed. been used predominantly for tissue and biological Congener analysis for the dioxin like PCBs analysis. Congener analysis by GC/LRMS (WHO-12 and/or NOAA-18) may be necessary Selective Ion Monitoring (SIM) is used when: and this case by case determination should be • Aroclor patterns have been altered or when determined by The Site Team as they establish the chlorinated species interferences are present. data needs (Data Quality Objectives) for the soil, It is especially sensitive in the low chlorination groundwater, surface water, and sediment data. range where mono-, di-, tri- and tetra- species are present. 4 • When the National Oceanic and Atmospheric Implement the Field Sampling Plan and QAPP.

1 NOTE: This paper will use the term Aroclor analysis which 5 are the Aroclors 1016, 1221, 1232, 1242, 1248, 1254, Submit the soil, sediment, groundwater, and 1260, 1262, and 1268. Method 8082A does not include 1262 and 1268, so this analysis must be added in the surface water location and depth data to the Work Plan. Region 4 SESD has incorporated Aroclor 1268 Region 4 DARTCoordinator for upload into DART. into their PCB Aroclor analysis process, but private CLP labs have not.)

Polychlorinated Biphenyl Characterization Ground Water Issue 7 6 Once the analytical data is returned, submit the analytical data to the Region 4 DART Coordinator for upload into DART.

7 Once the field work has been implemented and the analytical data is uploaded into the Region 4 DART data management system, convene The Site Team and review the data and determine if frozen, held samples need to be run and if additional samples need to be collected and analyzed.

8 Ground Water Issue Polychlorinated Biphenyl Characterization Region 4 Technical Services Section Issue Paper for Polychlorinated Biphenyl Sampling at Region 4 Superfund and RCRA Sites

INTRODUCTION the process of planning the site characterization Polychlorinated biphenyl’s (PCBs) were produced using appropriate analytical procedures on commercially in the United States between 1929 adequate samples with the endpoint being that and 1977. Approximately 99% of the PCBs used defensible data are available to support sound by U.S. industries were produced and marketed decision making at the often very complicated PCB under the trade name of Aroclor. PCBs have been contaminated sites. identified at over 1,600 hazardous waste sites proposed for inclusion on the EPA National Priorities List. This document provides a recommended approach for the evaluation and characterization of polychlorinated biphenyls (PCBs) in water, sediment, and soil. The approach presented is suggested in order to accurately determine the presence of PCBs in the environment; as well as, to support a defensible and protective remedy selection where PCB contamination is present. High voltage capacitors, transformers, switches, hydraulic fluids, caulks, and paint are some of the sources of PCB contamination. In a high percentage of cases PCBs are found in groundwater as the result of facilitated transport Figure 1. Boring for PCB NAPL in suspected source area either associated with solvents, colloids, or emulsions. Because of the facilitated transport mechanism, an evaluation is necessary that considers issues such as sampling techniques, turbidity, the presence of elevated carbon, etc. In general, the document uses the ambient water quality criteria (AWQC) of 0.014 µg/L (for water samples), as the quantitation limit goal for examining the impacts of PCBs to groundwater and to evaluate the possibility of facilitated transport. Impacts for soil and sediment can be compared to the EPA Remedial Screening Level (RSL) table concentrations (http://www.epa.gov/region9/ superfund/prg/). The AWQC was chosen as a goal because most ground waters will impact surface waters at some point during the migration of the Figure 2. An Example showing an actual site PCB water and this concentration is less than EPA’s Groundwater Contaminant distribution maximum contaminant level (MCL) of 0.5 µg/L. Determining site clean-up strategies and risk is an individual solution depending on what processes, PCB CHEMISTRY AND CHARACTERISTICS material types (i.e. soil sediment and waste textures PCBs in the US were produced by Monsanto from and characteristics), and site hydrogeologic setting 1930 to 1979, under the trade name of Aroclors. is present at the site. Using this document, a Project Manager/On-Scene Coordinator may begin PCBs are a family of chlorinated organic

Polychlorinated Biphenyl Characterization Ground Water Issue 9 compounds formed by two benzene rings linked semisolid at ambient temperature and had to be by a single carbon-carbon bond (the biphenyl diluted with trichlorbenzene (a.k.a. Askarel) so that molecule). Various degrees of substitution of it could be poured into a transformer and fill all the chlorine atoms for hydrogen are possible on the voids within copper windings. remaining ten carbons atoms. There are 209 Penning (1930), described that the Aroclor viscosity possible arrangements (congeners) of chlorine increases gradually up to 40 percent chlorine and atoms on the biphenyl molecule. Each individual then very rapidly when the chlorine content exceeds arrangement or compound is called a congener. 40 percent. The exception is Aroclor 1016 which is an oil despite the fact it is 41% chlorine. Figure 4 shows the congener and homolog make- up for Aroclors 1016, 1254, and 1268. This figure displays the percent by weight of the individual PCB congeners; as well as, the homolog designation for the PCB congeners. From this chart, Aroclor 1016 Figure 3. Chemical Structure of PCB is shown containing the lesser chlorinated PCB congeners and 1268 contains the most chlorinated The name of a congener specifies the total number PCB congeners. One thing to remember is that the of chlorine substituents and the position of each homologs are groupings of congeners based on the chlorine. For example: 4,4’-Dichlorobiphenyl is a number of chlorines. All the other Aroclors have a congener comprising the biphenyl structure with congener distribution that is also distinctive. The two chlorine substituents, one on each of the #4 other Aroclor make-ups are found in Appendix H. carbons of the two rings. Figure 5 on the following page shows the homolog Homologs are subcategories of PCB congeners composition of important Aroclors with an having equal numbers of chlorine substituents. explanation of the properties that generally control For example, the tetrachlorobiphenyls are all PCB the fate and transport of PCBs. The most soluble congeners with exactly 4 chlorine substituents Aroclor is 1221 and the least soluble is 1268. that may be in any arrangement. There are 42 Aroclor 1221 has the lowest log Kow so is the least tetrachlorobiphenyls. likely of the Aroclors to sorb to soil. On the other The most common Aroclor designations are 1016, hand, Aroclor 1268 has the highest log Kow and 1221, 1232, 1242, 1248, 1254, 1260, 1262, and the lowest solubility so it is most likely to sorb to 1268. The first number in the designation is related soil and less likely to move with groundwater flow. to the 12 carbons in the molecule, and the second Of course, under conditions of co-solvency and number is related to the average percentage of colloidal transport, Aroclor 1268 will dissolved more chlorine, by weight, attached to the molecule. For readily or become entrained in groundwater and example, Aroclor 1242 represents a biphenyl that become more mobile. has 12 carbons and is 42% chlorine. Aroclor 1016 Aroclor 1221 is made up of the lower chlorinated is an exception because it does not use this same homologs which are more soluble and less sorptive; numbering scheme; rather, Aroclor 1016 was whereas, Aroclor 1268 is made up of the highly made from a vacuum distillation fraction of Aroclor chlorinated homologs which are less soluble and 1242 and contains only mono-, di-, tri-, tetra-, and more sorptive. The reason these observations penta homologs. The percentage of chlorine is are significant is that if the subsurface soil shows approximately 41%. A series of Aroclors were up as containing highly chlorinated homologs or produced which varied in consistency from that of a congeners, and there is no transport with solvents light mobile oil (e.g. Aroclor 1016) through to a thick or colloids (see the following Section PCB “Physical syrupy stage (e.g. Aroclor 1254) to a solid resinous Properties That Control Fate and Transport” or crystalline state (e.g. Aroclor 1268). The higher for more detailed discussion), then migration to the percentage of chlorine the more viscous the groundwater is less likely and a higher subsurface Aroclor was at room temperature. For example, soil concentration for protection of groundwater can when Aroclor 1260 was produced, it was a waxy be considered protective.

10 Ground Water Issue Polychlorinated Biphenyl Characterization Congener and Homolgue Composition of Aroclor 1016 35.0 10 Aroclor 1016 Aroclor 1254 Aroclor 1260 Aroclor 1268 Homologue Group 9 30.0 Octa Homologue Group 8 25.0 Hepta 7 Hexa 20.0 6 Penta 5 15.0 Tetra 4 Weight Percent Weight 10.0 Tri 3 5.0 2 0.0 1 101 111 121 131 141 151 161 171 181 191 201 11 21 31 41 51 61 71 81 91 1

Congener Number

Figure 4. The composition of Aroclor 1016, 1254, and 1268. Note: For example, the Mono homolog designation means that the homolog group contains one chlorine; the Di homolog designation means that the homolog group contains 2 chlorines, and so on.

Homolog Distribution in Aroclors Deca 100 Nona 90 Octa 80 70 Hepta 60 Hexa 50 Penta 40 30 Tetra 20 Tri 10 Di 0 1016 1221 1232 1242 1254 1260 1268 Mono Aroclor ID 2.00 1.80 PCB Aroclor Density 1.60 1.40 Density g/cm3 1.20 1.00 1016 1221 1232 1242 1254 1260 1268 Aroclor ID

1.00

Aroclor Solubility (mg/L) 0.50 PCB Aroclor Solubility

0.00 1016 1221 1232 1242 1254 1260 1268 Aroclor ID

10.0 PCB Aroclor Log Kow 8.0

6.0

4.0 Log Kow 2.0 1016 1221 1232 1242 1254 1260 1268 Aroclor ID

Figure 5. Aroclor composition and some physical chemical properties affecting transport in groundwater

Polychlorinated Biphenyl Characterization Ground Water Issue 11 In the Aroclor pattern shown in Figure 6 for Aroclor appeared to match the Aroclor chromatograph 1254, the peak pattern is represented by the curve most closely. The reason this distinction is green lines. When Aroclor analysis for PCBs is important is that the lab analysis for determining the performed by gas chromatography (GC) with a total PCBs in soil or groundwater is more accurately conventional detector (e.g., electron capture), the determined by congener analysis because Aroclor chromatographic pattern for the Aroclor is matched analysis may yield false negative data. against the chromatographic pattern for the sample PCB was produced and under certain conditions is being run. If the peaks are a match then the Aroclor present as unweathered Aroclor. In one scenario, has been identified. The intensity (height) of a once the Aroclor comes to the soil column, various selected number of peaks, or the sum of the heights natural processes take place that change the make- of all of the peaks, establishes the concentration up of the Aroclor. The more chlorinated PCB (more for that Aroclor in the sample. If the PCB is chlorinated congeners within the Aroclor) will sorb to “weathered”, there may be a number of peaks that the soil and the more soluble congeners will move are displayed (i.e. PCB is present in the sample), down the soil column with pore water. When the but because the pattern is not matched, the Aroclor soil is analyzed the results might indicate that the cannot be identified, and the concentration for that Aroclor is a more chlorinated and look more like sample would either be reported as a non-detect, or Aroclor 1260, whereas a groundwater analysis may a very coarse estimate of the concentration would indicate a less chlorinated version of the Aroclor, be made. If a congener or homolog analysis is such as Aroclor 1221. Actually the original Aroclor performed on the sample, a total PCB concentration could have been 1242 or 1248. for the sample can be established that is accurate since no pattern matching is involved. Congener In another scenario Aroclor could be mixed with and/or homolog analysis is performed by GC with solvent, such as would develop when transformers a mass spectrometer detector (GC/MS). The mass were refurbished and cleaned with trichloroethylene spectrum will uniquely identify the congeners in the (TCE) prior to being refilled with Aroclor 1254 or sample, and the summation of a selected mass or 1260. This mixture of PCB and solvent will be very masses provides the homolog total. Weathering is soluble and the more chlorinated congeners, which discussed in detail in the following Section “PCB would ordinarily sorb to soil, could be carried down Environmental Weathering”. into deeper soil and groundwater. Note that if congener or homolog concentrations are In a third scenario, Aroclor that did not make the compared with the Aroclor concentrations and found specifications necessary for use in capacitors or not to be consistent with the Aroclor composition, transformers, could have been used for paint, Aroclor contaminant weathering has taken place caulk or other applications and could exist in both and the contaminant is really not an Aroclor, simply a weathered and unweathered form. The analysis an assemblage of PCB homologs/congeners that of samples won’t necessarily look like a discernible

Congener Peak Pattern for Aroclor 1254

12.0 Aroclor 1254 10.0

8.0

6.0

Weight Percent Weight 4.0

2.0

0.0 101 111 121 131 141 151 161 171 181 191 201 11 21 31 41 51 61 71 81 91 1

Congener Number

Figure 6. Congener peak pattern for Aroclor 1254.

12 Ground Water Issue Polychlorinated Biphenyl Characterization set of peaks for a specific Aroclor, but PCB could (Aroclors) were produced at manufacturing facilities be present in soil and sediment samples in an (Francis, 1994; Gold & Bloom, 2000) and shipped unrecognizable pattern at significant concentrations. to facilities that used them to produce capacitors, The density for all Aroclors is greater than water transformers, switches and other fire and heat so they create a contaminant mix that is a “sinker”. resistant products. During production of these The solubility decreases with increasing chlorine mixtures, some Aroclors also were compounded content so more chlorinated PCB is not as mobile with trichlorobenzenes to create a flowable fluid but when combined with chlorobenzenes or another that was dielectric and heat resistant at high solvent to decrease the viscosity, the effective temperatures. This resulted in the production of solubility increases. wastes in the form of PCBs, trichlorobenzenes, and trichloroethylene (used in cleaning operations). There are 12 PCB congeners that have been Some of the off specification waste was then designated by the World Health Organization packaged and sent to recyclers or other end (WHO) (Van-den Berg et al, 1998) as having users that compounded the PCB into paint, “dioxin-like” (or non-ortho-substituted) toxicity. They caulk, hydraulic oil, polymers, vinyl tile, rubber or are: 77, 81, 105, 114, 118, 123, 126, 156, 157, 167, heat transfer agents. If PCB is mixed with other 169, and 189. compounds, the weathering of these mixtures can There are 18 PCB congeners that have been produce a condition that can make sample analysis designated by the National Oceanic and more complex. As a result, capturing the nature Atmospheric Administration (NOAA) as always and extent of contamination with conventional appearing in sediment and fish tissue and that do Aroclor analysis (EPA Method 8082 which is gas not readily degrade. NOAA congeners are: 8, 18, chromatography (GC) with pattern recognition 28, 44, 52, 66, 77, 101, 105, 118, 128, 138, 153, analysis, explained in detail later in this document) 170, 180, 187, 195, and 206. is inadequate because of the weathering process and co-solvency issues. As a result congener PCB Physical Properties That Control Fate and analysis is recommended to evaluate the nature Transport and extent and risk for both soils and groundwater. Characterization of the fate and transport of PCBs In the resulting waste mixtures, PCB solubility is different from that of other compounds because and adsorption is altered so that the hydrophobic of the analytical peculiarities, facilitated transport paradigm historically conceived for PCBs is resulting from PCB mixtures, colloidal transport, and inaccurate for the development of proper site past disposal practices. Consequently, inaccurate characterization. Association with solvents creates conceptual site models for PCB migration may a highly soluble, migration-prone mixture that has state that migration of PCB in soil is not expected to the ability to migrate (leach) through subsurface reach groundwater; when, actually site data at many soil and into groundwater in both a non-aqueous sites, with the proper evaluations, show that PCB phase and a dissolved groundwater phase. Aroclor migration/leaching does develop and groundwater analysis of these mixtures is often inadequate. concentrations can exceed both the AWQC and the MCL. In settings such as fractured rock and karst, PCBs have been found at depths of greater than 175 feet, Site histories have shown PCB contamination with free phase PCB/trichlorobenzene mixtures results from many waste streams associated greater than 50 feet deep. PCB migration is with (1) primary manufacture and production of facilitated as a co-solvent mixture with chlorinated PCBs, (2) secondary uses of waste streams/off- solvents, colloids, and, as reported by Kueper et specification PCB material, (3) the known and al (2005), emulsions. The mixtures often present unknown incorporation of PCB into industrial analytical complications that can falsely present the products to meet flame retardant property nature and extent of PCB plumes. For instance, requirements, and (4) ruptured transformers and if extensive weathering has occurred, the Aroclor capacitors used in large industrial settings such analysis may be meaningless because the Aroclors as steel manufacturing, foundries, etc. PCBs have been altered, making pattern identification

Polychlorinated Biphenyl Characterization Ground Water Issue 13 (the method for determining Aroclor concentrations) bedrock, the DNAPL can migrate further down and impossible or inaccurate. Also, disposal practices be present at a much greater depth than expected. that mix PCB waste with other compounds could Once PCB mixtures are transported into create a mixture that can only be identified by groundwater, the altered solubility and adsorption congener analysis. properties allow migration to surface water, resulting Spills of Aroclors 1254, 1260, 1262, and 1268 will in contaminated sediment and surface water. tenaciously adhere to organic soils and do not Often the pathway from surface runoff to surface readily degrade or migrate. If the receiving soils water is the only pathway evaluated because are sandy and have a very low organic content, the groundwater is inadequately characterized. the PCB can migrate downward until it reaches Therefore, the ground water/surface water a confining layer such as clay or bedrock. Many connection is ignored; and the ecological risk times Aroclor 1260, diluted with trichlorobenzene evaluations and surface water, sediment, and (Askarel), will migrate to greater depths because the groundwater remedial alternatives are inadequate. viscosity of the mixture is much lower than the pure Surface soil and sediment are then remediated, PCB. The PCB is transported downward faster due but groundwater continues to migrate into surface to the solvent content and high density. water, and recontamination takes place. Highly chlorinated PCBs of low water solubility can, PCB Environmental Weathering during the process of migrating through the soil along with rainwater, become colloids due to the Environmental weathering is a complicated, natural surface active agents and humic substances multifaceted process that is manifested in the contained in natural soils. This allows the PCB to changes in the PCB mixture. These changes form very small particles that are in the colloidal show up in the gas chromatographic pattern particle range. The PCB colloid particles that when compared to the pattern found in the pure are surrounded by some surface-active material PCB standard. Weathering is due to one or (surfactant) can move through the ground water a combination of the following: solubilization, and can migrate through small soil pores with the volatilization, preferential adsorption, photolysis, same ease as water. When the water containing microbial degradation, changes due to metabolism the colloids is analyzed, the pattern found is usually by benthic organisms, and other unknown physical/ that of the original Aroclor with little environmental environmental factors. Lower chlorinated species weathering and congener losses. The amount of tend to weather faster because they are more pure PCB liquid released and the organic nature of volatile and water-soluble and eventually come in the soils may have a great deal to do with how and much closer proximity to the microbes in the water why colloids are formed. At the same time, humic column. The microbes in soils and sediments and fulvic acids in the organic soils can complex metabolize the PCB, chewing up the lower with the PCB forming a water soluble chelate that chlorinated species, and in some cases discharging will move with the percolating water or ground the higher chlorinated species into the surrounding water. The actual chelating action is not well media with no degradation changes (Natarajan et characterized at this time but is being researched. al, 1997; Quenson et al, 1998; Focht et al, 1999; Comeau & Stidsen, 1994). Highly chlorinated, insoluble, high specific gravity (1.5+) PCB oils released onto low organic soils or The following are examples of environmental sands can rapidly migrate downward and coalesce weathering found in actual settings. as a Dense Non-aqueous Phase Liquid (DNAPL) • The capacitor fluid Aroclor 1242 was discharged that resides within the groundwater. DNAPLs into the Hudson River and eventually found its usually migrate to some depth and are held by way into river sediments. It has fractionated/ some barrier layer such as dense clay layers or weathered over time, causing the Aroclor pattern bedrock. DNAPL has been found at the very bottom to change. The original Aroclor 1242 GC pattern of both shallow and deep residuum and bedrock in sediment changed considerably, indicating wells in layers up to 2 feet thick. Once there is a more congeners in the Aroclor 1221 range preferential downward path, such as fractures in (mono-, di-, and tri- substituted congeners).

14 Ground Water Issue Polychlorinated Biphenyl Characterization It still has the tetra- and penta-substituted determined and recorded in the Conceptual Site congeners in the Aroclor 1242 range, but less Model. of them. There is no actual Aroclor 1221 in Overheated PCB transformers and capacitor the original PCB, but due to environmental fires allow PCBs to volatilize and pyrolize, thus conditions in the sediment and river, the dispersing the PCB vapors into the air (Matson, predominant congeners now are less chlorinated. 2001). The PCB eventually cools and condenses • In the Hudson River, the PCBs in sediments on surrounding environment, whether it is soils, have changed from their original Aroclor 1242 water bodies, roads, or solid surfaces in buildings pattern. The farther from the original source, such as concrete pads, wood floors, and walls. the more drastic the pattern changes. These During this process of volatilizing and condensing changes happened at a very slow rate. The there is some fractionation of the PCB where the Hudson River sediments show that some of the lighter PCB stays in the air longer and moves away, lower congeners have solubilized into the water and the heavier PCB condenses on surrounding column and now can evaporate into the air above surfaces. PCB contamination on surfaces adjacent the surface of the water. to electrical equipment fires is expected, but the • There is evidence that Aroclor 1242, disposed PCB can disperse much farther. In buildings where in a landfill/wetland, has fractionated into higher a transformer fire or explosion has occurred, the chlorinated congeners in the soil/sediments. PCBs can be found on walls and floors and outside When these soils were analyzed, the GC pattern surfaces many yards away from the original source. resembled the higher chlorinated congeners in In some cases, air handling and exhaust equipment Aroclor 1248, whereas the GC pattern of the can amplify this. surface and groundwater had a lower chlorinated Concrete pads that support larger electrical GC PCB pattern that resembled Aroclor 1221. equipment have been shown to be highly absorbent The original Aroclor 1242 fragmented probably of PCBs. It has been observed that PCB migrating due to the adsorption of the high-chlorinated away from transformers with very slow leaks not congeners into the soils and dissolution of the only migrates down, but also spreads out laterally low chlorinated congeners into the water. Again, as much as ten feet from the origin, forming a the PCB in the groundwater was not Aroclor subsurface cone. This conical pattern of dispersal 1221, but a mixture of congeners. might not be seen on the surface, but under the surface (at the interface between the base of the Environmental Fate Due to Use concrete and the soil/crusher run) the PCB is At DoD, DOE, and NASA facilities, as well as a spreading out. The PCB can saturate the concrete heavily industrialized area where onsite power until it reaches the soil beneath, and even extend plants are present, the distribution of PCBs can take into the soil below the concrete. Remediation of place as the result of use. For example, when paint the concrete from these types of leaks can be very containing PCBs is sand blasted off of structures, expensive. the dust deposits on the ground surface and is Incineration of waste oils containing PCBs creates available for movement into surface soil, surface volatile PCB gases that can be released as an water and sediment through the infiltration and exhaust if the flue gases are not scrubbed before runoff process. Paint usually contained off-spec they reach the end of the stack. PCB gases and PCB that was mixed until the flame retardancy PCBs attached to dust particles can also escape paint specification was met. Another example is and can migrate into the upper atmosphere and PCB as insulating oil for electric equipment and move with the prevailing winds (Matson, 2001). other purposes because of its superior insulation Stack gases containing PCBs escaped in this and incombustibility properties. PCB was widely manner prior to the Clean Air Act and found their used at thermal power stations until around 1965. way via the jet stream and other currents into Consequently, the distribution and PCB type can colder climates, where gases and dust condensed be confusing unless the process activities are onto the ocean and land. Large concentrations of PCBs developed in seals and polar bears that

Polychlorinated Biphenyl Characterization Ground Water Issue 15 ate fish from the oceans that were affected by the move for miles down a river until the particles reach condensed PCB. The incineration of industrial a slower moving section, deeper section, or natural and municipal waste containing PCBs has caused or man-made barrier (dam or impoundment) and PCBs to spread over every inch of North America the particles fall out of suspension and deposit on and beyond [National Oceanic and Atmospheric the river bottom. In some cases this action happens Administration (NOAA), 1989]. only during flood events at different weather and seasonal periods. This seasonal action can form Associated Contaminants layers in the sediment column containing different During the production of Aroclor mixtures, the concentrations of PCB depending on the forces PCB became contaminated with very small of erosion at the time of the flooding. Marine concentrations (low parts per million [ppm]) of sediments also are impacted due to rivers flowing Polychlorinated dibenzofurans (PCDFs) and even into the water bodies during the daily tidal flow smaller quantities of polychlorinated dibenzodioxins events. Sediments, both marine and freshwater, (PCDDs) (Burkhard and Lukasewycz, 2008). When appear to be very good sinks for PCB released PCBs were used to cool high voltage electrical from the land into the adjacent water bodies. The devices, such as transformers and capacitors, the investigation of PCBs in sediments can pose a levels of PCDD/PCDF increased over time. This daunting task when the PCB particles have traveled increased amount (10-50 ppm) of PCDDs and considerable distances and have overflowed the PCDFs was combined with the waste PCB and also banks of the water body onto adjacent land such as ended up in the dense non-aqueous phase liquid happens along low lying flood plains and marshes. (DNAPL) found at some sites that reconditioned and The PCB Aroclor pattern may change due to refilled transformers. anaerobic microbes eating the PCB as food Chlorobenzenes used as diluents in Askarels (⅔ and degrading the original PCB pattern causing PCB 1260 + ⅓ trichlorobenzene) (USDoC, 1976) reductive dechlorination. Reductive dechlorination are also released when PCBs are released. The can occur when the chorines at the periphery of chorobenzenes can dissolve in water as well as the biphenyl molecule are removed lowering the evaporate into the air. Trichloro- and dichloro- chlorination level of the PCB. The dechlorination benzenes can dimerize when overheated to form in anaerobic conditions is a very slow process that 2,3,7,8-Tetrachlorodibenzo-p-dioxin (TCDD) and changes the ratios of peaks in the congener pattern 2,3,7,8-Tetrachlorodibenzofuran (TCDF). The and can be different from location to location due discovery of chlorobenzenes in soil and water to different anaerobic biomolecules. This type is usually a good indication to look for PCB of action, although not always, can cause major transformer or capacitor leaks and/or releases. changes in the PCB pattern; but, depending on the severity of the weathering changes homolog Sediment Conditions Affecting PCBs or congener analysis may be required to get good Organic sediment in drainage ditches, brooks, quantitative results. rivers, streams, lakes, and ponds is a very good absorber of PCB because of the natural presence of PCB Transport and Ecological Pathways total organic carbon from decaying organic matter. PCB transported via surface water run-off into When PCB is released into the environment, rain rivers and other water bodies ending up in surface washes the PCB into brooks, creeks and streams and subsurface sediments can impact many where the PCB sinks due to its high density. The different ecological receptors. Fish, frogs, ducks, natural sediment organics will adsorb the PCB onto benthic invertebrates, and aquatic mammals can the fine surface particles. When the water starts to be severely impacted by PCB wastes dissolved flow more rapidly due to high rainfall and flooding, in surface water, adsorbed to sediments, and these particles will erode and move with the water contaminated groundwater entering the surface and will eventually find their way to larger bodies of water. Surface runoff from PCB contaminated water. Surface sediments having very fine particles surface soil areas into wetlands is probably the are subject to erosional forces and depending on worst case scenario. If PCBs are located in the severity of the water flow, the PCB/particles can saturated surface soils and attached to small

16 Ground Water Issue Polychlorinated Biphenyl Characterization particulates, and, rainfall continually percolates gw_sampling_guide.pdf). At one site the filtering through these soils the water may run off into of the groundwater samples had results as follows sensitive wetland environments and may cause an (NOTE, this is NOT sequential filtering): ecological impact on lower and higher organisms via the food chain. PCB can also be sequestered Table 1. Data from Filtering of Groundwater Samples in sediments that are the habitat of benthic using multiple filter sizes invertebrates. These invertebrates are the food Total PCBs Well ID Filter Size Turbidity for smaller bottom feeding fish, which are the food (Homolog) in µg/L for larger fish and so on up to humans eating fish L-1 None 2.37 NTU 1.03 from the contaminated water body. The tracking of PCB through the food chain will require the use L-1 2 micron 2.37 NTU 0.23 of congener analysis because there will be slight L-1 0.1 micron 2.37 NTU non-detect changes in the PCB pattern through each step in L-5 None >1000 NTU 17.3 the food chain. If ecological risk is a major pathway L-5 2 micron >1000 NTU 3.37 evaluation, the analysis of the organisms may L-5 0.1 micron >1000 NTU 0.072 have to be performed using congener analysis via gas chromatography with high-resolution mass As the table above indicates, with a range spectrometry (GC/HRMS) to assess the risk from of turbidity, filtering with both a 2 micron and the World Health Organization (WHO) dioxin like 0.1 micron, the results show the presence of PCB’s PCBs. The fate and transformation of the PCBs in groundwater. The unfiltered samples have the through a project specific food chain such as was highest concentrations, then following the 2 micron studied in New Bedford Harbor is an example. The filtration PCB remains in solution. For sample L-1 common terns along the beaches adjacent to New in Table 1, the concentration between 2 micron and Bedford Harbor were found to be acting erratically, 0.1 micron appears to be attached to particles within having a very jerky step and jerky motion flying in the colloid range since removal of colloids would the air and in some cases could no longer fly. The be performed with the 0.1 micron filter. The sample terns ate silverside fish that spawned in the area L-5 has dissolved PCB too. A pertinent note here of the New Bedford Superfund Site Hot Spot and is that if a private well was installed at L-1 in Table lived on food in the contaminated sediments. The 1, colloidal material would be coming out the tap common terns ate several times their weight of because at 2.37 NTU there is no visible turbidity. silversides each day. The biomagnifications of PCB EPA calls into question the need for filtration for up the food chain caused the terns to build up PCBs this particular sample because the turbidity is in their brain tissue to a point where their brain was already below the Region 4 criteria of 10 NTU’s. In drowning in PCB and the birds could not control Region 4, any monitoring well sample with turbidity their movements and could no longer fly. The terns below 10 NTU’s does not require any further eventually died of a PCB overdose. The changes purging or developing. in PCB congener pattern were tracked using full congener analysis and the analysis showed that PCB PRODUCTION AND USES each organism preferentially eliminated certain Aroclor production involved the chlorination of congeners and metabolized and retained other biphenyl with anhydrous chlorine in the presence congeners in their tissue. of a catalyst, such as iron filings or ferric chloride. From 1971-1974 two Aroclors, 1016 and 1254 Determining the Presence of Colloidal Transport (produced in a separate syntheses) (Frame, 2001), Knowing if and how much the effects of colloidal were produced differently. In these separate transport are operating is important for the ground syntheses, commercial grade Aroclor 1242 was water remedial decision making process. The wells vacuum-distilled to produce a narrow boiling should be adequately constructed and developed range PCB dubbed Aroclor 1016. Aroclor 1016 and samples should be obtained following proper was produced for some small, specific capacitor purging using the low flow/low stress technique (see applications that required very tight physical Appendix) and http://www.epa.gov/tio/tsp/download/ properties such as specific gravity and viscosity.

Polychlorinated Biphenyl Characterization Ground Water Issue 17 When Aroclor 1016 was separated by vacuum Operation Aroclor Used distillation, the remaining PCB in the reactor was composed of 41% chlorine. This remaining material Cable insulation Aroclor 1248 and 1254 was again reacted with anhydrous chlorine to create Aroclor 1221, 1232, 1242, 1254, Adhesives and tapes a second type of Aroclor 1254, that was composed 1260 of 54% chlorine but had specific congeners in higher concentration than the normal Aroclor 1254 Oil-based paint and caulk Aroclor 1242 and 1254 (Frame, 1999; Kovanti et al, 2001). The second Plastics Aroclor 1242, 1254, and 1262 type of 1254 (sometimes referred to as “hot” or “heavy” 1254) had all the same physical properties Carbonless copy paper Aroclor 1242 except that it was later discovered that it contained Floor finish Aroclor 1254, 1260, and 1262 a much higher content of dioxin-like PCB congeners and a larger amount of dioxin-like polychlorinated Lost wax casting Aroclor 1254 dibenzofurans (Burkhard and Lukasewycz, 2008). The specific gravity and pour point2 were the same Estimated percentage for various PCB uses: as commonly produced 1254 so it would meet the • Closed system and heat transfer fluids electrical specifications for high voltage capacitors. (transformers, capacitors, fluorescent light In countries other than the US, PCB production ballasts, etc.): 60% included at least thirty types of PCBs [United States • Plasticizers: 25% Department of Commerce (USDoC), 1976]. A few trade names include Aroclor B, Chlophen, Phenclor, • Hydraulic fluids and lubricants: 10% Inerteen, Kanechlor, Phenoclor, Pyraleen, Pyranol, • Miscellaneous uses: 5% Santotherm, and Therminol. Most of the foreign PCB Aroclor used in each type of Transformer PCBs were produced in Germany, Italy, Japan, and Capacitor France, and Great Britain. High voltage AC In the Table 2, the types of operation and the Aroclor 1260/TCB (Askarel transformers for large 66.6% 1260, 33.3% TCB) Aroclor that was used in the production is provided industrial uses so that PCB type and suspected source Aroclor can ower voltage AC Aroclor 1254 be established. transformers High voltage AC switches Aroclor 1254 Table 2: Type of Operation Possible and PCB Aroclor used High voltage AC capacitors Aroclor 1254 Aroclor 1254 (70%)/TCB High voltage DC capacitors Operation Aroclor Used (30%) Medium voltage AC Transformers Aroclor 1260 and some 1254 Aroclor 1242 capacitors Capacitors Aroclor 1016, 1242, and 1254 Low voltage small can Aroclor 1242 and 1016 Other electrical capacitors and light ballasts equipment including voltage regulators, List of Heat Transfer operations and the PCB Aroclor 1248, 1254, and 1260 switches, reclosers, used bushings, and Heat cells Aroclor 1254 electromagnets Rubber milling Aroclor 1248, 1254 Oil used in motors and Aroclor 1248, 1254, and 1260 hydraulic systems Plastics molding Aroclor 1242, 1254 Plastics extrusions Aroclor 1242, 1254 Fluorescent light ballasts Aroclor 1254 and 1260 Metal molding Aroclor 1254 Plastics calendaring and Aroclor 1242 coating 2 Pour point is the the lowest temperature at which PCB becomes semi solid and losses its flow characteristics

18 Ground Water Issue Polychlorinated Biphenyl Characterization PCB hydraulic fluid Aroclor Type: when the five quantitative peaks do not change but other peaks do, the method of quantitation assumes High pressure forming Aroclor 1248 Presses that all peaks are present in the same ratio as those congeners in the Aroclor standard. Therefore, Forging operations Aroclor 1248, 1254 a congener or homolog analysis is preferred to High temperature presses Aroclor 1248, 1254 get a true total PCB concentration, since these Construction equipment Aroclor 1242, 1248 approaches allow for correct matching of individual compounds to their respective standards, rather than matching the pattern to the standard of an PCB ANALYTICAL ISSUES Aroclor/Aroclor mixture. Additionally, focusing the In a soil sample analysis, Aroclor 1242 can degrade analysis on individual compounds allows for the use into a chromatogram that is a closer match to the of more sensitive instrumentation and methodology, Aroclor 1248 standard, and in ground water, to a resulting in lower limits of detection. chromatogram that is a closer match to the Aroclor Example Data from a Site showing the relationships 1221. The loss of some congeners and the altering between Aroclor and Homolog data for soils and ground- of the concentration of other congeners can make water: quantitative analysis become only semi-quantitative, as the laboratory attempts to match the pattern to In Figure 7 it is clear that for the same sample, an Aroclor. Since Aroclors are mixtures, the closest the total PCB Homolog concentrations and Total match of the weathered chromatogram pattern to PCB Aroclor concentrations are not the same. an Aroclor standard may not be to the standard Note that the homolog analysis is the accurate of the Aroclor that was originally released. As the total PCB concentration data. The total PCB laboratory attempts to match the pattern to the homolog soil concentrations vary in that for some closest Aroclor standard, likely some of the PCB samples the total homolog concentration data is 2+ material is not included at all in the quantitation. orders of magnitude higher than the total Aroclor For example, if a tetra-substituted congener loses concentrations. In other instances the total Aroclor one chlorine atom due to biological action, then the data is up to an order of magnitude higher in corresponding remaining tri-substituted congener concentrations than the total homolog concentration (trichlorbiphenyl) concentration is increased. Even data. Noted above is that the concentration scale

Comparison of Soil Aroclor Vs Homolog Concentration Data 1000000 Total Aroclors in soil (µg/Kg) 100000

Total Homologs in soil (µg/Kg) 10000

1000

100

1 soil concentration in ug/Kg in concentration soil 0.1

0.01 S100 S101 S102 S103 S104 S105 S106 S107 S108 S109 S110 S111 S112 S113 S114 S115 S116 S117

Figure 7: Graphical Comparison of Total Aroclor and Homolog Soil Concentration Data. (Note: The log scale was chosen for concentration in order to represent all the data.)

Polychlorinated Biphenyl Characterization Ground Water Issue 19 is logarithmic so the variation is significant for some Table 4: Comparison of soil analytical results for of the samples. This site data shows that in some Aroclors and Homologs areas, if the total Aroclor soil concentration data is Total Aroclors in Total Homologs in used there is the possibility that the soil treatment SampleID would be excessive, or in other instances if the total soil (µg/Kg) soil (µg/Kg) Aroclor data was used to inform soil treatment, an S100 765000 319530.0 insufficient treatment area could occur. The take S101 255500.0000 574450.0 home here is that homolog total PCB concentration S102 0.0100 59.1 is the appropriate measure for determining total S103 3370.0000 1652.0 PCB soil and groundwater concentrations. S104 287.0000 445 In looking at the same dataset shown in Figure 7, S105 31.0000 14.9 an additional point is pertinent. In the soil S106 1837.0000 1887.0 Aroclor data, some of the samples show higher S107 0.0100 0.0 concentrations for the Aroclor. Going back to a S108 0.0100 0.0 figure shown earlier (Figure 4), one can see that for example Aroclor 1016 has a subset of congeners S109 0.0100 0.01 that straddle the homolog groups of Mono, Di, S110 0.0100 5.3 Tri and Tetrachlorobiphenyl. Aroclor 1254 has a S111 0.0100 3.8 subset of congeners that straddle Tetra, Penta, S112 80.0000 33.6 and Hexachlorobiphenyl. With various weathering S113 3000.0000 230.0 mechanisms and mixtures, there can be a double S114 590.0000 71.4 counting of congeners/homolog’s so that under S115 0.0100 7.1 certain conditions total Aroclors PCBs can be S116 0.0100 0.01 greater than total congeners/homologs PCBs. On S117 790.0000 38.5 the other hand, weathering of PCB can create a chromatographic curve plot that is not possible to match to any Aroclor so the total Aroclor PCB In another example, Figure 8, the soil concentrations could be a lot lower than the total concentrations were lower than the example shown homolog PCB concentration. in Figure 7 and the comparison is that 100% of the samples showed a Total PCB Homolog Table 4 is the data that informs Figure 7:

Soil Concentration Comparison between Total Homolog PCB Versus Total Aroclor PCB

10000.00 Total Homolog (µg/Kg)

Total Aroclor (µg/Kg) 1000.00

100.00

10.00 Concentration in in ug/Kg Concentration 1.00

0.10

SB1 SB2 SB3 SB4 SB5 SB6 SB7 SB8 SB9 SB10 SB11 SB12

Figure 8: Another comparison of Soil Total Homolog concentration versus Total Aroclor concentration.

20 Ground Water Issue Polychlorinated Biphenyl Characterization concentration greater than the Total PCB Aroclor Deca. In Sample L-5, the homologs are primarily concentration. Trichlorobiphenyl (Tri), Tetrachlorobiphenyl (Tetra) and Pentachlorobiphenyl (Penta) which is more Table 5 is the data that informs Figure 8: soluble and less sorptive. The other piece of the story is that L-1 and L-4 sit in an upland area and Table 5: Table of Data used to construct Figure 8 L-5 sits down in the floodplain so this area receives repeated flooding which also flushes the PCB to Total Aroclor (µg/ Total Homolog groundwater. Location Kg) (µg/Kg) The L-1 and L-4 data show that even if soil concentrations are high, the homolog distribution SB1 0.1 0.9 and the sampled area being in the uplands prevent SB2 0.1 1.9 migration of PCB, in large concentrations, to SB3 0.1 2.2 groundwater. The L-5 data shows that with the less SB4 0.1 9.3 chlorinated PCBs, in the presence of the periodic SB5 0.1 10.8 flooding, and with soil textures that include silt and SB6 0.1 44.4 sand (implying a higher hydraulic conductivity) SB7 0.1 89.9 leaching of PCB to ground water does occur. SB8 0.1 144.4 SAMPLING RECOMMENDATIONS SB9 105.0 2802.0 It is important to note that sampling of waste solids SB10 391.0 3202.6 such as concrete floors, pads, drains, chases SB11 569.0 4557.6 etc. using the EPA Region I power impact drilling SB12 2040.0 6838.0 technique (pp. 53 - 58 of http://www.epa.gov/osw/ hazard/tsd/pcbs/pubs/pcb-guid3-06.pdf) will yield Figure 9 illustrates two points. The first is that a fine powder that can be easily extracted and (1) high concentrations in soil do not necessarily analyzed using Aroclor analysis. All solid samples migrate to ground water and cause highly need to be thoroughly homogenized in the field contaminated ground water. The concentrations in and again in the laboratory to get representative groundwater from sample L-5 show that for lower samples. Surface soils need to be free of debris, soil concentrations, the resulting groundwater grass and other vegetative matter. The soil must concentration is 17.3 ppb versus the highest be thoroughly mixed. When collecting subsurface concentration soil leaching 0.1 ppb. (2) The figure soils from various depths the sub samples can be also demonstrates that if one PCB subsurface homogenized in a bowl and individual samples from soil concentration (protective of groundwater) was specific depths can be frozen for later analysis. The chosen as a clean-up level for the facility it would holding time starts at the point that the samples are not be appropriate for all scenarios. Further data collected. analysis revealed the reason for this leaching Sediment samples (surface and subsurface) pattern. need to be thoroughly homogenized in the field. In Figure 10, the pie charts reveal that the homolog Samples can be collected, frozen (for congener distribution is distinctive for L-1 and L-4 and analysis) and analyzed at a later date if necessary. represents one population of data; whereas, the It is particularly important to note that the percent homolog distribution for L-5 reveals it represents a moisture in sediments must be measured prior to different population. In the legend above the chart weighing out the analytical sample so that extra the homolog ID ranges from Monochlorobiphenyl sample can be added to the meet the dry weight (Mono - one chlorine atom) to Decachlorobiphenyl sample criteria set in the method. This means that (Deca - 10 chlorine atoms). The more chlorine, if the method requires 30 grams of dry solid then the less soluble and more sorptive the PCB is. So the amount of wet sample weighed must have a the soil samples L-1 and L-4 show a distribution dry weight of thirty grams. Very low percent solids that is primarily Nonachlorobiphenyl (Nona) and samples (<30% solids) should be considered

Polychlorinated Biphenyl Characterization Ground Water Issue 21 Soil Total Homolog 25 mg/Kg TSCA GW Total Homolog PCB MCL 1000000.0 20.0

18.0 100000.0 16.0

14.0 10000.0 12.0

1000.0 10.0

8.0 100.0 6.0 Soil Total Homolog ug/Kg GW Total Homolog ug/L Total Homolog GW 4.0 10.0 2.0

1.0 0.0

Sample Location ID L-1 4'-6' L-1 6'-8' L-1 8'-10' L-4 4'-6' L-4 6'-8' L-4 8'-10' L-4 10'-12' L-5 4'-6' L-5 6'-8'

Figure 9. Soil Concentration Total PCB (homolog) data with ground water Total PCB (homolog) concentration data.

Soil and Groundwater Concentration data with a depiction of the Homologue Distribution in Soil indicating That the homologue composition is a large factor in the leaching ability of PCBs from soil to groundwater

Soil Homologue ID Mono Di Tri Tetra Penta Hexa Hepta Octa Nona Deca

Total PCB (Homologue) in Soils Total PCB (Homologue) in Groundwater 1000000.00

100000.00

10000.00

1000.00

100.00 L 46

10.00 Foundry Related Samples Site Related Samples 1.00

Total PCB (Homologue) in ppb in (Homologue) PCB Total L-1 4'-6' L-1 6'-8' L-1 8'-10' L-4 4'-6' L-4 6'-8' L-4 8'-10' L-4 10'-12' L-5 4'-6' L-5 6'-8' 0.10

0.01 Sample Location ID

Figure 10. A depiction of the soil and groundwater Total PCB (homolog) concentration data accompanied by the soil homolog distribution.

22 Ground Water Issue Polychlorinated Biphenyl Characterization for air drying or freeze drying prior to sample manufacturing operations synthesizing PCBs, filling weighing, extraction and analysis. An alternate is to transformers and capacitors, transformer rework determine the percent solids (or percent moisture) operations, and using PCBs for heat transfer and on a small aliquot (e.g., 100 mg), and use the hydraulic fluids. percent solids/moisture to determine the weight of The following are a list of where to look for PCBs sample that will yield 30 g of solids. from the manufacturing process and primary use Sediment screening analysis using GC/ECD operations: Aroclor analysis is acceptable if there are no major • Production floors (concrete) and floor drains changes in the Aroclor pattern of the Aroclor known to be released. In most cases where fresh water • Production piping and piping sumps sediments show changes in the Aroclor pattern, • Concrete floors and drains congener analysis is recommended for total PCBs. • Sub floor concrete and soils under floors Aroclor analysis should be run for all data with no less than 10% (No less than 5 samples) of the • Air contamination/emissions within buildings with samples also being analyzed for congeners. If concrete contamination weathering is revealed as an issue, the Site Team • Uncontrolled floor drains, sumps and collection will need to make decisions about which held frozen tanks samples or additional sample locations should be • Drainage ditches that go to water bodies run for congeners. • Surface soils Samples that exhibit oil droplets or an oil sheen should be handled as if they were pure PCB • Subsurface soils oil. These samples should be screened (see • Landfill soils Appendix F) to determine how high the PCB • Landfill leachate concentration is prior to being sent to the laboratory for full quantitative analysis. Multi dilutions of • Groundwater near or under a production or PCB these samples may be necessary to get the equipment manufacturing/filling facility concentrations on scale. Landfill soils should be • Groundwater near to and under landfill soils treated the same as surface and subsurface soils. • Groundwater near saturated surface soils Leachate should be analyzed as if it were water and either homolog or congener analysis used. Landfill • PCB Particulates in air at any site where PCB leachate may require some special handling as soils are being moved or remediated it is a very reducing media and during extraction • Painted surfaces containing PCB paint may precipitate solids that can clog extraction • Caulking around windows, doors, between walls equipment. Landfill leachate may change as the and floors water takes on oxygen and the sample may have a solid phase and a liquid phase. Sediment Sampling Air samples that are collected on a filter or PUF may not indicate typical Aroclor patterns. High volume The investigation of PCBs in highly wet sediments samples collected on the filter of a TO-4 apparatus (less than 30% solids) usually creates difficulty may have the PCB stripped off the particles and all in extracting the PCB from the wet sediment. the PCB may be found in the PUF. The analysis The water must be removed first to get the best of both the filter and the PUF together must be PCB extraction efficiency. Sediments found in performed. Samples of air particulates caught on fresh water rivers and streams that have a low personnel air monitors may be analyzed by Aroclor percent solids may require processing using a low analysis if enough particulate is present. In some temperature oven drying (for higher chlorinated cases congener analysis may be necessary to meet PCBs) or freeze drying to acquire the correct low detection limits need to show that personnel amount of dry solids required to perform analytical are protected. The bullets at the end of this section extraction to get quantitative results. It has been are the potential waste streams locations for reported that extracting the very wet sediment

Polychlorinated Biphenyl Characterization Ground Water Issue 23 with water soluble solvents such as acetone or extraction, clean-up and analytical procedures isopropanol first, to initially remove the water, and to get quantitative results. This will depend on then extracting with the “method required” solvent the project data quality objectives (DQOs) and (that will more efficiently remove the residual PCBs) the final use of the data. PCB contaminated is the best method developed to date. The sample sediment remediation/clean-up is one of the largest extract must undergo clean up to remove sulfur and remediation problems presently facing the EPA and sulfur containing organics as well as other industrial the Army Corp of Engineers (ACOE) (see http:// interfering PAH compounds (see SW846 Method www.epa.gov/region1/topics/water/rim/rimweblink. 3660B Sulfur Cleanup). Fresh water sediments pdf). having very small particle sizes will require rigorous DEVELOPING A PCB SOIL AND WATER WORK PLAN