MIDWEST RESEARCH INSTITUTE VERIFICATION OF PCB SPILL CLEANUP BY SAMPLING AND ANALYSIS DRAFT INTERIM REPORT NO. 2 TASK 37 EPA Prime Contract No. 68-02-3938 MRI Project No. 8201-A(37) May 7, 1985 Prepared for U.S. Environmental Protection Agency Office of Toxic Substances Field Studies Branch (TS-798) 401 M Street, S.W. Washington, D.C. 20460 Attn: Mr. Daniel T. Heggem MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY MISSOURI 64110 • 816 753-7600 ------- MRI WASHINGTON, D.C. 20006-Suite 250, 1750 K Street, NW. • 202 293-3800 ------- VERIFICATION OF PCB SPILL CLEANUP BY SAMPLING AND ANALYSIS Bruce A. Mitchell 0. Stephen E. Gary L. David C. Bradley D. Boomer Erickson Swanson Kelso Cox Schultz DRAFT INTERIM REPORT NO. 2 TASK 37 EPA Prime Contract No. 68-02-3938 MRI Project No. 8201-A(37) May 7, 1985 Prepared for U.S. Environmental Protection Agency Office of Toxic Substances Field Studies Branch (TS-798) 401 M Street, S.W. Washington, D.C. 20460 Attn: Mr. Daniel T. Heggem MIDWEST RESEARCH INSTITUTE 425 VOLKER BOULEVARD, KANSAS CITY, MISSOURI 64110 • 816 753-7600 ------- DISCLAIMER This document is a preliminary draft. It has not been released formally by the Office of Toxic Substances, Office of Pesticides and Toxic Substances, U.S. Environmental Protection Agency, and should not at this stage be construed to represent Agency policy. It is being circulated for comments on its technical merit and policy implications. ------- PREFACE This Draft Interim Report was prepared for the Environmental Pro- tection Agency under EPA Contract No. 68-02-3938, Work Assignment 37. The work assignment is being directed by Mitchell D. Erickson. This report was prepared by Dr. Erickson, Bruce Boomer, Gary Kelso, and Steve Swanson of Midwest Research Institute (MRI). The sampling design (Section IV.A) was written by David C. Cox and Bradley 0. Schultz of the Washington Consulting Group, 1625 I Street, N.W. , Washington, D.C. 20006, under subcontract to Battelle Columbus Laboratories, Subcontract No. F4138(8149)435, EPA Contract No. 68-01—6721 with the Design and Development Branch, Exposure Evaluation Division. The EPA Task Managers, Daniel T. Heggern and John H. Smith, of the Office of Toxic Substances, provided helpful guidance and technical inforina- ti on. MIDWEST RESEARCH INSTITUTE Clarence L. Haile De y Pr ram Manager ohn E. Goi Program Manager Approved: James L. Spigarelli, Director Chemical and Biological Sciences i)epartment 11 ------- TABLE OF CONTENTS Page I. Introduction. . . . . . 1 II. Summary . . . . 1 III. Overview of PCB Spills and Cleanup Activities 3 A. Introduction to PCB Spills and Cleanup . . . . . 3 1. Current Trends 3 2. Limitations of This Overview 3 B. Components of the Cleanup Process 4 1. Health and Safety 4 2. Reporting the Spill 4 3. Quick Response/Securing the Site 6 4. Determination of Materials Spilled/Cleanup Plan 6 5. Cleanup Procedures 6 6. Proper Disposal of Removed PCB Materials. . . 7 7. Sampling and Analysis 7 8. Remedial Action 8 9. Site Restoration 8 10. Records 8 11. Miscellaneous Considerations 8 IV. Guidelines on Sampling and Analysis . . 9 A. Sampling Design. . . . . . . . 9 1. Proposed Sampling Design 9 2. Sample Size and Design Layout in the Field. . 11 3. Compositing Strategy for Analysis of Samples. 1] 4. Calculations of Average Number of Analyses, and Error Probabilities 25 B. Sampling Techniques . . . . 26 1. Solids Sampling 26 2. Water Sampling 34 3. Surface Sampling . 35 C. Analytical Techniques . . . 35 1. Gas Chromatography (GC) . . . . . . . 40 2. Thin-Layer Chromatography (TLC) . . . 42 3. Total Organic Halide Analyses . . . . . . 43 111 ------- Page D. Selection of Appropriate Methods 43 1. Criteria for Selection 2. Selection of Instrumental Techniques. 3. Selection of Methods 4. Implementation of Methods E. Quality Assurance 47 1. Quality Assurance Plan. 2. Quality Control . . F. Documentation and Records. G. Reporting Results 47 48 51 52 V. References. 52 TABLE OF CONTENTS (concluded) 43 • 44 • 44 • . 46 iv ------- I. INTRODUCTION The U.S. Environmental Protection Agency (EPA) under the authority of the Toxic Substances Control Act (TSCA) Section 6(e) and 40 CFR Section 761.60(d), has determined that polychlorinated biphenyl (PCB) spills must be controlled and cleaned up whenever the spill incident poses a substantial risk to human health or the environment. The Office of Toxic Substances COTS) has been requested to provide written guidelines for cleaning up PCB spills, with particular emphasis on the sampling design and sampling and analysis methods to be used for the cleanup of PCB spills. This work assignment is divided into two phases. The reports of Phase I are presented in Draft Interim Report No. 1, Revision No. 1, “Cleanup of PCB Spills from Capacitors and Transformers,” by Gary L. Kelso, Mitchell D. Erickson, Bruce A. Boomer, Stephen E. Swanson, David C. Cox, and Bradley D. Schultz, submitted to EPA on January 9, 1985. Phase I consists of a review and technical evaluation of the available documentation on PCB spill cleanup, contacts with EPA regional offices and industry experts, and preparation of preliminary guidelines for the cleanup of PCB spills. The document was aimed at providing guidance in all aspects of spill cleanup for those organizations which do not already have working PCB spill cleanup programs. Phase II, reported in this document, reviews the available sampling and analysis methodology for assessing the extent of spill cleanup by EPA en- forcement officials. This report includes some of the information from the Phase I report, incorporates comments on the Phase I report and the general issue which were received at a working conference on February 26-27, 1985, and addresses the issue from the perspective of developing legally defensible data for enforcement purposes. This report, intended primarily for EPA enforcement personnel, out- lines specific sampling and analysis methods to determine compliance with EPA policy on the cleanup of PCB spills. The sampling and analysis methods can be used to determine the residual levels of PCBs at a spill site following the completion of cleanup activities. Although the methodologies outlined in this document are applicable to PCB spills in general, specific incidents may require special efforts beyond the scope of this report. Future changes in EPA policy may affect some of the information presented in this document. Following a summary of the report (Section II), Section III presents an overview of PCB spilis and cleanup activities. The guidelines on sampling and analysis (Section IV) includes discussion of sampling design, sampling techniques, analysis, and quality assurance. II. SUMMARY This report presents the results of Phase II of this work assign- ment. Phase I consisted of a review and technical evaluation of the avail- able documentation on PCB spill cleanup, contacts with EPA regional offices, and preparation of preliminary guidelines for the cleanup of PCB spills. 1 ------- Phase II (this document) reviews the available sampling and analysis rnethodol- ogy for assessing the extent of spill cleanup by EPA enforcement officials. The report incorporates some of the information from the Phase I report and general issues received at a working conference on PCB spills. The EPA has set reporting requirements for PCB spills and views PCB spills as improper disposal of PCBs. Cleanup activities have not been stan- dardized since PCB spills are generally unique situations evaluated on a case- by-case basis by both the PCB owner (or his contractor) and the responsible EPA regional office. Components of the cleanup process may include health and safety; reporting the spill; quick response/securing the site; determina- tion of materials spilled; cleanup procedures; proper disposal of removed PCB materials; and sampling and analysis. The actual level of action is dependent on the amount of spilled liquid, PCB concentration, spill area and dispersion potential, and potential human exposure. A sampling design is proposed for use by EPA enforcement staff in detecting residual PCB contamination above an allowable limit after cleanup of a spill site is completed. The proposed design involves sampling on a hexagonal grid centered on the cleanup area and extending just beyond its boundaries. Guidance is provided for centering the design on the spill site and for staking out the sampling locations, taking possible obstacles into account. Compositing strategies in which several samples are pooled and analyzed together, are recommended for each of the three proposed designs. Since an enforcement finding of noncompliance must be legally defensible, the sampling design emphasizes the control of the false positive rate , the proba- bility of concluding that PCBs are present above the allowable limit when, in fact, they are not. Sampling and analysis techniques are described for PCB-contaminated solids (soil, sediment, etc.), water, oils, surface wipes, and vegetation. A number of analytical methods are referenced; appropriate enforcement methods were selected based on reliability. Since GC/ECD is highly reliable, widely used, and is included in many standard methods, it is a primary recommended method for most spill situations. Secondary methods may be useful for con- firmatory analyses or for special situations when the primary method is not applicable. Quality assurance (QA) must be applied throughout the entire moni- toring program. Quality control (QC) measures, including protocols, certifi- cation and performance checks, procedural QC, sample QC, and sample custody as appropriate, should be stipulated in the QA plan. 2 ------- III. OVERVIEW OF PCB SPILLS AND CLEANUP ACTIVITIES A. Introduction to PCB Spills and Cleanup The EPA has established requirements for reporting PCB spills based on the amount of material spilled and disposal requirements for the spilled PCBs and materials contaminated by the spill. Under TSCA regulations [ 40 CFR 761.30(a)(1)(iii) and 40 CFR 761.60d], PCB spills are viewed as improper disposal of PCBs. Although specific PCB cleanup requirements are not established in the TSCA regulations, each regional administrator is given authority by policy to enforce adequate clean-up of PCB spills to protect human health and the environment. 1. Current Trends Due to regional variations in PCB spill policy and the lack of a national PCB cleanup policy, PCB cleanup activities have not been standard- ized. Individual companies owning PCB equipment and contract cleanup com- panies have developed their own procedures and policies for PCB cleanup activities keyed to satisfying the requirements of the appropriate EPA regional office. In addition, the EPA regional offices typically have pro- vided suggestions for companies unfamiliar with PCB cleanup. PCB spills are generally viewed as unique situations to be evalu- ated on a case-by-case basis by both the PCB owner (or his contractor) and the EPA regional office. However, a general framework is often used to ap- proach the problem. Most cleanup activities involve quick response, removal or cleaning of suspected contaminated material, and post-cleanup sampling to document adequate cleanup. Major considerations involved in the cleanup process include minimizing environmental dispersion, minimizing any present or future human exposure to PCBs, protecting the health and safety of the cleanup crew, and properly disposing contaminated materials. The involvement of EPA regional offices is typically limited to phone conversations often including a follow-up call to receive the ana- lytical results of the post-cleanup sampling. If the EPA representative is not satisfied with the reported data, additional documentation, sampling and analysis, or cleanup (followed by further sampling and analysis) may be re- quested. In cases of special concern (e.g. , large spills), EPA regional of- fices may work more closely with the PCB owner or contractor in planning the cleanup, sampling and analysis activities, and on-site inspections. 2. Limitations of This Overview The general discussion in this chapter refer to the procedures, policy, and considerations that seem to be widely used at present by PCB owners and spill cleanup contractors in meeting the requirements of the EPA regional offices. The activities described do not involve EPA regulations or policy except where indicated, since the EPA has not established requirements on PCB cleanup procedures. 3 ------- Table 1 categorizes PCB spills into approximate levels of action for PCB spill cleanup based on concern. Potential environmental problems in- crease with increases in PCB concentrations, amount of spilled liquid, spill area and dispersion potential, and potential human exposure. The three spill types presented in Table 1 are based on very rough estimates. Severity in one key item such as human exposure could raise a spill to a Type 3 (i. e. requiring special attention). On the other hand a spill of a large volume of liquid may be considered a Type 2 spill due to a relatively low concentration of PCBs. The three categories are only approximate and are intended to demon- strate the flexibility needed in responding to PCB spills. EPA regional of- fices should provide guidance on spill cleanup activities whenever questions develop. The situations described in this chapter are limited to recent PCB spills of similar magnitude to the reported spills associated with PCB oil transformers and capacitors (i.e., Type 2 in Table 1). Unusually severe spill incidents (Type 3 in Table 1) involving large volumes of PCBs, a large spill area, a high probability of significant human exposure, and/or severe en- vironmental or transportation scenarios may require special considerations, beyond the scope of this discussion. Spills below the reporting requirements (< 10 lb or approximately 1 gal.), especially those involving mineral oil transformers, are typically not subject to the detail of effort outlined in this chapter. Although cleanup of these smaller spills (Type 1 in Table 1) is required if the concentration of PCBs in the spilled material is > 50 ppm, the spill and the cleanup activities normally are not reported to EPA. Future changes in EPA policy may invalidate some of the discussions appearing in this chapter. For example, if EPA adopts any type of formal categorization scheme for PCB spills, some of the assumptions made in this chapter may become inappropriate. B. Components of the Cleanup Process 1. Health and Safety Protection of the health and safety of the clean-up crew during the PCB cleanup operation is an important concern. References discussing health and safety considerations relevant to some PCB spill incidents include NIOSH Criteria for A Recommended Standard for Exposure to Polychlorinated Biphenyls ( PCBs ) (1977c) and Health Hazards and Evaluation Report No. 80-85-745 (NIOSH 1980). The appropriate level of health and safety protection is dependent upon the specifics of the spill. 2. Reporting the Spill If the regulatory limits are exceeded, the spill must be reported to federal, state, and local authorities as applicable. Under EPA regulations [ Fed. Reg. 50:13456-13475], spills over 10 lb must be reported to The National Response Center. The toll free phone number is (800) 424-8802. 4 ------- Table 1. Approximate Levels of Action for PCB Spill Cleanup Based on Concern Notes: Type 1 spill is usually not reported. • Type 2 spill is reported and discussed in this chapter. • Type 3 spill is not discussed in this chapter and may require special EPA assistance. • “Severity” in one key item may raise the spill to a higher risk category. 0, Categories of increasing concern Type 1 Type 2 Type 3 Approximate gallons of spilled liquid < 1 > 1 > 5 Area of spill (sq ft) < 250 250 (avg.) > 1,000 PCB concentration in spilled liquid (ppm) < 500 > 50 Variable or high Types of spilled liquid Mineral oil variable) (or Variable Variable, Askarel Exposure scenario Various Various Special concern for high exposure situations ------- 3. Quick Response/Securing the Site Quick response is desirable to mitigate the dispersion of the spilled material and to secure the site. Federal regulations require that cleanup actions commence within 48 hr of discovery of a spill [ 40 CFR 761.30(a)(1) (iii)]. More rapid response is highly preferable. f quick response allows removal or cleaning of the PCB-contaminated material before it is dispersed by wind, rain, seepage, and other natural causes or by humans or animals. In securing the site, the cleanup crew determines the spill boundaries, prevents unauthorized access to the spill site, and notifies all parties involved. The methods used to secure the site will vary on a case-by-case basis, depending on the specific circumstances. The extent of the spill is usually determined by visual inspection with the addition of a buffer area that may include PCBs finely dispersed from splattering. Evaluating the ex- tent of the spill involves considerable judgment, ihcluding consideration of the cause of the spill, weather conditions, and specifics of the site. Field analysis kits may aid the crew in determining the extent of the spill in some instances. The field kits, when used properly, can serve as a screening tool. The need for quick response has limited the usefulness of the more accurate field analytical techniques such as field gas chroma- tography. Practical problems associated with availability of the equipment and trained staff, set-up time, and cost have limit d the use of such tech- niques at this time. 4. Determination of Materials Spilled/Cleanup Plan After securing the site, the response crew will either (a) immedi- ately proceed with the cleanup operation, or (b) identify the materials spilled and formulate an appropriate cleanup plan. A suitable cleanup plan can be developed by identifying the type of PCB material (i.e., mineral oil, PCB oil, Askarel) and considering such factors as the volume spillec, area of the spill, and site characteristics. Based on reasoning similar to Table 1, the crew leader can determine the necessary level of effort in accordance with the policy of the PCB owner and the regional EPA office. He can determine if additional guidance is needed, plan the sampling and analysis, and make other decisions related to the level of effort and procedures needed. 5. Cleanup Procedures The cleanup procedure may include, but may not necessarily be limited to, the following activities: Removal or repair of failed/damaged PCB equipment, Physical removal of contaminated vegetation; 6 ------- Physical removal of contaminated soils, liquids, etc. • Decontamination, encapsulation, or physical removal (as appro- priate) of contaminated surfaces, and • Decontamination or removal of all equipment potentially con- taminated during the cleanup procedures. The specific procedures used in a cleanup are selected by the PCB owner or the cleanup contractor. Key considerations include removal of PCBs from the site to achieve the standards required by the EPA region, company, or other applicable control authority; avoidance of unintentional cross con- tamination or dispersion of PCBs from workers’ shoes, contaminated equipment, spilled cleaning solvents, rags, and other sources; and protection of workers’ health. The cleanup crew shall make every possible effort to keep the spilled PCBs out of sewers and waterways. If this has already occurred, the crew needs to contact the local authorities. Water is never used for cleaning equipment or the spill site. A simple PCB spill cleanup may involve the removal of the leaking equipment, removal of contaminated sod and soil by shovel, cleaning pavement with an absorbant material and solvents, and decontamination or disposal of the workers’ equipment (shovels, shoes, gloves, rags, plastic sheets, etc.). More complicated situations may include decontamina tion of cars, fences, buildings, trees and shrubs, electrical equipment, or water (in pools or bodies of water). In some cases, adequate decontamination of surfaces (pavements, walls, etc.) may not be possible. An alternate to physical removal of the surface material is encapsulation of the contaminated area under a coating impervious to PCBs. EPA Regional Offices may offer advice on this subject. 6. Proper Disposal of Removed PCB Materials All PCB-contaminated materials removed from the spill site, must be shipped and disposed in accordance with relevant federal, state, and local regulations. TSCA Regulations [ 40 CFR 761.60] outline the requirements for the disposal of PCBs, PCB articles, and PCB containers in an incinerator, high efficiency boiler, chemical waste landfill, or an approved alternative method. Facility requirements for incineration and chemical waste landfills are presented in 40 CFR 761.70 and 40 CFR 761.75, respectively. 7. Sampling and Analysis Although sampling and analysis will be discussed in detail in Chapter IV, this discussion gives an overview of applicable considerations and current practice. Sampling and analysis may not always be needed (especially for the spills described as Type 1 in Table 1), but enforcement authorities or property owners may ask for proof that the spill site has been 7 ------- adequately decontaminated. This can be accomplished by taking a number of samples representative of the area contaminated by the spill. Samples should represent the full extent of the spill, both horizontal and vertical, as well as the types of materials in the spill area (soil, surfaces, water, etc.). Sampling design and technique as well as sample handling and preser- vation should incorporate acceptable procedures for each matrix to be sampled and concern for the adequacy and accuracy for the samples in the final analysis. Analysis of the samples for PCB content should be performed by trained personnel using acceptable procedures with due consideration of qual- ity assurance and quality control. Further discussion of sampling and analysis (applicable to EPA en- forcement activities) appears in Chapter IV. 8. Remedial Action I If the analysis results indicate the cleanup was not in compliance with designated cleanup levels, additional cleanup is needed. Additional sam- pling can pinpoint the location of remaining contaminated areas if the original sampling plan was inadequate. If additional cleanup is needed, the cleanup crew will continue as before, removing more material or cleaning surfaces more thoroughly. Remedial action will be followed by additional sampling and anal- ysis to verify the adequacy of the cleanup. 9. Site Restoration This is not addressed under TSCA and is a matter to be settled be- tween the company responsible for the PCB spill and the property owner. 10. Records Although there are no TSCI\ requirements for records of PCB cleanup activities except for documentation of PCBs stored or transported for dis- posal [ 40 CFR 761.80(a)], the PCB owner must keep records of the spill cleanup in case of future questions or concern. Relevant information may include dates, a description of the activities, records of shipment and disposal of PCB-contaminated materials, and a report of collected samples and results of analysis. 11. Miscellaneous Considerations a. Expeditious and effective action are desired throughout the cleanup process to minimize the concern of the public, especially res- idents near the site or individuals with a special interest in the site. Likewise, speed and effectiveness in the cleanup may prevent any future con- cern or action related to the PCB spill. b. Education and training of the spill response crews and re- sponsible staff members is a constant concern. The employees need sufficient training to make proper judgements and to know when additional assistance or guidance is needed. 8 ------- IV. GUIDELINES ON SAMPLING AND ANALYSIS Reliable analytical measurements of environmental samples are an essential ingredient of sound decisions for safeguarding public health and improving the quality of the environment. Effective enforcement monitoring should follow the general operational model for conducting analytical measure- ments of environmental samples, including: planning, quality assurance/quality control, verification and validation, precision and accuracy, sampling, mea- surements, documentation, and reporting. Although many options are available when analyzing environmental samples, differing degrees of reliability, dictated by the objectives, time, and resources available, influence the protocol chosen for enforcement monitoring. The following section outlines the factors crit- ically influencing the outcome and reliability of enforcement monitoring of PCB spill cleanup. A. Sampling Design This section presents a sampling scheme, to be used by EPA Enforce- ment Staff, for detecting residual PCB contamination above the allowable limit after cleanup operations have been completed. Two types of error traceable to sampling and analysis are possible. The first is false positive , i.e. concluding that PCBs are present at levels above the allowable limit when, in fact, they are not. The false positive rate for the present situation should be low, because an enforcement finding of noncompliance must be legally de- fensible, that is, a violator must not be able to claim that the sampling re- sults could easily have been obtained by chance alone. The second type of error possible is a false negative , i.e., failure to detect the presence of PCB levels above the allowable limit. The false negative rate will depend on the size of the contaminated area and on the level of contamination. For large areas contaminated at levels well above the allowable limit, the false negative rate must, of course, be low, to en- sure that serious violators are caught. The false negative rate can be higher for slightly contaminated areas or for small areas. In the extreme case, no sampling scheme will be able to detect a tiny contaminated area with much re- liability. 1. Proposed Sampling Design In practice, the contaminated area from a spill will be irregular in shape. In order to standardize sample design and layout in the field, and to protect against underestimation of the spill area by the cleanup contractor, we are proposing to sample within a circular area surrounding the contaminated area. Guidance on choosing the center and radius of the circle, as well as the number of sample points to be used is provided in Section 2 below. We modeled the detection problem as follows: try to detect a circular area of uniform residual contamination whose center is randomly placed within the sampling circle. The implicit assumption that residual contamination is equally likely to be present anywhere within the sampling area is reasonable, at least as a first approximation (Lingle, 1985). This is because more ef- fort is likely to have been expended in cleaning up the areas which were ob- viously highly contaminated. 9 ------- Two general types of design are possible for the detection problem we have posed: grid designs and random designs. Random designs have two disadvantages compared to grid designs. First, they are more difficult to implement in the field, since the sampling crew must be trained to generate random locations onsite, and since the resulting pattern is irregular. Second, grid designs are more efficient in certain senses than random de- signs. This is because random designs do not result in even spacing of sam- ple points, but rather in a clustering effect which may over-sample some areas at the expense of others. As an illustration, a grid design is certain to detect a sufficiently large circle while some random designs are not. For example, our suggested design below with a sample size of 19 is certain to detect an area of radius 2.8 ft. By contrast, a design based on a simple random sample of 19 points has a 21% chance of failing to detect such an area. We are therefore proposing a grid design. A hexagonal grid based on equilateral triangles has two advantages for this problem. First, such a grid minimizes the circular area certain to be detected (among all grids with the same number of points covering the same area). Second, some previous ex- perience (Mason 1982; Matern 1960) suggests that the hexagonal grid performs well for certain soil sampling problems. The hexagonal grid may, at first sight, appear to be complicated to lay out in the field. Guidance is provided in Section 2 below and shows, we believe, that the hexagonal grid is quite practical in the field and is not significantly more difficult to deploy than other types of grid. The smallest hexagonal grid has 7 points, 1 the next 19 points, the third 37 points. In general, the nth grid has 3n 2 + 3n + 1 points. To com- pletely specify a hexagonal grid, the spacing d (distance between adjacent points) must be determined. We chose d to minimize, as far as possible, the size of the residual contaminated circle which is certain to be detected. Values of d so chosen, together with number of sampling points and radius of smallest circle certain to be detected are shown in Table 2 for a sampling circle of radius 10 ft. For a general sampling circle of radius r feet, the numbers in the table must be adjusted proportionally. For example, the grid spacing for a circle of radius 20 ft for the 7-point design is d = (20)(0.87) = 17.4 ft. Table 2. Parameters of Hexagonal Sampling Designs Design no. No. of points Spacing d (ft) Smallest radius certain to be detected 1 7 8.6 5.0 2 19 4.8 2.8 3 37 3.3 1.9 n 3 2 + 3 + 1 10(n 2 1/3)1/2 10(3n 2 + 1)1/2 10 ------- The first three hexagonal designs are shown in Figures 1 to 3. Re- member that these are scaled for a sampling circle of radius 10 ft. The choice of sample size depends on the cost of analyzing each sample and the reliability of detection desired for various residually contaminated areas. Subsection 2 below provides some suggested sample sizes for different spill areas, based on the distribution of spill areas provided by the Utility Solid Waste Activities Group (USWAG 1984; Lingle 1985). 2. Sample Size and Design Layout in the Field a. Sample Size The distribution of cleanup areas for PCB capacitor spill sites, based on data collected by USWAG (1984) is shown in Table 3. Based on this distribution, we recommend the sample sizes found in Table 4. For all except the very smallest spills a sample size of 19 is recommended. For spills under 25 ft 2 , 7 samples should suffice, while for very large spills over 1,000 ft 2 , 37 samples should be taken. From Table 3, 37 samples will be required in only about 4% of spills (provided the distribution of spill areas sampled by EPA enforcement staff follows Table 3). b. Design Layout in the Field The first step in laying out the design for an irregularly-shaped spill area is to determine the center and radius of the sampling circle which is to be drawn surrounding the spill area. The following approach is recom- mended: (a) Draw the longest dimension, L 1 , of the spill area. (b) Determine the midpoint, P, of L 1 . (c) Draw a second dimension, L 2 , through P perpendicular to L 1 . (d) The midpoint, C, of L 2 is the required center. (e) The distance from C to the extremes of L 1 is the required radius, r. Figure 4 gives some examples of the procedure, and demonstrates that the center and radius are reasonable for most spill shapes. Even if the center determined is slightly off, the sampling design will not be adversely affected. Once the sampling radius r has been determined, and the sample size selected based on Table 4, the grid spacing can be found from Table 2. Example: Suppose r = 5 ft. Then the sampling area is (3.14)(5 2 )ft 2 = 78.5 ft 2 . Thus, a sample size of 19 should be used. The grid spacing is d = (4.8/1O)(5)ft = 2.4 ft. 11 ------- Y to 9 0 0 6 5 4 3 2 0 0 0 —1 -2 -3 —4 -5 -6 : 0 0 -9 ________________________________________________ —10 • — — — — — — I — — — I — I . I — I — I — I . I . I — I • I x Figure 1. Location of sample points in 7 sample point plan. A square represents a sample location. The outer boundary of the contam- inated area is assumed to be 10 ft from the spill site. 12 ------- V 10 —10 j1.1 .1 .1 .I .I*I.11 I .I 111 .1111 ř (1) ot\ O O .... I I I I I I I I x Figure 2. Location of sample points in 19 sample point plan. A square represents a sample location. The outer boundary of the contam- inated area is assumed to be 10 ft from the spill site. 13 ------- :L 0 0 0 0 0 0 0 —10 I I I I I I I I I Figure 3. Location of sample points in 37 sample point plan. A square represents a sample location. The outer boundary of the contam- inated area is assumed to be 10 ft from the spill site. 14 ------- Table 3. Distribution of PCB Capacitor-Spill Cleanup Areas Based on 73 Cases Cleanup area (ft 2 ) Percent of cases 100 50.7 101-200 23.3 201-300 4.1 301-400 2.7 401-500 4.1 501-600 4.1 601-700 0 701-800 1.4 801-900 2.7 901-1,000 2.7 1,001-1,100 0 1,101-1,200 2.7 1,201-1,600 0 1,601-1,700 1.4 Table 4. Recommended Sample Sizes Sampling area (ft 2 ) Sample size 25 7 25-1,000 19 1,000 37 15 ------- Figure 4. Locating the center of an irregularly-shaped spill area. L 1 p / / 16 ------- To find the sampling locations, first lay out a baseline di- ameter of the sampling circle; this diameter can be chosen randomly or for the convenience of the samplers. This baseline should be used as the hor- izontal diameter of the grids as shown in Figures 1 through 3. Once the sampling locations on the grid diameter have been staked out, the remaining samples are located one at a time, always using two existing locations to stake out a new sampling point. Example : Refer to Figure 5 and consider the problem of staking out locations 5 and 6 once locations 1 through 4 have been found. For location 5, attach a piece of rope or sur- veyor’s chain to the stakes at each location 3 and 4. Draw the ropes (chains) taut horizontally until their endpoints meet, at location 5. Stake out and label the new location. To find location 6, use locations 3 and 5 in the same way. By proceeding one step at a time as indicated in the example, the entire grid can be laid out systematically. As an aid, a copy of the ap- propriate Figures 1 through 3 should be labeled before starting to determine the order and numbering of the layout. In practice, various obstacles may be encountered in trying to lay out the sampling grid. Many “obstacles” can be handled by taking a dif- ferent type of sample, e.g., if a fire hydrant is located at a point in a sam- pling grid otherwise consisting of soil samples, then a wipe sample should be taken at the hydrant, rather than taking a sample of nearby soil. The ob- stacle most likely to be encountered is a vertical surface such as a wall. To determine the sampling point on such a surface, simply draw taut the ropes (chains) of length d attached to two nearby stakes and find the point on the vertical surface where their common ends touch. See Figure 6 for an illustra- tion of the procedure. 3. Compositing Strategy for Analysis of Samples Once the samples have been collected at a site, the goal of the analysis effort is to determine whether at least one sample has a PCB con- centration above the allowable limit. A finding of even one unacceptably contaminated sample will trigger a requirement for the responsible party to reclean the entire spill area. Thus, it is not important to determine pre- cisely which samples are contaminatd or even exactly how many. This means that the cost of analysis can be substantially reduced by employing composit- jj g strategies, in which groups of samples are thoroughly mixed and evaluated in a single analysis. Then only if the composite or group shows a suspiciously high level, the individual samples are analyzed one by one to find out if in- deed a single sample has an unacceptably high level of PCB. For purposes of this discussion, we will assume that the maximum allowable PCB concentration in a single sample is 10 ppm. This is a reason- able level for soil samples (the predominant type). Different levels may be required for water samples or wipe samples. However, the calculations can easily be adapted to those cases. The proposed analytical method for soil samples has not been validated; however, existing data and the best judgement 17 ------- o 0 0 0 c i 0 a o 0 0 0 o ci o o 0 0 0 0 0 0 0 o 0 0 0 ‘ (‘)Co \ O)O I I I I I I I / / Figure 5. Locating a new sampling point. 0 0 10 9 8 7 6 5 4 3 2 I 0 —I -2 -3 —4 -5 -6 -7 —8 -g —10 0 2 c i 0 0 0 18 ------- Figure 6. Location of a sampling point on a vertical surface. 19 ------- of chemists experienced in PCB analyses indicate that performance criteria of 80% accuracy and 30% standard deviation should be attainable for concentra- tions above 1 ppm. To protect against false positive findings due to analytical error, the measured PCB level in a single sample must exceed some cutoff greater than 10 ppm for a finding of contamination. For example, suppose that a 5% false positive rate for a single sample were desired. Then, using standard sta- tistical techniques, the cutoff level for a single sample is (0.8)(10) + (1.645)(O.3)(0.8)910) = 11.9 ppm. Thus, if the measured level in a single sample is 11.9 ppm or greater, one can be 95% sure that the true level is 10 ppm or greater. In general, the cutoff is (0.8)(10) + k(O.3)(0.8)(10) = 8 + 2.4k where k chosen to control the false positive rate for the complete set of analyses. Now suppose that a composite of in samples is analyzed. The true PCB level in the composite (assuming perfect mixing) is simply the average of the m levels of the individual samples. Let X be the measured PCB level in the composite. If X (8 + 2.4k)/m, then all m individual samples are rated clean. If X > (8 + 2.4k)/m, then one or more indivjidual samples be con- taminated. The next step is to analyze all m samples individually. The applicability of compositing is potentially limited by the size of the individual specimens and by the performance of the analytical method at low levels of the analyte. First, the individual specimens must be large enough so that the composite can be formed while leaving enough material for individual analyses if needed. In the present situation, adequacy of speci- men sizes should not be a problem. The second limiting factor is the analyt- ical method. Here, we can be sure of performance down to about 1 ppm. Since the assumed permissible level is 10 ppm, no more than about 10 specimens should be composited at a time. In cornpositing specimens, the location of the sampling points to be grouped should be taken into account. If a substantial residual area of con- tamination is present, then contaminated samples will be found close together Thus, contiguous specimens should be composited, if feasible, in order to max- imize the potential reduction in the number of analyses produced by the corn- positing strategy. Rather than describe a (very complicated) algorithm for choosing specimens to composite, we have graphically indicated some possible compositing strategies in Figures 7 through 10. Based on the error probabil- ity calculations presented in Section 4 below, we recommend the compositing strategies shown in Table 5. For details on the reduction in number of analy- ses expected to result (as compared to individual analyses), see Section 4. 20 ------- —2 -3 —4 —5 -6 —7 -I -9 —10 x Figure 7. Location of sample points in a 7 sample point plan, with detail of a 2 group compositing design. 4I) 0 21 ------- V A Figure 8. Location of sample points in a 19 sample point plan, with detail of a 2 group compositing design. —4 — -6 —7 —O —9 -10 o a -. 0 ‘L, •‘) • (I•) 40 ‘\ Q U 0 , I I I I I I I I 22 ------- x Figure 9. Location of sample points in a 19 sample point plan, with detail of a 2 group compositing design. c Q).Q \ (p (1) A) fl .., c ••. ( , A) (r) (O \ ‘b 0) Q — I I I I I f I I 23 ------- Figure 10. Location of sample points in 37 sample point plan, with detail of a 4 group compositing design. —2 —3 —4 -5 —6 —7 -8 -g —10 , , , I I I I I / 24 ------- Table 5. Recommended Compositing Strategies Sample size Compositing strategy 7 One group of 7 19 One group of 10, one of 9 37 Three groups of 9, one of 10 4. Calculations of Average Number of Analyses, and Error Probabil- ities Estimates of expected number of analyses and probabilities of false positives (incorrectly deciding the site is contaminated above the limit), and false negatives (failure to detect residual contamination) errors were obtained for various scenarios. The calculations were performed by Monte Carlo simulation using 5,000 trials for each combination of sample size, compositing strategy, level, and extent of residual contamination. The computations were based on the following assumptions: a. Only soil samples are involved. In practice other types of samples will often be obtained and analyzed. Although the results of this section are not directly applicable to such cases, theydo indicate in gen- eral terms the type of accuracy obtainable and the potential cost savings from coinpositing. b. If the true PCB level in a sample is C, then the measured value is a normally distributed random variable with mean 0.8C and standard deviation (O.3)(O.8C) = O.24C. This accounts for random measurement error. c. The maximum allowable level in a single sample is 10 ppm. The cutoff on the measured value for a single sample for a finding of noncom- pliance is (0.8)(10) + (2.576)(0.3)(0.8)(1O) = 14.2 ppm. This corresponds to a single-sample false positive rate of 0.5%. d. The residual contamination present is modeled as a randomly placed circle of radius r and uniform contamination level X; both r and X can be varied. The PCB level outside the randomly placed circle of contamination is zero. e. Analysis of samples is terminated as soon as a positive re- sult is obtained on any individual specimen. If a composite reads positive, it is broken down into individual specimens and these are analyzed before any other composite. f. The compositing strategies used are shown in Figures 7 through 10. 25 ------- The results of our calculations are shown in Tables 6 through 12. Tables 6 through 8 show the performance of the compositing strategies recom- mended in Section 3. Tables 9 through 12 indicate why the compositing strate- gies of Section 3 are optimal (subject to the constraint of never compositing more than 10 samples) for each sample size. The major conclusions that can be drawn fromthese results are as follows. First, the proposed cutoff on the measured PCB level for a finding of noncompliance for a single sample, 14.2 ppm, is successful in controlling the overall false positive rate of the sampling scheme. For example, when an area half the size of the entire site remains contaminated just at the allow- able limit of 10 ppm, the false positive rate is 1% for the 7-point design, 3% for the 19-point design, and 6% for the 37-point design. Second, the detection capabilities of the design appear satisfactory, bearing in mind the difficulty of detecting randomly-located contamination without exhaustive sampling. As an example, the proposed 19-point design can detect 50 ppm contamination present in 9% of the cleanup area with 97.5% re- liability. Reliability is 95% for 20 ppm contamination present in 25% of the area. Third, the proposed compositing strategies are quite effective in reducing the number of analyses needed to reach a decision in all cases ex- cept those involving large areas contaminated near the cutoff of 10 ppm. For example, for contaminated levels of 25 ppm or greater, the expected number of analyses to reach a decision never exceeds 5 for the 7-point design, or 7 for the 19-point design and the 37-point design. Larger number of analyses are needed in marginal cases, up to 23 for the 37-point design when 50% of the area is contaminated at 10 ppm. B. Sampling Techniques The types of media to be sampled will include soil, water, vegeta- tion and solid surfaces (concrete, asphalt, wood, etc.). General sampling methods are described below. Additional sampling guidance documents are avail- able (Mason 1982, USWAG 1984). 1. Solids Sampling When soil, sand, or sediment samples are to be taken, a surface scrape samples should be collected. Using a 10 cm x 10 cm (100 cm 2 ) template to mark the area to be sampled, the surface should be scraped to a depth of 1 cm with a stainless steel trowel or similar implement. This should yield at least 100 g soil. If more sample is required, expand the area but do not sample deeper. Use a disposable template or thoroughly clean the template between samples to prevent contamination of subsequent samples. The sample should be scraped directly into a precleaned glass bottle. If it is free- flowing, the sample should be thoroughly homogenized by tumbling. If not, successive subdivision in a stainless steel bowl should be used to create a representative subsample. 26 ------- Table 6. Performance of Sampling Strategy with 7 Points Composited Together X R: 1 3 5 7 4 1.00 1.00 1.00 1.08 0.000 0.000 0.000 0.000 8 1.00 1.00 1.42 4.00 0.000 0.000 0.000 0.000 10 1.01 1.01 1.84 5.04 0.000 0.000 0.001 0.009 12 1.03 1.21 2.25 5.40 0.000 0.001 0.015 0.088 14 1.10 1.62 2.88 5.16 0.004 0.020 0.081 0.284 16 1.14 1.98 3.56 4.76 0.009 0.059 0.205 0.521 20 1.26 2.56 4.26 4.05 0.029 0.206 0.482 0.774 25 1.27 2.84 4.47 3.65 0.047 0.351 0.746 0.910 50 1.29 2.87 4.52 3.46 0.069 0.473 0.972 0.991 500 1.30 2.91 4.47 3.38 0.075 0.487 0.999 0.000 Note: Top number = average number of analyses. Bottom number = probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). R = radius of contaminated circle iii feet; X PCB contamination level in ppm. 27 ------- Table 7. Performance of Sampling Strategy with 19 Points, 2 Composites X R: 1 3 5 7 4 2.00 2.00 3.28 7.37 0.000 0.000 0.000 0.000 8 2.00 3.04 9.12 13.13 0.000 0.000 0.000 0.000 10 2.02 3.74 10.48 14.13 0.000 0.002 0.014 0.029 12 2.07 4.49 10.68 12.82 0.000 0.026 0.150 0.272 14 2.31 5.04 9.32 9.41 0.006 0.115 0.460 0.686 16 2.54 5.83 7.59 6.59 0.023 0.261 0.737 0.909 20 2.74 6.25 5.47 4.25 0.072 0.556 0.949 0.992 25 2.79 6.33 4.50 3.45 0.123 0.780 0.991 0.999 50 2.81 6.04 4.01 3.04 0.168 0.975 0.999 1.000 500 2.82 5.98 3.97 3.03 0.166 0.998 1.000 1.000 Note: Top number = average number of analyses. Bottom number probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). R = radius of contaminated circle in feet; X = PCB contamination level in ppm. 28 ------- Table 8. Performance of Sampling Strategy with 37 Points, 4 Composites X R: 1 3 5 7 4 4.00 4.35 9.67 15.58 0.000 0.000 0.000 0.000 8 4.00 9.03 15.94 22.02 0.000 0.000 0.000 0.000 10 4.02 10.50 17.17 22.96 0.000 0.009 0.029 0.056 12 4.16 10.97 15.74 17.83 0.001 0.108 0.309 0.479 14 4.56 10.24 11.27 10.32 0.014 0.358 0.723 0.898 16 4.90 9.04 7.87 6.43 0.044 0.620 0.937 0.991 20 5.22 7.25 5.51 4.33 0.137 0.888 0.996 1.000 25 5.31 6.44 4.67 3.57 0.237 0.968 0.999 1.000 50 5.22 5.86 4.20 3.09 0.331 0.997 1.000 1.000 500 5.25 5.86 4.13 3.08 0.350 0.999 1.000 1.000 Note: Top number = average number of analyses. Bottom number = probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). R = radius of contaminated circle in feet; X = PCB contamination level in ppm. 29 ------- Table 9. Comparison of Sampling Designs for r = 1 (1% of Spill Site Size) Level of contaminated area, x 1 7 Group, points 2 7 Groups, points Individually, 7 points 2 19 Groups, points 6 19 Groups, points Individually, 19 points 4 : 1.00 0.000 2.00 0.000 7.00 0.000 2.00 0.000 6.00 0.000 19.00 0.000 8 : 1.00 0.000 2.00 0.000 7.00 0.000 2.00 0.000 6.00 0.000 19.00 0.000 10 : 1.01 0.000 2.00 0.000 7.00 0.001 2.02 0.000 6.01 0.000 19.00 0.001 12 : 1.03 0.000 2.02 0.000 6.98 0.005 2.07 0.000 6.03 0.000 18.93 0.008 14 : 1.10 0.004 2.05 0.004 6.96 0.013 2.31 0.006 6.08 0.005 18.74 0.029 16 : 1.14 0.009 2.07 0.010 6.92 0.026 2.54 0.023 6.12 0.019 18.46 0.063 20 : 1.26 0.029 2.12 0.029 6.88 0.043 2’.74 0.072 6.08 0.070 18.06 0.110 25 : 1.27 0.047 2.12 0.048 6.84 0.052 2.79 0.123 6.00 0.121 17.75 0.143 50 : 1.29 0.069 2.12 0.066 6.80 0.067 2.81 0.168 5.94 0.166 17.49 0.173 500 : 1.30 0.075 2.13 0.071 6.81 0.063 2.82 0.166 5.93 0.167 17.46 0.177 — number o f -- - Note: Top number = average analyses; bottom number probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). 30 ------- Table 10. Comparison of Sampling Designs for r = 3 (9% of Spill Site Size) Level contami area, of nated x 1 7 Group, points 2 7 Groups, points Individually, 7 points 2 19 Groups, points 6 19 Groups, points Individually, 19 points 4 : 1.00 0.000 2.00 0.000 7.00 0.000 2.00 0.000 6.00 0.000 19.00 0.000 8 : 1.00 0.000 2.00 0.000 7.00 0.000 3.04 0.000 6.19 0.000 19.00 0.000 10 : 1.01 0.000 2.01 0.000 6.99 0.001 3.74 0.002 6.34 0.002 18.96 0.004 12 : 1.21 0.001 2.10 0.001 6.91 0.027 4 .49 0.026 6.53 0.015 18.40 0.067 14 : 1.62 0.020 2.31 0.020 6.69 0.099 5.04 0.115 6.77 0.087 16.90 0.232 16 : 1.98 0.059 2.48 0.059 6.49 0.165 5.83 0.261 6.80 0.224 14.86 0.448 20 : 2.56 0.206 2.73 0.206 6.06 0.314 6.25 0.556 6.36 0.533 11.89 0.731 25 : 2.84 0.351 2.82 0.350 5.65 0.426 6.33 0.780 5.83 0.781 10.22 0.874 50 : 2.87 0.473 2.79 0.473 5.45 0.494 6.04 0.975 5.20 0.976 8.94 0.990 500 : 2.91 0.487 2.81 0.488 5.46 0.499 5.98 0.998 5.13 0.999 8.62 0.999 Note: Top number = average number of analyses; bottom number probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). 31 ------- Table 11. Comparison of Sampling Designs for r = 5 (25% of Spill Site Size) Level contami area, of nated x 1 Group, 7 points 2 Groups, 7 points Individually, 7 points 2 Groups, 19 points 6 19 Groups, points Individually, 19 points 4 : 1.00 0.000 2.00 0.000 7.00 0.000 3.28 0.000 6.08 0.000 19.00 0.000 8 : 1.42 0.000 2.13 0.000 7.00 0.000 9.12 0.000 7.73 0.000 19.00 0.000 10 : 1.84 0.001 2.26 0.000 6.98 0.005 10.48 0.014 8.47 0.010 18.83 0.017 12 : 2.25 0.015 2.46 0.010 6.81 0.063 10.68 0.150 8.53 0.117 17.31 0.180 14 : 2.88 0.081 2.83 0.068 6.29 0.219 9.32 0.460 7.87 0.384 13.72 0.516 16 : 3.56 0.205 3.22 0.183 5.64 0.409 7.59 0.737 6.85 0.653 10.58 0.761 20 : 4.26 0.482 3.56 0.466 4.68 0.684 5.47 0.949 5.49 0.919 6.25 0.962 25 : 4.47 0.746 3.54 0.745 4.12 0.854 4.50 0.991 4.70 0.988 4.35 0.995 50 : 4.52 0.972 3.47 0.969 3.58 0.987 4.01 0.999 4.24 0.999 3.34 1.000 500 : 4.47 0.999 3.44 0.999 3.50 1.000 3.97 1.000 4.17 1.000 3.23 1.000 Note: iop number = average number of analyses; bottom number probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). 32 ------- Table 12. Comparison of Sampling Designs for r = 7 (50% of Spill Site Size) Level contami area, of nated x 1 7 Group, points 2 7 Groups, points Individually, 2 7 points 19 Groups, points 6 19 Groups, points Individually, 19 points 4 : 1.08 0.000 2.02 0.000 7.00 0.000 7.37 0.000 6.31 0.000 19.00 0.000 8 : 4.00 0.000 2.98 0.000 7.00 0.000 13.13 0.000 9.78 0.000 19.00 0.000 10 : 5.04 0.009 3.55 0.006 6.96 0.013 14.13 0.029 10.83 0.022 18.73 0.030 12 : 5.40 0.088 3.81 0.067 6.61 0.118 12.82 0.272 10.42 0.226 16.15 0.296 14 : 5.16 0.284 3.96 0.216 5.79 0.349 9.41 0.686 8.47 0.623 11.34 0.705 16 : 4.76 0.521 3.90 0.441 4.82 0.579 6.59 0.909 6.43 0.876 7.14 0.921 20 : 4.05 0.774 3.58 0.747 3.53 0.849 4.25 0.992 4.45 0.991 3.74 0.994 25 : 3.65 0.910 3.18 0.895 2.87 0.951 3.45 0.999 3.77 0.999 2.61 1.000 50 : 3.46 0.910 2.94 0.895 2.40 0.997 3.04 1.000 3.29 1.000 2.10 1.000 500 : 3.38 1.000 2.88 1.000 2.39 1.000 3.03 1.090 3.31 1.000 2.02 1.000 T number of ana lyses; bottom Note: op number = average number = probability of declaring out of compliance (for levels of PCB, x, 10 ppm and below this will be the probability of false positive; for levels above 10 this will be the probability of detection). 33 ------- In some cases, such as sod, scrape samples may not be appropriate. For these cases, core samples, not more than 5 cm deep, should be taken using a soil coring device. These core samples should be well—homogenized in a stainless steel bowl by successive subdivision. A portion of each sample should then be removed, weighed and analyzed. Samples should be stored at 4°C in precleaned glass bottles. Be- fore collection of verification samples, this equipment must be used to gen- erate a field blank as described in Section IV.E. 2. Water Sampling a. Surface Sampling If PCBs dissolved in a hydrocarbon oil were spilled, they will most likely be dispersed on the surface. Therefore, a surface water collec- tion technique should be used. Surface water samples should be collected by grab techniques. Where appropriate, the precleaned glass sample bottle may be dipped directly into the body of water at the designated sample collection point. A sample is collected from the water surface by gently lowering a pre- cleaned sample bottle horizontally into the water until water begins to run into it. The bottle is then slowly turned upright keeping the lip just under the surface so that the entire sample is collected from the surface. b. Subsurface Sampling If the PCBs were in an Askarel or other heavier-than-water matrix, the PCBs will sink. In these cases water nea ’ the bottom should be collected. To collect subsurface water, the bottle should be lowered to the specified depth with the cap on. The cap is then removed, the bottle allowed to fill, and the bottle brought to the surface. c. Other Sampling Approaches When the above approaches are not feasible, other dippers, tubes, siphons, pumps, etc. , may be used to transfer the water to the sample bottle. The sampling system should be of stainless steel, Teflon, or other inert, impervious, and noncontaminating material. Before collection of sam- ples, this equipment must be used to generate a field blank as described in Section IV.E. d. Sample Preservation The bottle is then lifted out of the water, capped with a PTFE- or foil-lined lid, identified with a sample number, and stored at approximately 4°C until analysis to retard bacterial growth. 34 ------- 3. Surface Sampling a. Wipe Samples If the surface to be sampled is smooth and impervious (e.g. rain gutters, aluminum house siding), a wipe sample should indicate whether the cleanup has sufficiently removed the PCBs. These surfaces should be sam- pled by first applying an appropriate solvent (e.g., hexane) to a piece of 11 cm filter paper (e.g. , Whatman 40 ashless, or Whatman “50” smear tabs) or gauze pad. This moistened filter paper or gauze pad is held with a pair of stainless steel forceps and used to thoroughly swab a 100-cm 2 area as mea- sured by a sampling template. Care must be taken to assure proper use of a sampling template. Different templates may be used for the variously shaped areas which must be sampled. A 100 cm 2 area may be a 10 cm x 10 cm square, a rectangle (e.g. 1 cm x 100 cm or 5 cm x 20 cm), or any other shape. The use of a template assists the sampler in the collection of a 100 cm 2 sample and in the selec- tion of representative sampling sites. When a template is used it must be thoroughly cleaned between samples to prevent contamination of subsequent samples by the template. The wipe samples should be stored in precleaned glass jars at 4°C. Before collection of verification samples, the selected filter paper or gauze pad and solvent should be used to generate a field blank as described in Sec- tion IV.E. b. Sampling Porous Surfaces Wipe sampling is inappropriate for surfaces which are porous and would absorb PCBs. These include wood and asphalt. Where possible, a discrete object (e.g. , a paving brick) may be removed. Otherwise, chisels, drills, saws, etc., may be used to remove a sufficient sample for analysis. Samples near (generally less than 1 cm deep) the surface most likely to be contaminated with PCBs should be collected. Where possible, the sample col- lection should be as unobtrusive as possible. C. Analytical Techniques A number of analytical techniques have been used for analysis of PCBs in the types of samples which may be associated with PCB spills. Some of the candidate analytical methods are listed in Table 13. The analysis method(s) most appropriate for a given spill will depend upon a number of factors. These include sensitivity required, precision and accuracy required, potential interferents, ultimate use of the data, experience of the analyst, availability of laboratory equipment, and number of samples to be analyzed. As shown in Table 13, many analytical methods are available. The general analytical techniques are discussed and then compared below. 35 ------- Table 13 Standard Procedures of Analysis for PCBs Procedure Determination Quanti tati on designation Matrix Extraction Cleanupc method Qual. method LOD QC Reference 03534-80 Water Hexane/CH 2 C1 2 (Florisil) PGC/ECDd No Total area or 0.1 pg/i No ASTM, 1981a (Silica Gel) Webb-McCall 608 Water CH 2 C 1 2 (Florisil) PGC/ECO No Area 0.04-0,15 pg/L Yes EPA, 1984a, (S removal) Longbottom and Lichtenberg, 1982 625 Water CH 2 C 1 2 None PGC/EIMS Yes Area 30-36 pg/L Yes EPA, 1984b, (CGC) Longbottom and Lichtenberg, 1982 304h Water Hexane/ Florisil/ PGC/ECD Yes Summed areas NS Yes EPA, 1978 CH 2 C1 2 silica gel or HECO or Webb-McCall (85/15) (CH 3 CN) (S removal) EPA (by- Water Several Several HRGC/EIMS Yes md. peaks NS Yes Erickson et al products) 1982, 1983d, EPA, 1984c ANSI Water Hexane (H 2 S0 4 ) PGC/ECD No Single peak or 2 ppm Yes ANSI, 1974 (Saponification) summed peaks Alumina Monsanto Water Hexane Alumina PGC/ECD No Individual or 2 ppb No Moein, 1976 total peak heights UK-DOE Water Hexane Silica gel PGC/ECO No NS 106 ng/L No UK-DOE, 1979; Devenish and Han ing-Bowen, 1980 03304-74 Air DI PGC/ECD No Total area NS Yes ASTM, 198]b Water Hexane (H 2 50 4 ) Soil, H 2 0/CH 3 CN (Saponification) sediment (Alumina) EPA (homolog) Solids and Several Several HRGC/EIMS Yes md peaks MS Yes Erickson et al liquids 1985a EPA 625-S Sludge CH 2 C1 2 Florisil, HRGC/EIMS or Yes Area MS Yes Haile and Silica gel, PGC/EIMS Lopez-Avila, or GPC 1984 ------- Table 13 (Continued) Procedure Determination Quantitation designation Matrix Extraction Cleanup method Qual method LOU QC Reference EPA Sludge Hexane/ GPC PGC/ECD Yes Peak area or US Yes Rodriguez (Halocarbon) CH 2 C1 2 / S removal peak height et al. , 1980 acetone (83/15/2) Priority Sludge CH 2 C1 2 GPC PGC/EIMS Yes MS MS Yes EPA, 1979c Pollutant (base/ neutral and acid fractions) 6100 Sludge CH 2 Cl 2 GPC HRGC/EIMS Yes NS NS Yes Ballinger, 1978 (3 fractions) Silica gel or PGC/EIMS 8080 Solid waste CH 2 C1 2 (Florisil) PGC/ECD No Area 1 pg/g Yes EPA, 1982e 8250 Solid waste CH 2 C1 2 None PGC/EIMS No MS 1 pg/g Yes EPA, 1982e c 8270 Solid waste CHC1 2 None CGC/EIMS NO NS 1 pg/g Yes EPA, 1982e EPA (spills) Unspecified Hexane/ (CH 3 CN) PGC/ECD No Total area or MS Plo Beard and acetone (Florisil) Webb-McCall Schaum, 1978 (Silica gel) (Mercury) EPA Soil and Acetone! Florisil PGC/ECD No Computer MS Yes EPA, 1982d Sediment Hexane Silica gel (S removal) - Monsanto Sediment CH 3 CN Saponification PGC/ECD No individual or 2 ppb No 1oein, 1976 H 2 S0 4 total peak Alumina heights ANSI Sediment, CH 3 CN Saponification PGC/ECD No Single peak or 2 ppm Yes ANSI, 1974 soil 112504 summed peaks Alumina EPA (by- Air collected Hexane (H 2 S0 4 ) HRGC/EIMS Yes md. peaks 1 15 Yes Erickson et al products) on Florisil or (Florisil) 1982, 1983d, XAD-2 Erickson, 1984b EPA (ambient Air near haz- Ilexane! Alumina PGC/ECD No Total area or 10-50 ng!in 3 No Lewis, 1982 air) ardous waste ether peak height sites col- lected on P1W ------- Quantitation method 100 Reference Table 13 (Continued) Procedure designation Matrix Extraction CleanupC Determination method Qual EPA (stack) Incinerator emissions and ambient air collected on Florisil Hexane (H 2 S0 4 ) Perchiorina- tion PGC/ECD No Area 10 ng EPA Combustion sources collected on Florisil Pentane or CH 2 C 1 2 (FlorisIl/ silica gel) PGC/MS Yes Area/homolog 0 1 nq/inj EPA (incin— Stack gas Pentane/ PGC/MS Yes Single peak MS erators) methanol ANSI Air (to luene impinger) - (H 2 5 0 4 ) (Saponification) (Alumina) PGC/ECD No Single peak 2 ppb NIOSH (P&CPN 244) Air collected on Florisil Hexane None PGC/ECD No Peak height or area from stan- dard curve or Webb-McCall 0 01 mg/rn 3 NIOSH Air collected Hexane None PGC/ECD No Peak height or 0 01 mg/rn 3 (P&CAM 253) on Florisil Perchlorina- tion area from stan dard curve EPA (gas) - Natural gas sampled with Florisil Hexane H 2 S0 4 - - PGC/ECD - Total area, peak height or Webb- McCall (Perchlorination) 0 1-2 pg/rn 3 EPA [ 5,A,(3)] Blood Hexane (Florisil) PGC/ECD No NS MS EPA [ 5,A,(1)] Adipose Pet ether! CH 3 CN Florisil PGC/ECD No MS MS EPA (9,D) Adipose Pet. ether/ CH 3 CN Saponification Florisil TLC No Semiquant. 10 ppm EPA (9,B) Milk Acetone! hexane CH 3 CN Florisil Silica acid PGC/ECD Yes md peaks 50 ppb QC No Haile and Baladi, 1977; Beard and Schaum, 1978 No levins et al. 1979 Yes Beard and Schaum, 1978 Yes ANSI, 1974 No NIOSH, 1977a Mo NIOSH, 1977b,c No Harris et al 1981 No Yes No Yes Watts, 1980 Watts, 1980 Watts, 1980 Watts, 1980 Sherma, 1981 ------- Table 13 (Continued) Procedure Determination designation Matrix Extraction CleanupC method Qual ADAC (29) Food CH 3 CN/Pet. Florisil MgO/ PGC/ECD No ether Celite Saponi fi cation Japan Food Pet. ether! Silica gel PGC/ECD Yes CH 3 CN Saponi fication (Florisil) PAM Food Pet ether! Silicic acid PGC/ECD No CH 3 CN (Saponification) (PGC/HECD) (Oxidation) (NP-TIC) (Florisil) (RP—TLC) Paper and Saponifica- Florisil MgO! PGC/ECO No paperboard tion Celite Saponi fication Capacitor 01 b None SCOT HRGC/FID No Askarels Mineral oil Dilute with Florisil slurry PGC/ECD Yes hexane or (H 2 S0 4 ) (PGC/HECD) isooctane (Florisil column) Transformer DI (H 2 S0 4 ) PGC/HECD No fluids or (Florisil) or /ECD or waste oils (Alumina) /EIMS (Silica gel) (HRGC) (GPC), (CH 3 CN) - - - - — EPA (by- Products or Several Several HRGC/EIMS Yes products) wastes DCMA 3 pigment A. Hexane/ None PGC/ECD No types H 2 S0 4 B CH 2 C1 2 Florisil DOW Chlorinated DI None PGC/EIMS Yes benzenes EPA (isomer Unspecified Not addressed Not addressed HRGC/EIMS Yes groups) Source. N LI Erickson, Ihe Analytical Chemistry of PCBs , Butterworths, Boston, MA, a No specilic details b Direct injection or dilute and inject. c Techniques in parentheses are described as optional in the procedure d Or PGC with microcoulornetric or electrolytic conductivity AOAC (29) 03303- 74 D4059-83 EPA (oil) Quanti tation method LOD QC Reference Total area or NSa No AOAC, 1980a md peaks Summed areas NS No Tanabe, 1976 perch lorination Area NS No FDA, 1977 Total area or NSa No AOAC, 198Ob md peaks Total area 2.8 x 108 mol/L Ho ASTM, 1980a md. peaks or SO ppm No ASTM, 1983 Webb-McCall Total area or 1 mg/kg Yes EPA, 1981 Webb-McCall Bellar and Lichtenberg, 1981 md peaks MS Yes Erickson et al 1982, 1983d; Erickson, 1984a , 10 isomers . 1 ppm!homolog Yes DCMA, 1982 Total peak MS Yes Dow, 1981 height/homolog md peaks MS Yes EPA, 1984d 1985, in press ------- 1. Gas Chromatography (GC ) As can be seen in Table 13, analysis of PCBs by gas chromatography is frequently the method of choice. PCBs are chromatographed using either packed or capillary columns and may be detected using either specific detec- tors or mass spectrometry. A comprehensive method for analysis of PCBs in transformer fluid and waste oils was developed by Bellar and Lichtenberg (1982). This method describes six different cleanup techniques, recommends three GC detectors, and suggests procedures for GC calibration and for mea- surement of precision and accuracy. This method also discusses several cal- culation methods. a. Gas Chromatograph/Electron Capture Detection Packed column gas chromatography with electron capture detec- tion (GC/ECD) is generally the method of choice for analysis of spill site samples, transformer oils, and other similar matric s which must be analyzed for PCB content prior to disposal (Copland and Gohmann 1982). GC/ECD is very sensitive, highly selective against hydrocarbon background, and relatively inexpensive to operate. The technique is most appropriate when the PCB resi- due resembles an Aroclor standard and other halogenated compounds do not inter- fere. While it is considered a selective detector, ECO also detects non-PCB compounds such as halogenated pesticides, polychiorinated naphthal- enes, chloroaromatics, phthalate and adipate esters, and other compounds. These compounds may be differentiated from PCBs only by chrornatographic re- tention time. Elemental sulfur can interfere with PCB analysis in sediment and other samples which have been subjected to anaerobic degradation condi- tions. There are also common interferences which do not give discrete peaks. An example of a nonspecific interference is mineral oil (ASTM 1983). Mineral oil, a complex mixture of hydrocarbons, can cause a general suppression of ECD response. Mineral oils from transformers often contain PCBs as a result of cross-contamination of transformer oils. A major disadvantage of ECD is the range of response factors which different PCB congeners exhibit. Zitko et al. (1971) and Hattori et al. (1981) published response factors ranges of about 540 and 9000, respectively. Boe and Egaas (1979), Onsuka et al. (1983) and Singer et al. (1983) have also published ECU response factors. The range of response factors seriously in- hibits reliable quantitation. When PCBs are analyzed by packed column gas chromatography, the PCBs are usually quantitated by total areas or individual peaks. In the total areas method, the areas of all peaks in a retention window are summed and this total compared with the corresponding response of an Aroclor stan- dard. With the individual peak quantitation method, response factors are calculated for each peak in the packed column chromátograrn. The most prom- inent individual peak quantitation method was originated by Webb and McCall (1973). These results may be reported as an Aroclor concentration or as total PCB. Packed column GC techniques are generally useful for quantitation 40 ------- of samples which resemble pure Aroclors but are prone to errors from inter- fering compounds or from PCB mixtures that do not resemble pure Aroclors (Albro 1979). For this reason analysts have been using capillary gas chro- matography for the analysis of PCB5. Capillary gas chromatography offers the analyst the ability to separate most of the individual PCB isomers. Bush et al. (1982) has proposed a method of obtaining “total PCB” values by inte- gration of all PCB peaks, using response factors generated from an Aroclor mixture. Zell and Ballschmiter (1980) have developed a simplified approach where only a selected few “diagnostic peaks” are quantitated. In a similar approach Tuinstra et al. (1983) have quantitated six specific, diagnostic con- geners which appear to be useful for regulatory cutoff analyses. b. GC/Hall Electrolytic Conductivity Detector Electrolytic conductivity detectors have also been used with packed column gas chromatography to selectively detect PCBs (Webb and McCall 1973, Sawyer 1978). The Hall electrolytic conductivity detector (HECD) mea- sures the change in conductivity of a solution containing HC1 or HBr which is formed by pyrolysis of halogenated organic GC effluents. The HECD exhibits 105_106 selectivity for halogenated compounds over other compounds. It also gives a linear response over at least a 10 range. HECD and ECO were com- pared for their use in detecting PCBs in waste oil, hydraulic fluid, capacitor fluid, and transformer oil (Sonchik et al. 1984). They found both detectors acceptable, but noted that the HECD gave higher results with less precision than the ECO. The method detection limits ranged from 3-12 ppm for HECD and 2-4 ppm for [ CD. Greater than 100% recovery of spikes analyzed by HECO indi- cated a nonspecific response to non-PCB components, since extraneous peaks were not observed. Another comparison of HECD and ECO for the analysis of PCBs in oils at the 30-500 ppm levels found that the type of detector made no significant difference in the results (Levine et al. 1983). The authors noted that higher accuracy had been expected from the more specific HECD. They postulated that the cleanup procedures (Florisil, alumina, and sulfuric acid) all had effectively removed the non-PCB species which would have caused interferences in the ECD and reduced its accuracy. c. GC/Mass Spectrometry Highly specific identification of PCBs is performed by GC with mass spectrometric (GC/MS) detection. High resolution gas chromatography is generally used with mass spectrometry, so individual PCB isomers may be separated and identified. A GC/MS produces a chromatogram consisting of data points at about 1-s intervals, which are actually full mass spectra. The data are stored by a computer and may be retrieved in a variety of ways. The data file contains information on the amount of compound (signal intensity), molecular weight (parent ion), and chemical composition (fragmentation pat- terns and isotopic clusters). GC/MS is particularly suited to detection of PCBs because of its intense molecular ion and the characteristic chlorine cluster Chlorine has two naturally occurring isotopes, 35 C1 and 37 C1, which occur in a ratio of 100:33. Thus, a molecule with one chlorine atom will have a parent ion, M, and an M+2 peak at 33% relative intensity. With two chlorine atoms, M+2 has an intensity of 66% and M+4, 11%. 41 ------- Because of its expense, complexity of data, and lack of sensi- tivity, GC/MS has not been used as extensively as other GC methods (particu- larly GC/ECD), despite its inherently higher information content. As the above factors have been improved, GC/MS has become much more popular for analysis of PCBs, and will probably continue to increase in importance. Sev- eral factors including the introduction of routine instruments without costly accessories, decreasing data system costs, and mass-marketing, have combined to keep the costs of GC/MS down while prices of other instruments have risen steadily. With larger data systems and more versatile and Huser_friendlyhl software, the large amount of data is more easily handled. However, data re- duction of a GC/MS chromatograni still requires substantially more time than for a GC/ECD chromatogram. In addition, the sensitivity of GC/MS has im- proved. d. Field-Portable Gas Chromatography Instrumentation Gas chromatography may be used for analysis of samples in the field. Gas chromatography is a well-established laboratory technique, and portable instruments with electron capture detectors are available (Splittler 1983, Colby et al. 1983, Picker and Colby 1984). A field-portable GC/ECD was used to obtain rapid measurements of PCBs in sediment and soil (Spittler 1983). The sample preparation consisted of a single solvent extraction. The PCBs were eluted from the GC within 9 mm. In a 6-h period, 40 soils and 10 QC samples were analyzed, with concentrations ranging from 0.2 to 24,000 ppm. The use of field analysis permits real-time decisions in a cleanup op- eration and reduces the need for either return visits to a site. Mobile mass spectrometers are also available. An atmospheric pressure chemical ionization mass spectrometer, marketed by SCIEX, has been mounted in a van and used for in situ analyses of soil and clay (Lovett et al. 1983). The instrument has apparently been used for field determination of PCBs in a variety of emergency response situations, including hazardous waste site cleanups. Other, more conventional mass spectrometers, should also be amenable to use in the field. 2. Thin-Layer Chromatography (TLC ) Thin—layer chromatography is a well-established analytical tech- nique which has been used for the determination of PCBs for many years. Since the publication of a TLC method for PCBs by Mulhern (Muihern 1968, Muihern et al. 1971), several researchers have used TLC to measure PCBs in various matrices. Methods have been reported by Willis and Addison (1972) for the analysis of Aroclor mixtures, by Piechalak (1984) for the analysis of soils, and by Stahr (1984) for the analysis of PCB containing oils. Even with a densitometer to measure the intensity of the spots, TLC is not generally considered quantitative. Order-of-magnitude estimates of the concentration are certainly obtainable, but the precision and accuracy probably do not approach that of the gas chromatographic methods. 42 ------- A spill site sample extract will probably need to be cleaned up before TLC analysis. Levine et al. (1983) have published a comparison of various cleanup procedures. Stahr (1984) has compared the Levine sulfuric acid cleanup to a SepPak® C 18 cleanup method. Different TLC techniques have been used to improve the sensitivity and selectivity of the method. Several researchers have reported that the use of reverse-phase TLC (C 18 -bonded phase) achieves a better separation of PCBs from interferences (DeVos and Peet 1971, DeVos 1972, Stalling and Huckins 1973, Brinkman et al. 1976). Koch (1979) has reported an order of magnitude improvement in the PCB limit of detection through use of circular TLC. The two most common methods of visualization are fluorescence (Kan et al. 1973, Ueta et a]. 1974) and reaction with AgNO 3 followed by UV irradiation (DeVos and Peet 1971, DeVos 1972, Kawabata 1974, Stahr 1984). No direct comparison of the performance of TLC with other techniques for analysis of samples from spill sites has been made. Two studies (Bush et al. 1975, Collins et al. 1972) compared TLC and GC/ECD. In both studies, the PCB values obtained were comparable. However, the study by Bush et al. indi- cated that the TLC results were generally lower than GC/ECD. 3. Total Organic Halide Analyses Total organic halide analysis can be used to estimate PCB concen- trations for guiding field work, but is not appropriate for verification or enforcement analyses. A total organic halide analysis indicates the presence of chlorine and sometimes the other halogens. Many of the techniques also detect inorganic chlorides (e.g., sodium chloride; common table salt). The reduction of organochlorine to free chloride ion with metallic sodium can be used for PCB analysis. The free chloride ions can be then detected calori- metrically (Chlor-N-Oil®) or by a chloride ion-specific electrode (McGraw- Edison). The performance of these kits has not been tested with any matrix other than mineral oil. X—ray fluorescence (XRF) has also been studied as a PCB screening technique (McQuade 1982, Schwalb and Marquez 1982). D. Selection of Appropriate Methods 1. Criteria for Selection The primary criterion for an enforcement method is that the data be highly reliable (i.e., they are legally defensible). This does not necessarily imply that the most exotic, state-of-the-art methods be employed; rather that the methods have a sound scientific basis and validation data to support their use. Many other criteria also enter into selection of a method, including accuracy, precision, reproducibility, comparability, consistency across ma- trices, availability, and cost. For PCB spills, it is assumed that the spills will be relatively fresh and therefore that PCB mixtures will generally resemble those in com- mercial products (i.e., Aroclor®). It is further assumed that, for most of the matrices likely to be encountered, the levels of interferences will be relatively low. 43 ------- 2. Selection of Instrumental Techniques Based upon the above criteria and assumptions, either GC/ECD or GC/MS should provide suitable data. Since GC/ECD is included in more stan- dard methods and since the technique is more widely used, it appears to be the technique of choice. The primary methods recommended below are all based on GC/ECD instrumental analysis. Some of the secondary and confirmatory tech- niques are based on GC/EIMS. 3. Selection of Methods Ideally, a standard method would be available for each matrix likely to be encountered in a PCB spill. The matrices of concern include solids (soil, sand, sediment, bricks, asphalt, wood, etc.), water, oil, surface wipes, and vegetation. The methods for these matrices are summarized in Table 14 and discussed in detail below. A primary recommended method is given and should be used in most spill instances. The secondary method may be useful for con- firmatory analyses, or where the situation (e.g. , high level of interferences) indicates that the primary method is not applicable. a. Solids (Soil, Sand, Sediment, Bricks, Asphalt, Wood, Etc. ) EPA Method 8080 from SW-846 (USEPA 1982e) is the primary recom- mended method. The secondary methods, Method 8250 and Method 8270, are GC/MS analogs. Method 8080 entails an acetone/hexane (1:1) extraction, a Florisil column chromatographic cleanup, and a GC/ECD instrurpental determination. A total area quantitation versus Aroclor standards is specified. No qualitative criteria are supplied. A detection limit of 1 pg/g is prescribed. No valida- tion data are available. Bulk samples (bricks, asphalt, wood, etc.) should be readily extractable using a Soxhiet extractor according to EPA Method 8080 (USEPA 1982e). The sample must be crushed and subsampled to ensure proper solvent contact. b. Water EPA Method 608 (USEPA 1984e) is recommended as the primary method. This is one of the “priority pollutant” methods and involves extrac- tion of water samples with dichlorornethane. An optional Florisil column chromatographic cleanup and also an optional sulfur removal are given. Sam- ples are analyzed by GC/ECD and quantitated against the total area of Aroclor standards. No qualitative criteria are given. This method has been exten- sively validated and complex recovery and precision equations are given in the method for seven Aroclor mixtures. The average recovery is about 86% and average overall precision about ± 26%. The average recovery and precision for the more common Aroclors (1242, 1254, and 1260) are about 78% and ± 26%, respectively. Detection limits are not given in the current version (USEPA 1984a), although they were listed as between 0.04 and 0.15 ig/L for the seven Aroclor mixtures listed as priority pollutants in the method validation study (Millar et al. 1984). 44 ------- Table 14. Summary of Recommended Analytical Methods Primary method (GC/ECD) Secondary method Matrix Designation Reference Designation GC detector Reference Solids 8080 USEPA 1982e 8250, 8270 MS USEPA 1982e Water 608 (JSEPA 1984a 625 MS USEPA 1984b Oil “oil” USEPA 1931a; “oil” MS USEPA 1981a; Bellar and Bellar and Lichtenberg, Lichtenberg, 1981 1981 Surface Hexane extrac- None Hexane extrac- MS None wipes tion/608 tion/625 Vegetation AOAC (29) AOAC 1980a None None None ------- c. Oils Spilled oil samples should be analyzed according to an EPA method (Bellar and Lichtenberg 1981). The method is written for transformer fluids and waste oils, but should also be applicable to other similar oils such as capacitor fluids. In this method, samples are diluted by an appro- priate factor (e.g. , 1:1000). Six optional cleanup techniques are given. The sample may be analyzed by GC/ECD as the primary method. Secondary instru- mental choices, also presented in the method, are GC/HECD, GC/MS, and capil- lary GC/MS. PCBs are quantitated by either total areas or the Webb-McCall (1973) method. No qualitative criteria are given. QC criteria are given. A detection limit of 1 mg/kg is stated, although it is highly dependent on the amount of dilution required. An interlaboratory validation study (Sonchik and Ronan 1984) indicated 81 to 126% recoveries for different PCB mixtures, with an average of 97% for Aroclors 1242, 1254, and 1260, as measured by ECD. The overall method precision ranged from ± 11 to ± 55%, with an average of ± 12% for Aroclors 1242, 1254, and 1260. The method validation statistics were presented in more detail as regression equations. d. Surface Wipes No standard method is available for analysis of PCBs collected on surface wipes. However, since this matrix should be relatively clean and easily extractable, a simple hexane extraction should be sufficient. Samples should be analyzed according to EPA Method 608 (USEPA 1984a), except for Section 10.1 through 10.3. In lieu of these sections, the sample should be extracted three times with 25 to 50 rnL of hexane. The sample can be extracted by shaking for at least 1 mm per extraction in the’ wide-mouthed jar used for sample storage. Note that the rinses should be with hexane so that solvent exchange from methylene chloride to hexane (Section 10.7) is not necessary. This method is proposed in this document and has not been validated. e. Vegetation The AOAC (1980a) procedure for food is recommended for analysis of vegetation (leaves, vegetables, etc.). This method involves extraction of a macerated sample with acetonitrile. The acetonitrile is diluted with water and the PCBs extracted into petroleum ether. The concentrated extract is cleaned up by Florisil column chromatography by elution with a mixture of ethyl ether and petroleum ether. The sample is analyzed by GC/ECD with quantitation by total areas or individual peak heights as compared to Aroclor standards. No qualitative criteria are given. Validation studies with chicken fat and fish (Sawyer 1973) are not relevant to the types of matrices to be encountered in PCB spills. 4. Implementation of Methods Each laboratory is responsible for generating reliable data. The first step is preparation of an in-house protocol. This detailed 11 cookbook” is based on methods cited above, but specifies which options must be followed and provides more detail in the conduct of the techniques. It is essential that a written protocol be prepared for auditing puprposes. 46 ------- Each laboratory is responsible for generating validation data to demonstrate the performance of the method in the laboratory. This can be done before processing of samples; however, it is often impractical. Valida- tion of method performance (replicates, spikes, QC samples, etc.) while ana- lyzing field samples is acceptable. Changes in the above methods are acceptable, provided the changes are documented and also provided that they do not affect performance. Some minor changes (e.g. , substitution of hexane for petroleum ether) do not generally require validation. More significant changes (e.g., substitution of a HECD for ECD) will require documentation of equivalent performance. E. Quality Assurance Quality assurance must be applied throughout the entire monitoring program including the sample planning and collection phase, the laboratory analysis phase, and the data processing and interpretation phase. Each participating EPA or EPA contract laboratory must develop a quality assurance plan (QAP) according to EPA guidelines (USEPA 1980). Ad- ditional guidance is also available (USEPA 1983). The quality assurance plan must be submitted to the regional QA officer or other appropriate QA official for approval prior to analysis of samples. 1. Quality Assurance Plan The elements of a QAP (U.S. EPA, 1980) include: Title page Table of contents Project description Project organization and responsibility QA objectives for measurement data in terms of precision, ac- curacy, completeness, representativeness, and comparability Sampl ing procedures Sample tracking and traceability Calibration procedures and frequency Analytical procedures Data reduction, validation and reporting Internal quality control checks Performance and system audits Preventive maintenance Specific routine procedures used to assess data precision, accuracy and completeness Corrective action Quality assurance reports to management 47 ------- 2. Quality Control Each laboratory that uses this method must operate a formal quality control (QC) program. The minimum requirements of this program consist of an initial and continuing demonstration of acceptable laboratory performance by the analysis of check samples, spiked blanks, and field blanks. The labora- tory must maintain performance records which define the quality of data that are generated. The exact quality control measures will depend on the laboratory, type and number of samples, and client requirements. The QC measures should be stipulated in the QA Plan. The QC measures discussed below are given for example only. Laboratories must decide on which of the measures below, or additional measures, will be required for each situation. a. Protocols Virtually all of the available PCB methods contain numerous options and general instructions. Effective implementation by a laboratory requires the preparation of a detailed analysis protocol which may be followed unambiguously in the laboratory. This document should contain working instruc- tions for all steps of the analysis. This document also forms the basis for conducting an audit. b. Certification and Performance Checks Prior to the analysis of samples, the laboratory must define its routine performance. At a minimum, this must include demonstration of acceptable response factor precision with at least three replicate analyses of a calibration solution; and analysis of a blind QC check sample (e.g. , the response factor calibration solution at unknown concentration submitted by an independent QA officer). Acceptable criteria for the precision and the ac- curacy of the QC check sample analysis must be presented in the QA plan. Ongoing performance checks should include periodic repetition of the initial demonstration or more elaborate measures. More elaborate mea- sures may include control charts and analysis of QA check samples containing unknown PCBs, and possibly with matrix interferences. c. Procedural QC The various steps of the analytical procedure should have qual- ity control measures. These include, but are not limited to, the following: Instrumental Performance : Instrumental performance cri- teria and a system for routinely monitoring the performance should be set out in the QA Plan. Corrective action for when performance does not meet the criteria should also be stipulated. 48 ------- Qualitative Identification : Any questionable results should be confirmed by a second analytical method. A least 10% of the identifications, as well as any questionable results, should be confirmed by a second analyst. Quantitation : At least 10% of all calculations must be checked. The results should be manually checked after any changes in com- puter quantitation routines. d. Sample QC Each sample and each sample set must have QC measures applied to it to establish the data quality for each analysis result. The following should be considered when preparing the QA plan: Field Blanks : Field blanks are analyzed to demonstrate that the sample collection equipment has not been cqntaminated. A field blank may be generated by using the sampling equipment to collect a blank sample (e.g. , using the water sampling equipment to sample laboratory reagent grade water) or by extracting the sampling equipment (e.g., extracting a sheet of filter paper from the lot used to collect wipe samples). A field blank must be collected and analyzed for each type of sample collected. Replicate Samples : One sample from each batch of 20 or fewer will be analyzed in triplicate. The sample is divided into three rep- licate subsamples and all these subsamples carried through the analytical procedure. The results of these analyses must be comparable within the limits required for spiked samples. Analysis of Spiked Samples : The sensitivity and re- producibility must be demonstrated for any method used to report verification data. This can be done by analyzing spiked blanks near the required detec- tion limit. To demonstrate the ability of the method to reproducibly detect the spiked sample, one or more spiked samples should be analyzed in at least triplicate for each group of 20 or fewer samples within each sample type col- lected. Samples will be spiked with a PCB mixture similar to that spilled (e.g., Aroclor 1260). Example concentrations are: Matrix Spike Level Soil, etc. 10 pg/g (10 ppm) Water 100 pg/L (100 ppb)) Wipes 100 pg/wipe (100 pg/100 cm 2 ) Quantitative techniques must detect the spike level within ±30% for all spiked samples. 49 ------- e. Sample Custody As part of the Quality Assurance Plan, the chain-of-custody protocol must be described. A chain-of-custody provides defensible proof of the sample and data integrity. The less rigorous sample traceability docu- mentation merely provides a record of when operations were performed and by whom. Sample traceability is not acceptable for enforcement activities. Chain-of-custody is required for analyses which may result in legal proceedings and where the data may be subject to legal scrutiny. Chain-of-custody provides conclusive written proof that samples are taken, transferred, prepared, and analyzed in an unbroken line as a means to maintain sample integrity. A sample is in custody if: - It is in the possession of an authorized individual; - It is in the field of vision of an authorized individual; - It is in a designated secure area; or - It has been placed in a locked container by an authorized individual. A typical chain-of-custody protocol contains the follow- ing elements: 1. Unique sample identification numbers. 2. Records of sample container preparation and integrity prior to sampling. 3. Records of the sample collection such as: - Specific location of sampling. - Date of collection. - Exact time of collection. - Type of sample taken (e.g., air, water, soil). - Initialing each entry. - Entering pertinent information on chain-of- custody record. - Maintaining the samples in one’s possession or under lock and key. - Transporting or shipping the samples to the analysis laboratory. 50 ------- - Filling out the chain-of-custody records. — The chain—of-custody records must accompany the samples. 4. Unbroken custody during shipping. Complete shipping records must be retained; samples must be shipped in locked or sealed (evidence tape) containers. 5. Laboratory chain-of-custody procedures consist of: - Receiving the samples. — Checking each sample for tampering. - Checking each sample against the chain-of-custody records. - Checking each sample and noting its condition. - Assigning a sample custodian who will be responsible for maintaining chain-of-custody. - Maintaining the sign—offs for every transfer of each sample on the chain—of-custody record. - Ensuring that all manipulations of the sample are duly recorded in a laboratory notebook along with sample number and date. These manipulations will be verified by the program manager or a designee. F. Documentation and Records Each laboratory is responsible for maintaining complete records of the analysis. A detailed documentation plan should be prepared as part of the QAP. Laboratory notebooks should be used for handwritten records. Digi- tal or other GC/MS data must be archived on magnetic tape, disk, or a similar device. Hard copy printouts may also be kept if desired. Hard copy analog data from strip chart recorders must be archived. QA records should also be retai ned. The documentation must completely describe how the analysis was performed. Any variances from a standard protocol must be noted and fully described. Where a procedure lists options (e.g., sample cleanup), the op- tion used and specifics (solvent volumes, digestion times, etc.) must be stated. The remaining samples and extracts should be archived for at least 2 months or until the analysis report is approved by the client organization (whichever is longer) and then disposed unless other arrangements are made. 51 ------- The magnetic disks or tapes, hard copy chromatograms, hard copy spectra, quan- titation reports, work sheets, etc. , must be archived for at least 3 years. All calculations used to determine final concentrations must be documented. An example of each type of calculation should be submitted with each verifi- cation spot. G. Reporting Results Results of analysis will normally be reported as follows: Matrix Reporting Units Soil, etc. pg PCB/g of sample (ppm) Water mg PCB/L of sample (ppm) Surfaces (wipes) pg PCB/wipe (pg PCB/100 cm 2 ) In some cases, the results are to be reported by homolog. In this case, 11 values are reported per sample: one each for the 10 homologs and one for the total. Some TSCA analyses require reporting the results in terms of resolvable gas chromatographic peak (U.S. EPA, 1982c, 1984e). In these cases, the number of results reported equals the number of peaks observed on the chromatogram. These analyses are generally associated with a regulatory cutoff (e.g., 2 pg/g per resolvable chrornatographic peak (U.S. EPA, 1982c, 1984). In these cases it may be sufficient, depending on the client organi- zation’s request, to report only those peaks which are above the regulatory cutoff. Even if an Aroclor is used as the quantitation standard, the re- suits are never to be reported as “pg Aroclor®/g sample.” TSCA regulates all PCBs, not merely a specific commercial mixture. V. REFERENCES Albro PW. 1979. Problems in analytic methodology: sample handling, extrac- tion, and cleanup. Ann NY Acad Sci 320:19-27. American National Standards Institute, Inc. 1974. American national standard guidelines for handling and disposal of capicator- and transformer-grade as- karels containing polychlorinated biphenyls. ANSI C107.1-1974. New York, NY. American Society for Testing and Materials. 1980. Standard method for rapid gas chromatographic estimation of high boiling homologues of chlorinated bi- phenyls for capacitor askarels. ANSI/ASTM 0 3303-74 (Reapproved 1979). In: Annual book of ASTM standards, Part 40. Philadelphia, Pennsylvania, pp. 870-876. American Society for Testing and Materials. 1981a. Standard method for poly- chlorinated biphenyls (PCBs) in water. 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