Hazard Ranking System Issue Analysis: Consideration of Contaminant Concentration MITRE ------- Hazard Ranking System Issue Analysis: Consideration of Contaminant Concentration Thomas F. Wolfinger June 1987 MTR-86W40 SPONSOR: U.S. Environmental Protection Agency CONTRACT NO.: EPA-68-01-7054 The MITRE Corporation Civil Systems Division 7525 Colshire Drive McLean, Virginia 22102-3481 ------- Department Approval: MITRE Project Approval: . JUk. ii ------- ABSTRACT This report examines the issue of the extent to which concentration data can play an increased role within the Hazard Ranking System (HRS) for the evaluation of uncontrolled waste sites. The report examines general limitations in concentration data, limitations arising from programmatic constraints in the site evaluation program, and limitations arising during the data development process. The report concludes that there is a large number of important limitations that restrict the utility of concentration data in the HRS. The report also examines, to the limited extent possible, the potential costs of developing representative concentration data at uncontrolled waste sites. Several options for increasing the role of concentration data in the HRS are described. These options were designed within the context of limitations in the availability and extent of concentration data. Suggested Keywords: Superfund, Hazardous ranking, Hazardous waste, Concentration, Hazardous constituents. iii ------- ACKNOWLEDGMENT The author would like to acknowledge the contributions of John A. Cioffi of the Chemical and Biological Systems Department of the MITRE Corporation. Mr. Cioffi's preliminary work on the issue of the use of concentration data in the Hazard Ranking System formed the basis for many of the ideas, examination, and conclusions contained in this report. iv ------- TABLE OF CONTENTS Page LIST OF ILLUSTRATIONS vii LIST OF TABLES vlii 1.0 INTRODUCTION ! 1.1 Background 1 1.2 Issue Description 3 1.3 Scope and Approach of Analysis 5 1.4 Organization of the Report 6 2.0 GENERAL LIMITATIONS IN CONCENTRATION DATA 9 3.0 LIMITATIONS ARISING FROM PROGRAM CONSTRAINTS 13 3.1 Funding Constraints 13 3.2 Time Constraints 14 3.3 Variation in Levels of Expertise 14 3.4 Quality Control and Quality Assurance 15 4.0 LIMITATIONS IN CONCENTRATION DATA QUALITY 17 4.1 Spatial Variation 18 4.1.1 Environmental Data 20 4.1.2 Wastes 45 4.2 Temporal Variation 48 4.2.1 Environmental Data 49 4.2.2 Wastes 56 4.3 Limitations in the Data Development Process 57 4.3.1 Sampling 58 4.3.2 Handling 75 4.3.3 Analysis 78 4.3.4 Interpretation 90 5.0 COSTS 93 5.1 Problems in Estimating Costs 93 5.2 Media 96 5.3 Contaminants 100 ------- TABLE OF CONTENTS (Concluded) 5.4 Number of Sampling Locations 5.5 Number of Samples Per Location HI 5.6 Unit Sampling, Handling, and Analysis Costs H4 5.7 Illustrative Example 117 6.0 SUMMARY OF PRECEDING DISCUSSIONS AND IMPLICATION H9 FOR THE HRS 7.0 OPTIONS FOR EMPLOYING CONCENTRATION DATA 123 7.1 Basic Philosophy 123 7.2 Benchmarks 126 7.3 Options 127 7.3.1 Options in the HRS Release Category 127 7.3.2 Options in the HRS Waste Characteristics 131 Category 7.3.3 Options in the Targets Category 142 8.0 OVERALL CONCLUSIONS AND RECOMMENDATIONS 147 9.0 REFERENCES AND BIBLIOGRAPHY 153 APPENDIX A - COMMENTS ON THE HRS RELATED TO HAZARDOUS 177 WASTE CONCENTRATIONS APPENDIX B - DATA QUALITY 183 vi ------- LIST OF ILLUSTRATIONS Figure Number Page 1 DCE Profile at Site in February 1984 23 2 PCE Profile at Site in February 1984 24 3 Thomas Solvent Ground Water Total VOC 26 Concentration Profile, August 1984 4 Vertical Distribution of Representative 27 Organic Compounds From Upgradient and Dowugradient Multilevel Monitoring System 5 Vertical Distribution of Representative 28 Inorganic Compounds From Upgradient and Downgradient Multilevel Monitoring System 6 Vertical Nitrate and Dissolved Oxygen 32 Distribution in Shallow Sandy Aquifer (after Hendry et al., 1983) 7 Range and Mean for Vinyl Chloride Monitoring 40 Near BKK Landfill, West Covina, California 8 Isoarea Map of Kriging Estimate of Lead 43 Concentrations (ug/g) in Soil 9 Fluctuations of Nitrate Concentrations in 51 Water from Individual Shallow Wells Over Time 10 Change in Shallow Plume Over Time, as Measured 53 by Em Conductivity 11 Water Quality Fluctuations with Time of Pumping 67 VI1 ------- LIST OF TABLES Table Number 1 Horizontal Variation in Ground Water 30 Contamination Biscayne Aquifer/Dade County, Florida 2 Vertical Variation in Ground Water 31 Contamination Biscayne Aquifer/Dade County, Florida 3 Spatial/Temporal Variability in Atmospheric 34 Benzene Concentrations: Kin-Buc Landfill (1976) 4 Spatial/Temporal Variability in Atmospheric 35 Carbon Tetrachloride Concentrations: Kin-Buc Landfill (1976) 5 Spatial/Temporal Variability in Atmospheric 36 Chloroform Concentrations: Kin-Buc Landfill (1976) 6 Ranges of Landfill Gas Concentrations at BKK 38 Landfill 7 Coefficients of Variations (%) for Soil 41 Parameters Reported in Mason (1983) 8 Examples of Spatial Variation in Surface Water 44 Contaminant Concentrations 9 Spatial Variability in Waste Concentration 47 10 Concentrations of Total Organic Compounds in 52 Water from Four Long Island, New York Wells Over a One-Year Period (1977-1978) 11 Potential Sources of Bias in Sampling Ground 63 Water 12 Sampling Methods for Airborne Organics 71 13 Sampling Equipment for Particular Waste Types 76 viii ------- LIST OF TABLES (Continued) Table Number Pa8e 14 RCRA Appendix VIII Compounds for Which No 80 Suitable Analytical Parameter Methodology or Standards Exist, or for Which a Surrogate Has Been Suggested as an Analyte 15 Acceptable Ranges for Precision and Accuracy 81 in the EPA Contract Laboratory Program 16 CLP Performance Evaluation Sample Results, 83 1982 17 Analysis of CLP Performance Evaluation Sample 84 Data, 1982 18 Summary of Inter-Laboratory Comparison 85 19 Summary of Inter-Laboratory Comparison 86 20 Comparison of Gas Chromatography (GC) and Gas 88 Chromatography/Mass Spectroscopy (GC/MS) Results 21 Magnitude of Laboratory Variability 89 22 Ranges of Selected Organic Contaminant 92 Concentrations in Urban Air 23 Summary of Sampling Costs 99 24 Recommended Media in Which to Sample RCRA 101 Appendix VIII Hazardous Constituents 25 Expected Confidence Intervals for a Parameter 113 Mean as a Function of Number of Samples 26 Example Representative Pre-Sampling Costs 116 Ten^Well Sampling Field 27 Hypothetical Examples of Release Category 130 Option 28 Illustrative Concentration Factor Table 133 ix ------- LIST OF TABLES (Concluded) Table Number Page 29 Hypothetical Examples of Concentration Factor 135 Option 30 Illustrative Concentration Factor 139 31 Illustrative Toxicity Factor Matrix 141 32 Illustrative Table for Evaluating Population 144 (Ground Water Pathway) 33 Illustrative Tables for Evaluating Population 145 (Air Pathway) 34 Guidance on Concentration Data Development: 149 Selections from the Literature ------- 1.0 INTRODUCTION 1.1 Background The Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) (PL 96-510) requires the President to identify national priorities for remedial action among releases or threatened releases of hazardous substances. These releases are to be identified based on criteria promulgated in the National Contingency Plan (NCP). On July 16, 1982, EPA promulgated the Hazard Ranking System (HRS) as Appendix A to the NCP (40 CFR 300; 47 FR 31180). The HRS comprises the criteria required under CERCLA and is used by EPA to estimate the relative potential hazard posed by releases or threatened releases of hazardous substances. The HRS is a means for applying uniform technical judgment regarding the potential hazards presented by a release relative to other releases. The HRS is used in identifying releases as national priorities for further investigation and possible remedial action by assigning numerical values (according to prescribed guidelines) to factors that characterize the potential of any given release to cause harm. The values are manipulated mathematically to yield a single score that is designed to indicate the potential hazard posed by each release relative to other releases. This score is one of the criteria used by EPA in determining whether the release should be placed on the National Priorities List (NPL). ------- During the original NCP rulemaklng process and the subsequent application of the HRS to specific releases, a number of technical Issues have been raised regarding the HRS. These Issues concern the desire for modifications to the HRS to further improve its capability to estimate the relative potential hazard of releases. The issues include: • Review of other existing ranking systems suitable for ranking hazardous waste sites for the NPL. • Feasibility of considering ground water flow direction and distance, as well as defining "aquifer of concern," in determining potentially affected targets. • Development of a human food chain exposure evaluation methodology. • Development of a potential for air release factor category in the HRS air pathway. • Review of the adequacy of the target distance specified in the air pathway. • Feasibility of considering the accumulation of hazardous substances in indoor environments. • Feasibility of developing factors to account for environmental attenuation of hazardous substances in ground and surface water. • Feasibility of developing a more discriminating toxicity factor. • Refinement of the definition of "significance" as it relates to observed releases. • Suitability of the current HRS default value for an unknown waste quantity. • Feasibility of determining and using hazardous substance concentration data. ------- • Feasibility of evaluating waste quantity on a hazardous constituent basis. • Review of the adequacy of the target distance specified in the surface water pathway. • Development of a sensitive environment evaluation methodology. • Feasibility of revising the containment factors to increase discrimination among facilities. • Review of the potential for future changes in laboratory detection limits to affect the types of sites considered for the NPL. Each technical issue is the subject of one or more separate but related reports. These reports, although providing background, analysis, conclusions, and recommendations regarding the technical issue, will not directly affect the HRS. Rather, these reports will be used by an EPA working group that will assess and integrate the results and prepare recommendations to EPA management regarding future changes to the HRS. Any changes will then be proposed in Federal notice and comment rulemaking as formal changes to the NCP. The following section describes the specific issue that is the subject of this report. 1.2 Issue Description It is intuitively and intellectually attractive that knowledge of the actual concentrations resulting from releases from uncontrolled waste sites should lead to better characterizations of the risks associated with the sites. The extent of (actual or potential) damage to human health or the environment caused by a release of hazardous substances is a function of dose which is, in turn, directly related 3 ------- to the concentration of the substance found at the point of exposure and the duration of time that the concentration is maintained. Thus, risk from contaminant releases is a direct function of the exposure concentrations. Individuals and organizations commenting on the MRS and its subsequent application to uncontrolled waste sites and other releases have expressed several considerations. The commenters have indicated that concentration data are needed to: 1) determine if a contaminant has been released from the site, 2) estimate the quantity of hazardous substances present at the site, and 3) determine the human and environmental threat posed by the substances at or released from the site. A more extensive review of the comments received by EPA concerning the concentration issue can be found in Appendix A. Currently, concentration data are used in the HRS to determine whether a release of contaminants has occurred, termed an "observed release". These data are also used to assist in determining the substances present at the site. The avoidance of increased reliance on concentration data to assess site risks using the HRS is based on: 1) the current role of the HRS as a screening tool, 2) shortcomings in the representativeness of concentration data, 3) the quality of data that can be collected, 4) the costs of data collection, and 5) limitations in inferring exposure concentrations from environmental and waste concentrations. ------- 1.3 Scope and Approach of Analysis Several different types of concentration data can be developed during preliminary assessments (PA) and site inspections (SI). Generically, the types of data can be grouped by media as follows: • Ground water • Surface water • Soil • Air • Wastes For the purposes of this report, the first four media are considered "environmental" media as are samples collected from those media. For example, ground water is considered an environmental medium and ground water samples are considered environmental samples. For purposes of distinction, waste samples are considered separately. A sixth medium of concern, sediments, is discussed, as applicable, under the categories of soil or wastes. Several factors determine the role that concentration data can play in any regulatory or scientific program. The primary factor is the objectives of the program. Of nearly equal importance, however, are the inherent limitations in concentration data, the programmatic constraints placed on the development of such data, and the quality of the data that can be developed in support of the program given programmatic and other constraints. The role of the data should further the achievement of the objectives within the constraints ------- posed by the quality and other limitations of the data. In the context of the HRS, the objective of the program is to develop a ranking of uncontrolled waste sites in a fashion that reflects the relative, multi-media, risks of the sites as accurately as possible within the resource and knowledge constraints of the program. The resulting list of sites is used in evaluating sites for further, more detailed, investigation. Given this objective, a thorough understanding of the limitations in concentration data is needed to define the appropriate role for concentration data in the HRS. In order to determine the appropriate role for concentration data, an examination of the limitations in concentration data developed during activities such as preliminary assessments and site inspections was undertaken. The purpose of this examination was to delineate the limitations in such data that would restrict its use in the HRS. Once the limitations were understood, options of employing concentration data within the HRS were developed. 1.4 Organization of the Report This report presents the results of an examination of the nature of concentration data developed during PAs and Sis and the results of the effort to develop options for using such data in the HRS. Sections 2, 3, and 4 discuss the limitations associated with the types of concentration data collected during site inspections as they relate to the utility of such data in the HRS. A limited discussion of the probable costs associated with developing ------- representative concentration data is presented in Section 5. Section 6 discusses the implications of data limitations for the use of concentration data in the HRS while Section 7 presents several options for using concentration data within the framework of the HRS. These options were developed to make optional use of the concentration data as warranted by limitations in the data. Ultimately, the question of which uses of concentration data are acceptable, given the limitations, must be decided by EPA. Section 8 presents the overall conclusion and recommendations of the issue analysis. A bibliography is presented in Section 9. Appendix A contains a discussion of the comments made by interested parties on the issue of using concentration data in the HRS. Appendix B contains a short discussion on the meaning of representativeness in terms of concentration data. ------- 2.0 GENERAL LIMITATIONS IN CONCENTRATION DATA A principal limitation with concentration data is that they rarely represent the concentrations to which individuals will actually be exposed. This limitation is important in assessing risk since human health risk from environmental contamination is a function of exposure concentrations; there are generally no simple relationships between overall environmental or waste concentrations and exposure concentrations. This limitation may be minimized when sampling is performed at the point of exposure, although other problems may arise when sampling "exposure" concentrations. For example, samples drawn from drinking water taps are likely to yield samples representative of exposure concentrations, although such data may suffer from interferences from nonsite-related contaminants (such as chloroform arising from water chlorination or lead from lead solder in pipes). Moreover, the technology of sampling exposure concentrations is, in some cases, not in an advanced stage of development. For example, special equipment was developed to assess personal airborne contaminant exposure during the Total Exposure Assessment Methodology (TEAM) EPA project (Wallace, 1985). A second important limitation in concentration data is that concentration data are fundamentally retrospective in nature. At best, the data represent contaminant concentrations at the sampling locations at some point in the past. This point may be a few minutes or several months in the past. As such, concentration data are ------- never totally complete. It is only with the aid of models (Including simple models that assume that conditions and concentrations will not change over time) that one can infer future concentrations from past concentrations. The importance of this limitation in terms of the utility of concentration data in the HRS depends upon the objectives for the use of the data in the HRS. If the purpose of the HRS remains to assess relative risks associated with actual or potential contaminant releases, then this limitation may be critical. The above limitations are important; however, in perform-frig risk assessments scientists have found it necessary to accommodate then. A third important limitation associated with concentration data arises from the statistical nature of concentration data. Even given a high state of quality control for a particular data set, one cannot be certain of the true concentration. Ihere is always some probability that the true contaminant concentration is significantly higher or lower than that Indicated by the data. In general, the probability that the true concentration will be significantly higher (or lower) than the estimated concentration will decrease as the representativeness of the concentration data increases. Conversely, uncertainty will increase as the degree of representativeness decreases. This is particularly important if the data set represents only a portion of the true spatial/temporal distribution of concentrations, or if it represents only one of the many spatial/temporal concentration distributions associated with the 10 ------- site due to problems of specificity, homogeneity, accuracy, and completeness. This is discussed further in Section 4. Further, the temporal limitation discussed above could act to increase the uncertainty associated with inferences associated with low levels of detected contamination. This concern is particularly important when inferring that a site poses no risk to individuals living near the site or when inferring that the site will not release contaminants (e.g., when contaminants have simply not yet been released from the site). 11 ------- 3.0 LIMITATIONS ARISING FROM PROGRAM CONSTRAINTS Several aspects of the current structure of the CERCLA preliminary assessment and site inspection (PA/SI) program limit the representativeness and utility of the concentration data developed for use in evaluating sites. The most important of these aspects are: • Funding constraints • Time constraints • Variation in levels of expertise • Current quality assurance and quality control (QA/QC) program Since the PA/SI program would likely be revised in concert with revisions to the HRS, these aspects of the program may become less limiting in the future. 3.1 Funding Constraints Currently, a site inspection cost is about 35-50 thousand dollars (Caldwell, 1986). Preliminary assessment costs are a relatively minor component of overall PA/SI costs. Some site inspections cost less than the average while others cost considerably more. Given the range of costs associated with data development (addressed in Section 5), it is certain that the availability of monetary resources will restrict the extent of the collection of concentration data at most sites. The effects of these constraints are seen in the current program, in part in the emphasis on ground water and soil sampling* and on the number of samples taken. *This emphasis also derives from a perception that ground water and soil contamination are the sources of the principal component of site risks. 13 ------- 3.2 Time Constraints A similar constraint arises from the need to inspect sites as quickly as possible to ensure that the risks from those sites requiring cleanup are mitigated as soon as possible. This, generally implicit, time constraint is reflected in the Congressional discussions on requirements for sites to be placed on the NPL, for remedial investigations to be performed, and for sites to be cleaned up by specific dates. This concern is addressed in the Superfund Amendments and Reauthorization Act of 1986 Conference Report. The Joint Conference Committee states in this report that the requirement that the HRS rank sites as accurately as possible does not require that long-term monitoring be conducted during site inspections and that the role of the HRS is to expeditiously identify sites for response actions. This time constraint restricts the duration of sampling and, together with other resource constraints, may restrict the spatial, media, and contaminant completeness of the data development effort. 3.3 Variation in Levels of Expertise A third limitation arises from the wide mix of interested parties involved in concentration data development. The PA/SI program is designed to make use of a wide range of resources available to the Federal government, State and local governments and other interested parties. The use of these resources is generally desirable for many reasons including cost and time savin 14 ------- However, three aspects of this practice are of concern if increased reliance is to be placed on concentration data. First, are the differences in the objectives for which the samples are collected. For example, some samples are collected to ensure investigator safety, utilizing measurements to support short-term acute effects risk assessments. This objective frequently results in the use of specialized sampling techniques that may not yield sufficiently reliable data to support longer-term chronic risk determinations. The second aspect of concern is the wide variation in the quality of the data developed outside of EPA. This variation results in part from variations in the level of technical expertise available to interested parties that might develop concentration data. This variation indicates the need for using trained professionals in site inspections, as indicated by Glaccum, Benson, and Noel, 1982, to ensure the representativeness of data collected. The final aspect is the degree of control that EPA can exercise over concentration data development activities in order to ensure that adequate QA/QC practices are employed by all parties collecting data to support site evaluations. Almost all of the Superfund program is implemented by the States and the degree to which EPA can ensure QA/QC for site inspections conducted by such other parties is problematic. 3.4 Quality Control and Quality Assurance A final programmatic constraint relates to potential problems in the field and laboratory quality control and quality assurance program 15 ------- that is applied to the concentration data, particularly to those data developed outside of the EPA PA/SI program. The uncertainty of data that have not been developed subject to a uniformly applied, comprehensive field and laboratory QA/QC program must be considered to be high. Increased reliance on concentration data in the HRS would require accompanying changes in the QA/QC program, especially in regard to data developed outside of EPA, to insure that the concentration data were developed properly, in all cases, to the extent possible given current capabilities. The Superfund program is not alone in requiring a high state of QA/QC for the collection of concentration data. Cooperative efforts with other organizations can help promote consistency in data collection. Other organizations emphasizing the need for concentration data QA/QC in decision making include the American Chemical Society (Keith, Lawrence H. et al., 1983), the U.S. Geological Survey (Claassen, 1982) and parts of EPA outside of the Superfund program (Scalf et al., 1981; Riggin, 1983; and Gosse et al., 1986). 16 ------- 4.0 LIMITATIONS IN CONCENTRATION DATA QUALITY The purpose of this chapter is to present a general discussion of the limitations, uncertainties, and confounding factors that affect the quality of concentration data and its utility in the HRS. Quality, as discussed in Appendix B, is determined by comparing the representativeness of a data set with the requirements for representativeness imposed by the uses to which the data will be put. The determination of what constitutes an acceptable degree of representativeness is an issue that must be resolved by the user (in this case, EPA) based on the objectives of the program and the role the data play in achieving those objectives. It is apparent in examining the literature that a large number of factors interact to affect concentration data. These factors determine the degree to which the results of a particular sampling program are representative. These factors generally fall into two categories, those reflected in "natural" variation in concentrations (i.e., arising from variation in the environmental and waste disposal processes that influence concentrations) and those of human origin that relate to errors and resulting variations in concentrations that arise during data development. A lack of knowledge of these factors and the degree to which they affect an individual data set increases the uncertainty associated with that data set, limiting its usefulness. These factors include, for example, contamination of well samples by materials used in well construction, temporal 17 ------- variations in atmospheric characteristics inducing variations in contaminant concentrations, safety considerations in sampling sealed drums, spatial variations in soil contaminant concentrations caused by differential deposition patterns, gaps in knowledge of how to analyze nonnormal data, and gaps in technologies and procedural standards for determining sample concentrations for many contaminants of concern. A large amount of information has been published concerning such confounding factors (e.g., Barcelona, 1983; Driscoll, 1986; Fetter, 1983; Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Gillham et al., 1983; Keith et al., 1983a and I983b; Scalf et al., 1981; Sgambat and Stedinger, 1981; Weber and Mims, 1981; and Zachowski and Borgianini, 1984). Procedures to partially alleviate the effects of these factors have been developed in many cases. A truly comprehensive discussion of these factors in all five of the media of interest is beyond the scope of this paper. This chapter deals with an overview of these factors and their implications for limiting the use of concentration data in the MRS. The factors play greater or lesser roles depending on the media to be evaluated. The chapter is divided into three sections, the first two address spatial and temporal variability, respectively. The third section addresses limitations in the data development process. 4.1 Spatial Variation Spatial variation is the first of the two natural sources of variation in concentration data. Spatial variation is defined as 18 ------- the variation in a parameter of interest (e.g., contaminant concentrations) seen at a given point in time, between different locations on or near a site. It is important to note that both horizontal and vertical spatial variation are important at many sites. Spatial variation in contaminant concentrations is three dimensional and is induced by several environmental factors and the spatial variability of these factors. Factors of particular importance include transport media characteristics (e.g., for ground water, the direction of flow, stability, porosity, and soil clay content), contaminant and waste characteristics (e.g., for air, the physical state, vapor pressure, solubility, and molecular weight); and site characteristics (such as location and containment of deposited materials). These characteristics may act singly to induce variations or may interact, such as in the case of photodegradation. Spatial variation is a critical factor in determining the number, density, and location of sampling points. Generally, those sites expected to have a high degree of spatial variability would require a greater number of sampling locations to ensure a given level of representativeness in the data. Conversely, spatially homogeneous sites (those with a low degree of spatial variability) would require fewer sampling locations. As might be expected, few sites are spatially homogeneous in any of the five media of concern. 19 ------- A major problem in dealing with spatial variation is determining the degree of spatial variability. It is necessary to know the state of variability to determine how many samples must be collected to obtain an adequate representation of the range and arithmetic mode of site concentrations. A determination of the degree of homogeneity itself may require extensive sampling. 4.1.1 Environmental Data This section discusses examples from the literature illustrating the extent and importance of spatial variation in the four environmental media. Ground Water. Several authors indicate that there is a fairly high degree of spatial variability in ground water conditions and contaminant concentrations (e.g., Berg, 1982; Driscoll, 1986; Gillham et al., 1983; Gosse et al., 1986; McKown, Schalla, and English, 1984; Nazar, Prieur, and Threlfall, 1984; Quinn, Wittmann, and Lee, 1985; Sgambat and Stedinger, 1981; and U.S. Environmental Protection Agency, 1977 and 1985b). Many indicate that spatial variability is most evident in the vertical direction (Driscoll, 1986; Singh et al., 1984; and U.S. Environmental Protection Agency, 1985b). As noted by Sgambat and Stedinger (1981). ground water is not well mixed, in any dimension. Among the parameters that vary spatially and might affect ground water contaminant concentrations are (McKown, Schalla, and English 1984): 20 ------- • Horizontal and vertical conductivity • Coefficient of storage • Porosity • Specific yield and retention Additional parameters include hydraulic gradient and rate of transport, contaminant chemical properties, geochemical and biological properties of the aquifer matrix, and discharge/recharge parameters. Of particular importance are discontinuities in soil strata, particularly with regard to fractures (Gillham et al., 1983 and Gosse et al., 1986). It is important to note that contaminants do not necessarily move in the same direction and at the same speed as the ground water (Aller et al., 1985). A final, critical set of parameters that affect the spatial distribution of contaminant concentrations are the location and release characteristics of the waste site and any other possible contamination sources (such as other, unrelated sites). The extent of spatial variability in ground water contaminant concentrations can be seen in studies by Sgambat and Stedinger (1981); Quinn, Wittmann, and Lee (1985); Nazar, Prieur, and Threlfall (1984); Singh et al. (1984); and Gillham et al. (1983). For example, Sgambat and Stedinger (1981) reproduced a table in their article showing the results of an analysis of variance (ANOVA) conducted on observed nitrate concentrations in shallow wells located on Long Island, New York. The ANOVA indicates that 70 percent of 21 ------- the total variation in nitrate concentrations could be accounted for by well-to-well (or spatial) variation. About 27 percent could be accounted for by within-well variation (temporal and other well- specific variation) while only about 3 percent was considered to be due to measurement error. The authors believe that the spatial variation in concentrations was due to spatial variation in the principal sources of nitrate contamination: cesspool leachate and lawn fertilizers. Quinn, Wittmann, and Lee (1985) analyzed the spatial distribution of contamination at the Verona Well Field near Battle Creek, Michigan as part of a CERCLA remedial investigation (RI). Figures 1 and 2, illustrate the spatial distribution of 1,2- dichloroethene (DCE) and tetrachloroethylene (or perchloroethylene, PCE) in the area of the well field. The study identified three probable sources of DCE and PCE: two Thomas Solvent facilities and the railroad marshalling yard. DCE concentrations ranged from over 10,000 near one of the sources, declining to 50 ug/1 and below within the well field. Environmental PCE concentrations arising from the Thomas Solvent facilities (the southern PCE plume) have a much smaller range, from 50 to 100 ug/1 near the source, and below detection limits further out. Concentrations in the eastern PCE plume range from about 100 ug/1 to below detection limits within the boundaries of the well field. The authors stress that the two wells immediately downgradient of the facility (source) showed no 22 ------- Thomas. Solvent Annex Thomas Solvent Raymond Road 0 300 600 Scale In Feet Note: Contour lines show 1,2 DCE concentration pg/l (Dashed where inferred) Source: Quinn, Witman, and Lee, 1985. FIGURE 1 DCE PROFILE AT SITE IN FEBRUARY 1984 23 ------- Thomas Solvent , Raymond Road lKf'\$ 0 300 600 Scale In Feet Note: Contour lines show PCE concentrations in ?g/l (Dashed where inferred) Source: Qulnn, Wltman, and Lee, 1985. FIGURE 2 PCE PROFILE AT SITE IN FEBRUARY 1984 24 ------- contanilnation above the detection limit. Presumably, these two wells missed the plume, indicating the importance of vertical variability. The importance of hydraulic and chemical characteristics in determining contaminant spatial distributions is also evident in this study. The authors indicate that the probable causes for the differences in spatial distributions of concentrations between the DCE plume and the southern PCE plume are: 1) the higher retardation factor for PCE and 2) the fact that DCE is a transformation product of PCE. Wide variation in the concentrations in the eastern plume is indicated in Figure 2, a map of the railroad yard PCE concentrations. Contaminant concentrations ranged from 1,000 to 10 ug/1 within a distance of less than 400 feet. A wide variation in ground water contaminant concentrations is also indicated by the spatial distribution of soil gas VOC concentrations, illustrated in Figure 3. Within a distance of less than 200 feet, soil gas VOC concentrations range over 5 orders of magnitude. The potential for variability in the vertical dimension is further evident from the concentration profiles presented in Nazar, Prieur, and Threlfall (1984) (Figures 4 and 5). These samples were taken in the area of an abandoned chemical plant that produced specialty intermediates. There is a large degree of vertical variation in the concentrations of both organic and inorganic contaminants. For example, chlorobenzene ranges from about 0.01 mg/1 25 ------- \ 7 / RAYMOND RD m 30 50 1—(— Scale In Feet 100 Note: Contour lines show total groundwater VOC concentrations in Source: Quinn, Witman, and Lee, 1985. FIGURE 3 THOMAS SOLVENT GROUND WATER TOTAL VOC CONCENTRATION PROFILE, AUGUST 1984 26 ------- 0.0 - 10.0 - 50.0 -1— 001 Water Table jenac ^ oichloroethane Chlorobenzene Upgradient I I I I I I I I I I I I I I I I I I I i I I I I I I I 0.10 1.00 Concentration (mg./L) 100.00 Water Table 40.0 - 50.0 - Downgradlent 0.01 Source: Nazar, Prleur, and Threlfall, 1984. 100 Concentration (mg./L) 100.00 FIGURE 4 VERTICAL DISTRIBUTION OF REPRESENTATIVE ORGANIC COMPOUNDS FROM UPGRADIENT AND DOWNGRADIENT MULTILEVEL MONITORING SYSTEM 27 ------- 30.0 - 50.0- Upgradlent I I I I I I I ll X So" I I I I I I I I 100 Concentration (mgJL) 1000 10.000 0.0 - 10.0 - 0 10 Source. Nazar, Prleur, and Threltall, 1984 100 Concentration (mg/L) 10,000 FIGURE 5 VERTICAL DISTRIBUTION OF REPRESENTATIVE INORGANIC COMPOUNDS FROM UPGRADIENT AND DOWNGRADIENT MULTILEVEL MONITORING SYSTEM 28 ------- (at a depth of less than 10 feet) to about 10 mg/1 (at a depth of between 200 and 300 feet). Iron concentrations also exhibit strong variations ranging from about 20 mg/1 at less than 100 feet, reaching a maximum of over 5,000 mg/1 at between 100 and 200 feet, and returning to a concentration below 100 mg/1 at a depth of about 400 feet. Nazar, Prieur, and Threlfall believe that the overall vertical distributions of the upgradient and downgradient contaminant concentrations indicate the presence of multiple sources. Sometimes when specific sources of contamination are unknown and/or multiple sources are present, a large area, such as an aquifer can be designated as a site. Such sites can have marked spatial variation. Both horizontal and vertical variations in ground water contaminant concentrations were found in a study of contamination in the Biscayne aquifer in Florida (Singh et al., 1984). As indicated in Tables 1 and 2, contaminant concentrations varied by up to two orders of magnitude between locations within the aquifer and between the three depths sampled. In another aquifer, significant vertical variation in nitrate and dissolved oxygen concentrations was observed by Gillham et al., 1983 (Figure 6). Air. Overall, the atmosphere is the most variable medium of concern associated with uncontrolled waste sites. Atmospheric conditions and contaminant concentrations can change significantly within the space of seconds and within distances measured in feet. Contaminant concentrations can vary over orders of magnitude, in 29 ------- TABLE 1 HORIZONTAL VARIATION IN GROUND WATER CONTAMINATION BISCAYNE AQUIFER/DADE COUNTY, FLORIDA (ug/1) Area Hialeah Upper Miami Springs Lower Miami Springs Airport (36th Street) 58th Street Landfill Unsewered Industrial Area Mean Total VOC 57 33 20 10 6.2 1.1 Mean Chloride 23 17 8.7 3.5 0.31 0.25 Trans-1, 2- dichloroethene 28 7.3 3.6 1.1 0.53 0.25 Source: Singh et al., (1984). 30 ------- TABLE 2 VERTICAL VARIATION IN GROUND WATER CONTAMINATION BISCAYNE AQUIFER/BADE COUNTY, FLORIDA (ug/1) Parameter Vinyl Chloride Trans-1, 2-Dichloroethene Total VOCs Upper Level 0.35 0.36 7.8 Middle Level 12 6.7 22 Lower Level 10 4.3 19 Source: Singh et al., (1984). 31 ------- 0.0 CD TD c 2.0 - 4.0 - 1 6.0- m ZL. Q. 8.0 10.0 N03 -(mgL-i) 10 20 1 DO (mgL1) 10 20 Water Table • Location of Sampling points • Measured Data Note: The dashed-lines represent the weighted average concentrations Source: Gillham et al., 1983. FIGURE 6 VERTICAL NITRATE AND DISSOLVED OXYGEN DISTRIBUTION IN SHALLOW SANDY AQUIFER (after Hendry et al., 1983) 32 ------- both time and space as the wind direction shifts and plumes meander. Spatial variation in the atmosphere has been identified as important in determining concentrations by several authors including Gosse et al. , 1986; Riggin, 1983; and Zachowski and Borgianini, 1984. Spatial variability in atmospheric contaminant concentrations arises from three different sources: variation in the atmosphere itself (e.g., wind speed, wind direction, and stability), variation in locations and release characteristics of contaminant sources, and effects of terrain. Each of these sources of variation play an important role in determining the spatial (and temporal) distribution of atmospheric contaminant concentrations. The extent of spatial variation in atmospheric contaminant concentrations is illustrated by sampling data reported in Pellizzari, 1978 (Tables 3 through 5). These data are abstracted from an extensive set of sample data based on several days of sampling conducted on and near the Kin-Buc Landfill in New Jersey. Analyses were performed for a large number of organic contaminants. The data presented in this report are for benzene, carbon tetrachloride, and chloroform. Temporal average (mean) benzene concentrations varied by more than a factor of 3 3 2 (13 ug/m to 30 ug/m ) between locations within a one-mile radius of the site. Individual benzene concentrations varied by over an order of magnitude off-site. The highest detected on-site concentration (July 1, 191,000 ng/m ) was nearly 30 times the lowest detected off-site concentration taken at the same time (6,875 ng/m ) . 33 ------- TABLE 3 SPATIAL/TEMPORAL VARIABILITY IN ATMOSPHERIC BENZENE CONCENTRATIONS: KIN-BUG LANDFILL (1976) (ng/m3) Locations* Date 6-29 6-30 7-1 Mean RSD Time** 1207 1607 1029 1457 1006 1425 Tower Marina 20,343 7,718 NS trace 15,969 10,156 13,457 42% Meadow Road 93,750 14,093 5,906 NS NS 6,875 30,156 141% East NS 10,656 NS NS 7,000 27,343 14,500 72% On-Site NS NS NS NS trace 191,000 NA *Locations: • Tower Marina is approximately 1 mile from the site at a direction of 255 degrees. • Meadow Road is approximately 0.25 miles from the site at a direction of 345 degrees. • The East location is approximately 0.1 miles from the site at a direction of 40 degrees. **Approximate time sampling began at each location. NA: Not applicable. NS: Not sampled. RSD: Relative standard deviation (or coefficient of variation); the ratio of the sample standard deviation to the sample mean. Source: Adapted from Pellizzari, 1978. 34 ------- TABLE 4 SPATIAL/TEMPORAL VARIABILITY IN ATMOSPHERIC CARBON TETRACHLORIDE CONCENTRATIONS: KIN-BUG LANDFILL (1976) (ng/nr) Locations* Date 6-29 6-30 7-1 Mean RSD Time** 1207 1607 1029 1457 1006 1425 Tower Marina ND 12,687 NS 1,127 ND 3,125 5,646 109% Meadow Road ND 13,687 trace NS NS 625 7,156 129% East NS 7,250 NS NS ND 7,000 7,125 2% On-Site NS NS NS NS ND 10,600 NA *Locations: • Tower Marina is approximately 1 mile from the site at a direction of 255 degrees. • Meadow Road is approximately 0.25 miles from the site at a direction of 345 degrees. • The East location is approximately 0.1 miles from the site at a direction of 40 degrees. **Approximate time sampling began at each location. NA: Not applicable. ND: Not detected. NS: Not sampled. RSD: Relative standard deviation (or coefficient of variation); the ratio of the sample standard deviation to the sample mean. Source: Adapted from Pellizzari, 1978. 35 ------- TABLE 5 SPATIAL/TEMPORAL VARIABILITY IN ATMOSPHERIC CHLOROFORM CONCENTRATIONS: KIN-BOC LANDFILL (1976) (ng/m3) Locatioas* Date 6-29 6-30 7-1 Mean RSD Time** 1207 1607 1029 1457 1006 1425 Tower Marina 6,389 1,999 NS 186 17,222 944 5,348 132% Meadow Road ND trace 12,333 NS NS 2,500 7,416 94% East NS trace NS NS 8,334 260 4,297 133% On-Site NS NS NS NS 19,444 27,200 23,322 24% *Locations: • Tower Marina is approximately 1 mile from the site at a direction of 255 degrees. • Meadow Road is approximately 0.25 miles from the site at a direction of 345 degrees. • The East location is approximately 0.1 miles from the site at a direction of 40 degrees. **Approximate time sampling began at each location. ND: Not detected. NS: Not sampled. RSD: Relative standard deviation (or coefficient of variation); the ratio of the sample standard deviation to the sample mean. Source: Adapted from Pellizzari, 1978. 36 ------- Similar variations can be seen in the carbon tetrachloride and chloroform concentration data. Measured chloroform concentrations varied 100-fold between the East location and the on-site location on July 1. The sources of the variation seen at Kin-Buc are undetermined. The site is located near a chemical plant and the New Jersey Turnpike. An analysis of the full data set indicates that both of these sources contribute to organic contamination near the landfill. The data also indicate that the landfill is emitting organic contaminants (e.g., the 191 ug/1 measurement on-site). The difficulty in determining the contribution of the landfill supports the observation of Riggin (1983) that the determination of waste site contributions to polluted atmospheres may require a spatial sampling resolution of tens or hundreds of meters; finer than was used in the Kin-Buc study. The potential for spatial variation in atmospheric concentrations near waste sites is also evidenced by the data on landfill gas contaminant concentrations presented in California Department of Health Services, California Air Resources Board, and South Coast Air Quality Management District, 1983 (Table 6). As can be seen in this table, the measured emission concentration varied greatly at BKK Landfill in California, by as much as two, possibly three, orders of magnitude. Furthermore, emissions were not always detected. It is uncertain, however, whether these data represent 37 ------- TABLE 6 RANGES OF LANDFILL GAS CONCENTRATIONS AT BKK LANDFILL Compound Range (ppa) Vinyl Chloride 83 - 12,800 Vinylidene Chloride ND - 1,200 Acetylene Bichloride ND - 800 Trichloroethylene ND - 1,000 Tetrachloroethylene KD - 1,500 Ethylene Dichloride ND - 5,000 Benzene 10 - 2,000 Chlorobenzene ND - 500 ND: Not detected. Source: Adapted from California Department of Health Services, California Air Resources Board, and South Coast Air Quality Management District, 1983. 38 ------- spatial or temporal variation, although it is likely that both are involved since BKK has a large number of gas vents. Regardless of the source of the variation, vinyl chloride concentrations around BKK Landfill vary greatly from location to location (see Figure 7). Soil. Soil contaminant concentrations and other soil characteristics also exhibit a significant degree of spatial variation (Bruehl, Chung, and Diesl, 1980; Flatman, 1984; Ford and Turina, 1985; Gosse et al., 1986; Mason, 1983; and Schweitzer and Black, 1985). Variation in natural parameters as well as variations in waste deposition and migration patterns, induce variations in soil contaminant concentrations. At an investigation at an unnamed site, Bruehl, Chung, and Diesl (1980) measured chromium concentrations in soils ranging from 20 to 280,000 mg/kg. This compares with an average site background concentration of about 100 mg/kg. In contrast, these authors note that naturally occurring chromium concentrations in soils in the United States range from 5 to 3,000 mg/kg. Mason (1983) summarizes the results of several studies of variability in soil properties (see Table 7). Mason states that coefficients of variation (the ratio of the sample standard deviation to the sample mean) in natural soil properties reported in the literature range from a low of 1 to 2 percent to as high as 850 percent. As indicated in the table, natural soil properties and phosphorus properties of soils varied over a range from 6 to 39 ------- 60 40 20 .a Q. 0. B 10 ra 0) o c o O 0 A /-^. Mean for ^-' Laboratory 1 A Mean for Laboratory 2 o _L _L A B C D E p Monitoring Stations Source: California Department of Health Services, California Air Resources Board, and south Coast Air Quality Management District, 1983. FIGURE 7 RANGE AND MEAN FOR VINYL CHLORIDE MONITORING NEAR BKK LANDFILL, WEST COVINA, CALIFORNIA 40 ------- TABLE 7 COEFFICIENTS OF VARIATIONS (%) FOR SOIL PARAMETERS REPORTED IN MASON (1983) Original Sources Parameter Range (%) White and Hakonsen (1979) Mathur and Sanderson (1978) Plutonium Natural soil constituents 62 - 840 5.6 - 75.2 Harrison (1979) Hind in, May, and Duns tan (1966) Phosphorus properties Insecticide residue* 11 - 140 156 *Soil square 30 inches on a side. Original Sources: Harrison, A. F., "Variation of Four Phosphorus Properties in Woodland Soils," Soil Biology and Biochemistry, Vol. 11, 1979, pp. 393-403. Hindin, E., D. S. May, and G. H. Dunstan, "Distribution of Insecticide Sprayed by Airplane on an Irrigated Corn Plot, Organic Pesticides in the Environment, A. A. Rosen and H. F. Kraybill, eds.,(Advances in Chemistry Series Number 60), American Chemical Society, Washington, DC, 1966, pp. 132-145. Mathur, S. P- and R. B. Sanderson, "Relationships Between Copper Contents, Rates of Soil Respiration and Phosphatase Activities of Some Histosols in an Area of Southwestern Quebec in the Summer and Fall, Canadian Journal of Soil Science, Vol. 58, No. 5, 19/», pp. 125-134. White, G. C. and I. E. Hakonsen, "Statistical Considerations and Survey of Plutonium Concentration Variability in Some Terrestrial Ecosystem Components," Journal of Environmental Quality, Vol. 8, No. 2, 1979, pp. 176-182. 41 ------- 140 percent. Variation in plutonium concentrations was significantly higher; coefficients of variation ranged from over 60 percent to 840 percent. Mason also notes that insecticide residue concentrations have been seen to vary significantly (156 percent coefficient of variation) within a soil square 30 inches on each side. Flatman (1984) and Schweitzer and Black (1985) present estimates of the spatial distributions of lead contamination in soil at the Dallas Lead Smelter site. These estimates, seen in Figure 8, were created using the estimation method known as kriging. As can be seen from the figure, soil lead concentrations vary considerably, ranging from less than 100 ug/g to over 2,500 ug/g. It is interesting to note both the non-uniform shape of the contamination isoareas and the location of zones of less than 100 ug/g within higher contamination zones. Surface Water. Depending on the size and other characteristics (such as degree of turbulence) of a water body as well as the location and other characteristics of contaminant sources, surface water contaminant concentrations may vary greatly or nearly not-at-all. Well-known phenomena that lead to significant spatial variation in surface water bodies include thermal stratification, in lakes and impoundments, and for large water bodies, the formation of contaminant plumes (Gosse et al., 1986). Table 8 illustrates spatial variation in contaminant concentrations in streams at two CERCLA NPL sites, Whitehouse Oil 42 ------- 12500 10500 8500 S 6500 4500 2500 500 Site: DMC | | <100 frX'l 100 < 250 K,'j| 250 < 500 P%;| 500 < 1000 \fffj\ 1000 < 2500 till 2500 < 5000 I I I 500 2500 4500 6500 8500 X (feet) 10500 12500 Source: Flatman, 1984. FIGURES ISOAREA MAP OF KRIGING ESTIMATE OF LEAD CONCENTRATIONS (ug/g) IN SOIL 43 ------- TABLE 8 EXAMPLES OF SPATIAL VARIATION IN SURFACE WATER CONTAMINANT CONCENTRATIONS Location Upstream Downstream Whitehouse Oil Pits (ug/1) Distance (ft) Iron Magnesium 300 1,000 2,500 3,800 1,200 1,700 1,000 1,200 700 2,200 1,700 1,700 Zinc 20 80 30 70 Location Upstream Downstream Fields Brook (ug/kg) Distance (ft) Trichloroethene Tetrachloroethene 10 635 1,429 1,694 2,118 2,753 3,547 3,812 6,989 7,011 9,107 9,319 ND 7.5 74 64 41 61 25 NQ ND 62-65 51 31 72 48 NQ ND: Not detected. NQ: Not quantifiable. Note: Distance is measured upstream or downstream from the probable point of entry of contaminants from the source to the surface water body. Source: Adapted from Burger and Kushner, 1986. 44 ------- Pits, and Fields Brook. At the Whitehouse Oil Pits site, a sizeable relative increase in magnesium and zinc concentrations was detected between the upstream and the downstream samples accompanied by a smaller relative increase in iron concentrations, all within a distance of 1,300 feet of the probable point of entry of contaminants from the site. Both magnesium and iron concentrations remained somewhat stable for almost 3,000 feet downstream while zinc concentrations fluctuated, declining by over 50 percent and then more than redoubling within the same distance. At Fields Brook, concentrations of both trichloroethene and tetrachloroethene increased significantly between upstream and downstream sampling points. Concentrations of both contaminants decline with distance, although both exhibit fluctuations at different distances from the site. Although the reason for these fluctuations is unknown, it is probable that they are caused by a combination of measurement error and/or the presence of additional contaminant sources. 4.1.2 Wastes The concentration of hazardous substances in the wastes at a site varies considerably at different locations at the site. Even at a given location, waste concentrations may vary with depth. The reasons for this variation are straightforward. Variation arises from different patterns in the original deposition of wastes; from physical, chemical, and biological processes that act on the wastes 45 ------- after deposition; and from differences in the migration patterns of the waste constituents. An example of the extent of on-site variation in waste constituent concentrations is indicated in Table 9. These data were abstracted from site inspection and remedial investigation reports as part of the HRS issue analysis of waste constituent concentrations (Wusterbarth, 1986). The values shown in the table represent the sum of the concentrations of CERCLA contaminants found in the wastes at various locations on each site. As can be seen from the data, there is significant variation in total hazardous substance concentrations within sites. Relative standard deviations range from a low of 47 percent in the waste pile(s) at the Micronutrients International site to a high of 265 percent at the drum portion of the Morgantown Ordnance site. The data also support the conclusion drawn by others (e.g., in Ford and Turina, 1985) that concentrations of hazardous constituents in drummed waste is highly variable between drums. The relative standard deviations of the hazardous substance concentrations measured in drums are consistently above 100 percent while the ranges are very large (generally over two to about five orders of magnitude) indicating a high degree of spatial variation in waste contaminant concentrations. Ford and Turina (1985) also indicate that waste contaminant concentrations may vary with depth within a drum, as a result of 46 ------- TABLE 9 SPATIAL VARIABILITY IN WASTE CONCENTRATION (SUM OF HAZARDOUS CONSTITUENT; ppm) Site Name Cosden Chemical Morgantown Ordnance Hunterstown Road Cleve Reber Old Mill Cecil Lindsay Mill Creek Micronutrients Int. Texarkana Wood Preserving Laskin Poplar Laskin Poplar Old Inger Number of Type Samples Mean Drum Drum Drum Drum Drum Drum Drum Pile Pond Sludge Tank Sludge Tank Liquid Tank 5 8 28 7 11 3 4 10 5 4 32 9 143,629 110,243 50,843 11,158 136,764 352,391 30,537 201,194 84,605 30,298 3,750 486 Standard Deviation 266,393 292,660 92,715 14,462 159,130 365,028 46,829 94,641 78,261 45,509 3,193 560 RSD (%) 185 265 182 130 116 104 153 47 93 150 85 115 Min. 427 202 4 17 61 4,870 469 38,678 494 3,751 28 2 Max. 610,400 834,120 459,060 41,374 451,800 732,712 99,765 339,759 163,100 98,339 12,882 1,431 Source: Wusterbarth, 1986. ------- stratification. The extent to which the data in Table 9 represent horizontal versus vertical variation is unknown. 4.2 Temporal Variation Temporal variation is the second of the two "natural" sources of variation in concentration data (i.e., variation resulting from environmental and waste disposal processes as opposed to human error). Temporal variation is defined as the variation in a parameter of interest at a given location at different points in time. The effect of undetected temporal variation on data utility is similar to that of spatial variation. Together, the two represent the "natural" variation in estimated contaminant concentrations. Temporal variation is caused by many of the same factors that induce spatial variations. Generally, temporal variations in contaminant concentrations arise from temporal variations in environmental factors such as flow rates and stability. However, temporal variations in contaminant concentrations may arise from the interaction of spatially varying and temporally varying factors. For example, a flood may inundate a landfill located in the flood plain releasing additional contaminants into a stream. This phenomenon can be viewed as arising from the interaction of a temporally varying factor (stream flow) and a spatially varying factor (waste concentration). Similarly; spatial variations can arise from the interaction of temporally and spatially varying factors such as the interplay of atmospheric deposition and solar radiation in determining soil contaminant concentrations of photodegradable materials. 48 ------- Temporal variation is a critical factor in determining the frequency and duration of sampling. As in the case of spatial variation, those sites with a high degree of temporal variation generally require a greater sampling frequency and longer sampling duration to achieve a particular level of representativeness. Conversely, sites that are temporally homogeneous generally require lower sampling frequencies and durations. Few sites and media are temporally homogeneous. 4.2.1 Environmental Data This section discusses examples from the literature illustrating the extent and importance of temporal variation in determining contaminant concentrations in the five environmental media. Ground Water. Natural temporal variation in ground water contaminant concentrations at a specific location and the characteristics that determine those concentrations is considered to be small (Sgambat and Stedinger, 1981). These and other authors indicate, however, that in areas affected by human activities, temporal changes in ground water contaminant concentrations may be relatively large, although the variation is usually evident only on a seasonal or longer scale (Everett, 1981; Gillham et al., 1983; McKown, Schalla, and English, 1984; Nacht, 1983; Possin, 1983; Schuller, Gibb, and Griffin, 1981; and Sgambat and Stedinger, 1981). As cited by these and other authors, causes of temporal variation in ground water quality and other related parameters include: 49 ------- • Variations in contaminant source release characteristics. • Changes in recharge patterns due to climatic variation. • Variations in water use patterns. Everett (1981) also indicates that seasonal variations are likely in areas characterized by the presence of highly permeable soils and geologic materials lying above the water table and in areas in which wells tap the shallow portions of aquifers. The extent of temporal variation of ground water contaminant concentrations is illustrated by information contained in Sgambat and Stedinger, 1981 (Figure 9 and Table 10) and Benson, Glaccum, and Beam, 1981. The former figure shows nitrate concentrations in a single well varied by a factor of three over the period of approximately one year. The ranges and standard deviations of the concentration of total organic compounds in the four wells listed in Table 10, further illustrates the extent of temporal variation. In two of the four wells, the standard deviation exceeded the mean while in the third it was nearly 80 percent of the mean. As an additional example, Benson, Glaccum, and Beam (1981) illustrate the temporal variation in the extent of contamination in a shallow plume arising from a spill as measured by Em conductivity (Figure 10). In contrast, in their investigation of contamination in the Biscayne Aquifer in Florida, Singh et al. (1984) found little variation in contaminant concentrations over a period of six months. 50 ------- 12 Well 1 12 Well 2 O) E 0 12 Well 3 III I I I 1 1 1 1 I I I I I I I I I I I I I III I I I I I I I I I I I I I I I I I I I 0 I I I I I I I I I I 1 I I I I I I I I I I I I 16 12 Well 4 I I I I I I I I I I I I I I I I I I I I I I JFMAMJJASOND JFMAMJJASOND Time, in Months Source: Sgambat and Stedinger, 1981. FIGURE 9 FLUCTUATIONS OF NITRATE CONCENTRATIONS IN WATER FROM INDIVIDUAL SHALLOW WELLS OVER TIME 51 ------- TABLE 10 CONCENTRATIONS* OF TOTAL ORGANIC COMPOUNDS IN WATER FROM FOUR LONG ISLAND, NEW YORK WELLS OVER A ONE-YEAR PERIOD (1977-1978) Well No. N-8326 N-8327 N-5962 S-27259 Number of Analyses 25 14 13 9 Mean 93 148 33 19 Standard Deviation 110 115 17 30 Range 0 4 10 1 - 430 - 455 - 46 - 79 Concentration in ug/1. Source: Sgambat and Stedinger, 1981. 52 ------- Point of Spill Regional Ground-Water Flow I Acre A) I Day B) 26 Days Source: Benson, Glarcson, and Beam, 1981. FIGURE 10 CHANGE IN SHALLOW PLUME OVER TIME, AS MEASURED BY Em CONDUCTIVITY 53 ------- Air. As stated previously, the atmosphere is probably the most variable medium of concern with regard to measurements of contaminant concentrations and other related characteristics from uncontrolled waste sites. Contaminant concentrations at a given location can vary over orders of magnitude within a period of hours. Numerous authors identify temporal variation as important in determining concentrations (for example, Gosse et al. , 1986; Riggin, 1983; and Zachowski and Borgianini, 1984). The same factors that determine spatial variability, also determine temporal variability: variation in the atmosphere itself (e.g., wind speed, wind direction, and stability), variation in locations and release characteristics of contaminant sources, and effects of terrain. The extent of temporal variability in atmospheric concentrations can be seen in the data presented earlier on Kin-Buc Landfill (as reported in Pellizzari, 1978; see Tables 3 through 5). Concentrations of benzene, carbon tetrachloride, and chloroform varied substantially over a three day period, particularly at the Meadow Road location. The temporal coefficients of variance (or relative standard deviations) at this location were 141 percent, 129 percent, and 94 percent, respectively. Variation at the East location (0.18 km from the landfill) was high for both benzene and chloroform (72 percent and 133 percent, respectively), while variation in measured carbon tetrachloride concentrations was small (about 2 percent). A particularly high degree of variation was seen at th 54 ------- on-site location. Within a matter of four hours, detected benzene 3 concentrations increased from a trace level to 191,000 ng/m , while carbon tetrachloride concentrations increased from below the detection 3 limit to 10,600 ng/m . Chloroform concentrations were relatively 3 3 more stable, increasing from 19,444 ng/m to 27,200 ng/m . The on-site benzene concentration variation clearly illustrates the problems that temporal variation in concentrations can cause in assessing site risks. A single measurement taken in the morning would indicate that the site posed no risk from benzene emissions. A measurement taken only four hours later would lead to the opposite conclusion. Surface Water. It is well known that surface water contaminant concentrations and other characteristics exhibit a significant degree of temporal variability, both short-term and longer-term (e.g., seasonal). The sources of variation include changes in the locations and release characteristics of contaminant sources, natural variation in background contaminant concentrations, and climatic variations in rainfall and other factors (Gosse et al., 1986 and Sherwani and Moreau, 1975). According to Gosse et al. (1986), sampling surface water bodies should be sensitive to a number of temporally varying factors including: • Mixing • Freeze over • Dry/wet seasons 55 ------- • Flow and elevation • Micro- and macrobiotic communities • Runoff patterns • Diurnal variations in chemistry • Contaminant sources • Plant growth patterns Soil. The extent of temporal variation in soil contaminant concentrations is problematic. Significant variation is possible due to chemical and biological transformation and degradation. This possibility is illustrated by the previously discussed Verona Well Field ground water example in which a plume of DCE originated from a source of PCE through chemical transformation (see Figures 1 and 2). 4.2.2 Wastes Temporal variations in waste contaminant concentrations is also problematic. Significant variations in waste concentrations over time are possible due to differences in contaminant transformation, degradation, and migration patterns. Especially important in this context is the potential for waste concentrations to decline over time as materials escape into the environment. A "site" may have little or no hazardous constituents remaining in it (and thus have low waste constituent concentrations) but may have created a substantial plume of contaminated ground water. in such cases, waste quantity as indicated by the quantity of hazardous constituents remaining on a site (calculated from waste contaminant concentrations) 56 ------- may be a very poor indicator of the potential magnitude and duration of releases from the site. Additionally, contaminants not deposited at the site may be created at the site through chemical interactions. The previously discussed Verona Well Field ground water example illustrates this point. No DCE was deposited at the site and yet DCE can now be found at the site. This phenomena is also evidenced by the generation of methane and vinyl chloride in municipal landfills (see, for example, Lipsky and Jacot, 1985). 4.3 Limitations in the Data Development Process In addition to the natural factors affecting data quality, numerous factors of human origin also affect data quality in each of the four semi-independent stages of the data development process: • Sampling • Handling • Analysis • Interpretation The following discussion addresses each of these stages separately. It is important to note that the problems identified in data development vary greatly in importance from site to site. Further, many of the problems are well known and their effects can be minimized by the use of proper procedures, reinforced by a comprehensive QA/QC program. 57 ------- 4.3.1 Sampling Several factors interact to adversely affect the quality of data obtained from environmental and waste samples. So«e of these factors are environmental in nature while others are related to sampling techniques and technologies. 4.3.1.1 Environmental Factors. A comprehensive discussion of the environmental factors affecting contaminant concentrations is beyond the scope of this report. However, numerous authors (e.g., Barcelona et al., 1985; Berg, 1982; Driscoll, 1986; Ford and Turina, 1985; Ford, Turina, and Seeley, 1984; Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Gibb, Schuller, and Griffin, 1981; Gillham et al. , 1983; Gosse et al. , 1986; Kazaann, 1981; Mason, 1983; McKown, Schalla, and English, 1984; Nacht, 1983; Riggin, I983? Scalf et al., 1981; Schuller, Gibb, and Griffin, 1981; Sisk, 1981; Tirsch and Male, 1983; U.S. Environmental Protection Agency, 1977; U.S. Environmental Protection Agency. 1985a and I985b; and Zachowski and Borgianini, 1984) have emphasized the importance of adequately characterizing the site-specific environment before a sampling plan is developed and sampling activities are begun. The aspects of the environment to be characterized consist of the major components of the processes that determine concentrations (e.g., media flow rates, directions, and diffusion characteristics). Knowledge of these factors is also necessary to assess the representativeness of the samples once they are taken. 58 ------- The types of background environmental information that should be collected at a particular site, before sampling, depend on the physical characteristics of the site, the types of wastes deposited at the site, and the nature of the threat posed by the site (e.g., human health). Several authors have expressed opinions on the minimum information that they feel is necessary to determine sampling locations, frequencies, and methods for ground water and air sampling. These authors indicate that such sampling parameters must be developed on a site-specific basis. They believe that it is not possible to develop values for such parameters generically. The principal guidance documents on ground water sampling (Barcelona et al., 1985; Claassen, 1982; Gibb, Schuller, and Griffin, 1981; Gosse et al., 1986; Scalf et al., 1981; U.S. Environmental Protection Agency, 1977; and U.S. Environmental Protection Agency, 1985a and 1985b, as well as other authors) list the following as important ground water parameters that should be assessed before sampling: • Ground water flow gradient • Ground water flow rate • Aquifer transmissivity and related parameters (e.g., conductivity, porosity, and permeability) • Extent of fracturing • Locations of recharge/discharge areas The feasibility of measuring many of these parameters within the confines of a PA/SI is open to question (Gerstein, 1986). The use of other information (e.g., regional ground water flow parameters), 59 ------- while possible, may not provide sufficiently accurate, site-specific values. This concern is reinforced by the known effects of drinking water well capture zones on local ground water flow patterns (see, for example, Quinn, Wittmann, and Lee, 1985 and Absalon and Starr, 1980). The removal of water from aquifers by pumping drinking water wells may affect the local hydraulic gradient. The regional gradient may be determined largely by geologic conditions and may be unaffected by pumping the wells. The size of the affected area and the degree of change in the gradient will depend on local conditions such as the rate of pumping, the number of wells, and local hydraulic conditions. A similar set of background information requirements to support air sampling is indicated by authors such as Riggin (1983) and Gosse et al. (1986). These authors list the following parameters that should be assessed prior to sampling: • Wind speed • Wind direction • Temperature • Pressure • Relative humidity • Precipitation patterns • Locations and characteristics of sources Ideally, these parameters would be evaluated at the site, although the data are more frequently available only from the nearest airport. 60 ------- The limitations, however, in using such "regional" information to infer local conditions has been noted by authors such as laccarino et al., 1984, particularly in areas of complex terrain. Thus, it is clear from the literature that a fairly extensive program of background data collection and sampling is needed prior to contaminant sampling to ensure that the samples are as representative as possible within the limitations (e.g., cost and time constraints) placed on the sampling program. However, such extensive background data collection is rarely performed in support of current site inspections. At best, information from secondary sources, often regional information, is used to infer local conditions. The lack of actual site specific knowledge of these important environmental parameters increases the uncertainty in the data, limiting its usefulness. As a simple final example, without site specific information on the wind direction during air sampling (as is the case for some site investigations, one cannot determine if a sample constitutes a background (i.e., upwind) sample or a site (downwind) sample. 4.3.1.2 Sampling Techniques and Technologies. In addition to the environmental factors, several factors of human origin can adversely affect the quality of concentration data during the sampling process. Two inter-related concerns arising from the need to produce representative data with minimal errors, are of particular importance during sampling. These concerns are: 1) that the 61 ------- samples collected represent to the greatest extent possible, in situ concentrations at the instant of sampling and 2) that the samples do not become contaminated during the sampling process. Several additional concerns common to most media can be identified. These include the potential for sample contamination from a wide variety of sources, potential for interaction between the sample and the environment after the sample has been taken, gaps in sampling technology (both in terms of contaminants that can be sampled and in terms of critical operating parameters such as minimum sampling times), lack of standardization and validation of some existing techniques, cross-contamination between samples taken with the same sampler, safety considerations that might preclude the collection of otherwise needed samples (e.g., in buried drums), and the potential for needed, but unvalidated, modifications to sampling equipment to meet site-specific conditions. The following discussion illustrates these concerns in each of the five environmental media and in wastes. Ground Water. The literature yielded more information on problems associated with ground water sampling technologies and techniques than for any of the other media, reflecting, as indicated by several authors, the relative difficulties inherent in ground water sampling in comparison with other media. Gillham et al. (1983) presents the best overall discussion of the alteration in chemical concentrations that can be induced in ground water samples. Table 11 lists the sources of sample bias identified in their analysis. 62 ------- TABLE 11 POTENTIAL SOURCES OF BIAS IN SAMPLING GROUND WATER INORGANIC AND RADIOACTIVE PARAMETERS DIRECT INDIRECT INORGANIC Contamination Parameters Electrical Cond. PH Redox Condition Non Toxlo Conatltuenta Chloride SuIfate Sodium Ammonium Calolum Magnesium Iron, Manganese Toxlo Constituents Nitrate Fluoride Araenlo Selenium Barium Cadmium Chromium Lead Silver Mercury RADIOACTIVE Radium Gross Alpha and Beta temperature, suspended particles, precipitation, adsorption / exchange O>2 degassing, precipitation of carbonates and oxides oontaot with akin precipitation of gypsum, reduction adsorption / exchange, leaohlng from glass, oontact with akin adsorption / exchange, volatilization at low pH adsorption / exchange adsorption / exchange, precipitation denltrlfloatlon, nitrification precipitation adsorption / exchange / leaohlng from sampling equipment, precipitation adsorption / exchange, precipitation, degasalng degassing, changes In Eh, pH J 0, Invasion, temperature, mloroblal aotl vlty 02 Invasion, C0? degassing C0» degassing, 0- Invasion ' Cross-contamination Is a problem for all parameters, but la Indicated here as a source of bias only If It Is especially likely to occur. Source: Gilham et al., 1983. ------- TABLE 11 (Concluded) BIOLOGICAL AND ORGANIC PARAMETERS DIRECT INDIRECT BIOLOGICAL Colifora Bacteria ORGANIC Drlnklng-Water SKla. Endrln Llndana Methoxychlor Touphene 2,»-D 2,*,1-1T Sllvex Quality Paraaatera Phenols Contamination Parantera Total Organic Carbon Total Organic Halogai Caaollne Coaponanta B«nz«n« Tolu«na I»l«n« Mathjrl t-butyl «th*r croaa-contaalnatlon aorptlon, orono-oontaalnallon , blodagradatlon during atoraga aorptlon, oroaa-oontaalnatlon ,l«aohlng, blodegradatlon during atoraga aorptlon, oroaa-oontaailnatlon , leaching, volatlllr.atlon, blodagradatlon during atoragA dlffualon through plaatloo"] aorptlon, oroaa-conta>lnatlon J laaohlng, volatllnation, blodagradation during atoraga 0. Invasion, pH, precipitation of other ooapounde 0 Invasion • Croaa-oontaalnatlon la a problaai for all paraautara, but la Indicated here aa a source of blae only IT It le (specially likely to ooour. Source: Gilham et al., 1983. ------- Possibly the most frequently identified problem in ground water sampling is the problem of sample contamination by stagnant casing water (see, for example, Berg, 1982; Driscoll, 1986; Gibb, Schuller, and Griffin, 1981; Gosse et al., 1986; McKown, Schalla, and English, 1984; Nacht, 1983; Scalf et al., 1981; and Sisk, 1981). Concentrations in the casing water are not representative of the concentrations actually in the aquifer. Thus, this water must be purged from the well before sampling. Generally, most authors recommended purging between 4 and 10 well volumes from the well to achieve a level of no more than 5 percent casing water. McKown, Schalla, and English (1984), however, raise the possibility that purging of five well volumes may not appreciably decrease the probability of significant sample contamination. These authors indicate that greater reliance should be placed on natural purging. In either case, the resultant observed concentration may not reflect risk with respect to the actual concentration of pollutants to which the user is exposed (e.g., in water from a tap). Additionally, numerous authors have identified problems with ground water sampling techniques and technologies. Most authors, such as Barcelona et al. (1985) and Claassen (1982) stress the importance of not overly disturbing the geomedia during well construction and sampling so as to ensure that natural conditions are maintained and in-situ conditions are sampled. 65 ------- Both Driscoll (1986) and Claassen (1982) identified pump and well residues as important sources of sample contamination. Driscoll specifically identifies entrained sediments as a source of contamination. Claassen (1982) identified the problem of contamination of ground water by chemicals resulting from the degradation of well materials in old wells. Ihis problem is of particular interest since current PA/SIs rely heavily on existing wells in order to reduce sampling costs. Several other authors have identified well construction and drilling equipment as potential sources of sample contamination (for example, Absalon and Starr, 1980; Fetter, 1983; Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Gillham et al., 1983; and Keith et al., 1983b). Along similar lines, McKown, Schalla, and English (1984) note the effect that well diameter has on estimates of transmissivity, indicating that transmissivity estimates in two inch diameter wells range over two orders of magnitude. The duration of pumping has been specifically identified as an important contributor to sample uncertainty by Driscoll (1986); Geraghty and Miller, Inc. and American Ecology Services, Inc. (1985); Nacht (1983); Keith et al. (1983b); and Sgambat and Stedinger (1981). Figure 11 illustrates the changes that can occur in contaminant concentration and related parameters during pumping. As indicated in this figure, contaminant concentrations as well as other 66 ------- 350 300 250 25 20 15 10 15 10 EC, ^mho/cm Cl, mg/L - N03, mg/L 26.0 25.5 Temp., °C 1 10 100 Time after Start of Pumping, Minutes Source: Keith et a/., 1983b. FIGURE 11 WATER QUALITY FLUCTUATIONS WITH TIME OF PUMPING 67 ------- indicators of the stability of the ground water environment may vary considerably over time as a result of pumping. Claassen (1982) also identified the importance of pump operation in adversely affecting sample quality. Time for withdrawal of samples from a well and the possibility of changes in the water samples during withdrawal have been identified as important sources of uncertainty (Driscoll, 1986; Gillham et al., 1983; Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Ford and Turina, 1985; and Scalf et al., 1981). The concern is that the water environment of the sample will change even during the short time for withdrawal, altering the contaminant concentrations. Particular phenomena identified include degassing and volatilization of volatile compounds (Gillham et al., 1983), introduction of oxygen and possible changes in the oxidizing/reducing nature of the sample (Gillham et al., 1983), changes in the carbon dioxide concentration in the water (Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985), changes in biological activity (Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985), and changes in sample pH and temperature (Driscoll, 1986; Gillham et al., 1983; Ford and Turina, 1985; and Scalf et al., 1981). As noted by Ford and Turina (1985), the rates of many chemical reactions (including gas exchange, microbial growth) double with each increase of 10 degrees Centigrade in temperature. They also note that the presence of sunlight and oxygen may produce near instantaneous changes in sample chemistry. 68 ------- Gillham et al. (1983) also identify the potential for sample contamination arising from sampler and well materials (e.g., bentonites and plastics). Geraghty and Miller, Inc. and American Ecology Services, Inc. (1985) also identify the possibility of contamination by the sampling apparatus. The problem of cross contamination arising from using the same drilling or sampling equipment in two different locations was noted by Absalon and Starr (1980); deVera et al. (1980); and Seanor and Brannaka (1981). Gibb, Schuller, and Griffin (1981) indicate that the type of pump used can have an adverse effect on sample quality. The use of air or nitrogen pumps appears to affect sample concentrations while peristaltic pumps or bailing do not. This conclusion is supported by Seanor and Brannaka (1981) who indicate that air squeeze, piston, jet, and submersible pumps are those most likely to cause contamination problems. The extent of these problems was investigated under laboratory conditions by Ho (1983). Ho investigated the effects that transport line materials, pump rate, lift (travel distance in the sampler), and initial contaminant concentration had on final sample concentration. He determined that all were important factors in determining sample concentration although to differing degrees for different contaminants. Overall, he found that line material was the most consistently important factor, pump rate was important for volatiles, 69 ------- and initial contaminant concentration was important for the more volatile compounds. Lift was found to be important for compounds _2 3 with Henry's constants greater than 10 atm-m /mol. Air. The most common problems associated with techniques and technologies for air sampling cited in the literature, disregarding those directly related to the extreme spatial and temporal variability of the atmosphere and its effects on contaminant concentrations, are gaps in the availability of sampling equipment (Ford, Turina, and Seeley, 1984; Gosse et al., 1986; Harrison, undated; Riggin, 1983; and Zachowski and Borgianini, 1984). This problem is primarily apparent in the lack of commonly accepted methods for the sampling of many organic vapors, gases, and particles. Ford, Turina, and Seeley (1984) note that currently available portable equipment is unable to detect certain compounds of possible interest in site investigations. This problem is primarily related to limitations of sorbents such as Tenax and to limitations in field gas chromatography. Gosse et al. (1986) present a list of methods available for sampling organic vapors and gases (Table 12). It is interesting to note the relatively small number of compounds listed and the lack of methods for maleic anhydride, methyl acetate, and phthalic anhydride in this short list (all CERCLA hazardous substances). Riggin (1983) also notes that no standard methods are available for many toxic air pollutants at low ambient concentrations. This is addressed by Harrison (undated) who 70 ------- TABLE 12 SAMPLING METHODS FOR AIRBORNE ORGANICS Hazardous Constituent Tenax Charcoal Cryogenic Hl-Vol DNPH Cartridge Cartridge Trapping PUF Impinger Other Acetaldehyde Acrolein Acrylonitrile Ally! chloride Benzene Benzyl chloride Carbon tetrachloride Chlorobenzene Chloroform Chloroprene Cresol Cumene 1,4-DCB 1,2-DCB Dichlorome thane Dioxin Epichlorohydrin Ethylbenzene Ethylene oxide Formaldehyde X X X X X X XXX X X XXX X X X X X X X X X X X X X X X Aarvan, 1981 X X X X X X Source: Gosse et al., 1986. ------- TABLE 12 (Concluded) TABLE 8-13 (continued) Hazardous Constituent Tenax Charcoal Cryogenic Hl-Vol DNPH Cartridge Cartridge Trapping PDF Impinger Other Hexachlorobutadlene Hexachlorocyclopentadiene Hydrogen cyanide Maleic anhydride Methyl acetate N-Dlmethylnitrosamine Naphthalene Nitrobenzene X Phenol X Phosgene Phthalic anhydride PCBs Propylene oxide 1,1,2,2-tetrachloroethane X Tetrachloroethylene X Toluene X 1,1,1-Trichloroethane X Trichloroethylene X Vinyl chloride Vinylidene chloride Xyleae X X X X X X X X X X X X X X X X X No method identified No method identified ASTM STP 721, 198 p. 80-91 NIOSH Method 3502 Ruggle, et al., 1979 No method identified Source: Gosse et al., 1986. ------- states that the analysis of low molecular weight hydrocarbons at low concentrations requires a difficult chromatographic separation. Although the exact reasons for the problems encountered are not discernible, Weber and Mims (1981) rejected the walk-through survey method for detecting organic compound leaks because of severe problems with the reproducibility of organic compound measurements using portable devices. To the extent that walk-through surveys of chemical plants are similar to air contaminant surveys of waste sites with portable equipment, this study raises questions about the use of portable equipment surveys in site inspections. Ford, Turina, and Seeley (1984) also note problems of insensitivity and slow response time in organic samplers. The problem of equipment gaps affects more than simply the samplers. Zachowski and Borgianini (1984) found that no suitable sampling pumps were available to support their investigations of uncontrolled waste sites in New Jersey. The authors had to fabricate their own pump in order to calculate daily exposures using a 24-hour sampling period and relatively low flow velocities. This problem is also noted by Ford, Turina, and Seeley (1984). In comparison, the state of the art in particle sampling is fairly well advanced (see, for example, Farthing, 1982; Harrison, undated; and Stevens, 1984). The outstanding problems in these areas are concerned with the details of sampler design and with the extraction of organics from filter media. 73 ------- Overall, these problems indicate the possibility that, given the variability of air concentrations and the wide range of contaminants found at uncontrolled waste sites, concentrations of concern for some contaminants may not be detected during site inspections. Wastes. Four problems were identified with techniques and technologies for sampling wastes. The primary problem associated with waste sampling is maintaining sampling personnel safety (see, for example, Wetzel, Wagner, and Tafuri, 1982). This problem also occurs in sampling any environmental media. It is a more significant problem in sampling waste, however. As noted by Ford, Turina, and Seeley (1984), care must be taken to minimize disturbance to the waste matrix during sampling. Some of the reasons for this are the same as for ground water, as discussed above. Unlike ground water, however, sufficient disturbance of the wrong wastes may cause them to explode or otherwise react with serious consequences. For these reasons, for example, it is considered unwise to sample the interiors of landfills unless waste locations and waste characteristics are known. Associated with the need to minimize disturbance for safety reasons and to ensure collection of a representative sample is the need to avoid increasing the mobility of wastes that are not currently mobile. For example, drilling into a landfill not only may pose a safety risk, but it may also cause an increase in the rate of release of gaseous contaminants from the landfill. Further, drilling 74 ------- through waatea into ground water may increase the rate of waste migration to ground water. Accessibility is a third problem in waste sampling which is also common to sampling any environmental media. It may be extremely difficult or hazardous to sample wastes in certain locations, e.g., from the middle of a large surface impoundment or from buried containers. This difficulty has led to the development of specific technologies such as dippers with telescoping handles (Gosse et al., 1986). Finally, according to Gosse et al. (1986), different sampling techniques are needed to sample wastes at different sites depending on the type of waste and waste management unit (see Table 13). Waste samplers have been developed to address most types of wastes in most types of waste management units. However, Gosse et al. note that equipment for the following situations must be selected or designed on a site-specific basis: sludges, sand or powdered granules from waste piles, landfills, land treatment facilities, surface impoundments (including ponds and lagoons), and pits as well as sand or powdered granules from tanks and other containers. Other Media. The problems associated with the techniques and technologies of sampling soils, surface water, and sediments are similar to the problems already discussed. 4.3.2 Handling Generally, once a sample has been taken, it must be transported to an analysis location. This location may be off-site (such as an 75 ------- TABLE 13 SAMPLING EQUIPMENT FOR PARTICULAR WASTE TYPES Source Unit Type Storage Waste piles. Ponds, tanks landfills, lagoons. Waste Type Drua or bins & Land treataent & pits Free flowing COLIWASA* Weighted N/A Dipper liquids and glass tube bottle slurries Sludges Trier Trier a « Moist powders Trier Trier Trier, Trier, cr granules scoop scoop Irv powder j Thief Thief Thief Thief or granules Sand or Auger a a a packed powders and granulea Large Large Large Large Large grained Trier Trier Trier, Trier, solids scoop scoop Other Waste Saaple Sources Sacks Open bed Closed Convery and baga truck bed truck belt Pipe N/A N/A COLIWASA* N/A Dipper glass tube N/A Trier Trier Shovel, Dipper scoop Trier Trier Trier Shovel, Dipper acoop Thief Thief Thief Shovel, Dipper scoop Auger Auger Auger Dipper dipper Large Large Large Trier Dipper Trier Trier Trier •Adapted frosi U.S. EPA, 1982. This situation can present significant logistical sampling problems) equlpMnt Bust be specifically selected or designed based on sit* and wast* conditions. N/A - Hot applicable. Source: Gosse et al., 1986. ------- EPA Contract Laboratory) or on-site (as in a mobile laboratory). Alternately, there may be no appreciable handling component as in the case of automatic sampling and analysis equipment such as mobile gas chromatography/mass spectroscopy (GC/MS) units. In any case, the problems encountered in handling samples, though important, are not as numerous as those of sampling and analysis. There is one pervasive problem associated with sample handling. This is the need to minimize changes in the sample between the time of sampling and the time of analysis. This problem is noted by numerous authors including Berg, 1982; Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Gillham et al., 1983; Kirchmer, 1983; Plumb, 1984; Riggin, 1983; and Schuller, Gibb, and Griffin, 1981. There are two semi-independent aspects to the problem. First, the integrity of the sample must be maintained and sample contamination avoided. This usually means that the sample must be sealed and handled in a sealed container. This is required to minimize the interaction between the sample and the atmosphere and to prevent the accidental introduction of foreign substances into the sample. Sealing prevents, for example, outgassing of volatiles from liquid and sorbent samples and changes in sample chemistry that may induce changes in contaminant concentrations. These problems are similar to those discussed previously concerning the interaction of samples with the non-in-situ environment. 77 ------- The second aspect of the problem is that of sample stability. A minimum of "natural" changes in sample chemistry should be allowed to occur between the time of sampling and time of analysis. Naturally occurring reactions (those that were in progress in-situ) that would otherwise affect contaminant concentrations should be halted. This commonly requires that the sample be either frozen or preserved with a preservative such as hydrochloric acid. These two aspects of the handling problem also interact to create the need to minimize the interaction between the sample and its container. This problem is particularly wellknown in regard to liquid samples where care must be taken to prevent loss of metals through ion exchange with the container material (Fitzgerald, 1986). An additional problem, noted by Geraghty and Miller, Inc. and American Ecology Services, Inc. (1985), is the potential contamination that may occur when an aliquot of a sample is withdrawn from a sample for analysis. 4.3.3 Analysis Once a sample has been taken and transported (if necessary) to a laboratory, the process of analyzing that sample begins. As mentioned above, the analysis may be performed off-site, on-site, or as an integral part of sampling. Though it presents more problems than that of handling, the analysis component of data development is considerably more amenable to control than the sampling component. The analysis component occurs generally in a laboratory where conditions are, in principle, controllable. 78 ------- One of the most critical problems with sample analysis, one noted by many authors (including Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985; Gurka et al., 1982; Keith et al., 1983a; Kirchmer, 1983; Plumb, 1984; and Riggin, 1983), is the lack of consistent, acceptable analytical methods for many contaminants of concern at the concentrations encountered at waste sites. Table 14 presents a list of over 90 RCRA hazardous constituents for which there are analytical problems (Gosse et al., 1986). These constituents represent almost 25 percent of the RCRA hazardous constituents (all of which are CERCLA hazardous substances). EPA has recently proposed changes in required ground water analyses for RCRA facilities, reducing the list of RCRA contaminants to be analyzed in part because of analytical constraints (51 FR 26632, 24 July 1986). In addition, Fitzgerald (1986) indicates that a significant number of CERCLA contaminants cannot be analyzed by the EPA Contract Laboratories at this time. Overall, these gaps in analytical capabilities lead to possibly undetected gaps in the coverage of contaminant compounds at sites. In support of this contention, Keith et al. (1983a) note the acceptable ranges for accuracy and precision employed in the EPA Contract Laboratory Program (see Table 15). The acceptable accuracy of 200 percent indicates that the estimated concentration of a contaminant may be consistently twice as high as the true value and still be acceptable. 79 ------- TABLE 14 RCRA APPENDIX VIII COMPOUNDS FOR WHICH NO SUITABLE ANALYTICAL PARAMETER METHODOLOGY OR STANDARDS EXIST, OR FOR WHICH A SURROGATE HAS BEEN SUGGESTED AS AN ANALYTE l-acetyl-2-thiourea acrylamide aflatoxins aldicarb 5-(aminomethyl)-3-isoxazolol amitrole auramine azaserine benz(c)acridine benzenearsonic acid benzo(j)fluoranthene brotnoacetone brucine chlorambucil chlornaphazine citrus red no. 2 cycasin 2-cyclohexyl-A,6-dinitrophenol cyclophospharaide daunomycin diallate dibenz(a,h)acridine dibenz(a,j)acridine 7H-dibenzo(c,g)carbazole dichlorophenylarsine 1,2:3,4-diepoxybutane diethylarsine diethylestilbesterol dihydrosafrole 3,4—dihydroxy- -(methylamino) methyl benzyl alcohol 2,4-dithiobiuret 3,3-dimethyl-l-(methyl thio)- 2-butanone, 0-[(methyl amino) carbonyl] oxime endothal ethyl carbamate ethylenebis dithiocarbamic acid, salts and esters ethylenethiourea 2-fluoroacetamide fluoroacetic acid, sodium salt formic acid hydrazine hydroxydimethylarsine oxide iron dextran lasiocarpine lead subacetate maleic hydrazine raelphalan mercury fulminate methanethiol raethomyl 2-methylaziridine methylthiouracil mitomycin C n-methyl-n'-nitri-n-nitrosoguanidine n-napthyl-2-thiourea N,N-diethyIhydrazine n-nitrodiethanolamine 4-nitroquinoline-l-oxide n-nitroso-n-ethylurea n-nitroso-n-methylurea n-nitroso-n-methylurethane n—nitrosoarcosine n-nitrosomethylvinylamine n—nitrosonornicotine n-phenylthiourea n-popylamine nickel carbonyl nicotine and salts nitrogen mustard-N-oxide and hydrochloride salt nitroglycerine l-(o—chlorophenyl) thiorea o,o,o-triethyl phosphorothionate o,o-diethyl S-methyl ester of phosphorodithioic acid octamethylpyrophosphoramide phenyl mercury acetate phenylenediamine phosphine propylthiouracil reserpine saccharin and salts selenourea streptozotocin strychnine and salts sym-trinitrobenzene tetraethyl lead thiosemicarbazide thiourea thiuram toluenediamine 0-toluidine hydrochloride tris(1-aziridinyl) phosphine sulfide trypan blue uracil mustard warfarin and salts Source: Gosse et al., 1986 80 ------- TABLE 15 ACCEPTABLE RANGES FOR PRECISION AND ACCURACY IN THE EPA CONTRACT LABORATORY PROGRAM Class of Compound Volatiles Acids Base/Neutrals Precision (%) 15 40 50 Accuracy (%) 40 - 50 - 15 - 200 200 200 Source: Keith et al., 1983a. 81 ------- Gurka et al. (1982) summarize the results of an early (pre-1983) performance evaluation performed on the CLP EPA Contract Laboratory Program (CLP) (see Tables 16 and 17). For example, the authors note that at that time several laboratories were unable to detect benzidine and endosulfan II. The results for chloroform, a common waste site contaminant, regarded from a low of 14 ug/1 to a high of 303 ug/1, in comparison with a true value of 120 ug/1. All but one laboratory estimated the concentration as below 70 ug/1. Further, for endrin there was about a five order of magnitude difference between the highest and lowest measurement among the laboratories. These data also indicate a wide variation between laboratories. A similar evaluation is not available for the CLP program at the present time. Isaacson, Eckel, and Fisk (1985) list three factors most likely to account for the low occurrence of many compounds found at waste sites: non-optimum analytical methodologies, degradation of compounds prior to analysis, and incorporation into sample matrices. Low occurrence compounds are those that were either: 1) undetected in the CLP Analytical Data Base of the EPA National Enforcement Investigation Center Data Base or 2) detected at less than one-tenth the average frequency of compound occurrence in each data base. The problem of inter-laboratory differences is also a common problem outside of the CLP. As indicated in Tables 18 and 19, analytical results can vary markedly between laboratories. 82 ------- TABLE 16 CLP PERFORMANCE EVALUATION SAMPLE RESULTS, 1982 Contractor L»boratorle« Conpound Chlorobenzene 1.1,2, 2,-Tetrachloro- ethane Hethylene chloride 1,1, 2-Trlchloro- ethane Chlorofom 1 , 4-Dlchlorobenzene Napthalene Acenapthalene Isophorone llexachlorocyc lo- pentadlene ftenzldlne Dlbenz(a,h)anthracene N-Nltroao-dlphenyl anlne 2-Chloronapthalene 4-Nt tropheaol PentacKlorophenol Phenol 1-BHC p.p'-DDD Endoaulfan II Endrln 1 46 NDb 20 10 14 160 100 40 100 380 ND ISO 330 50 375 210 170 ND 140 ND ND 95 59 99 150 69 ND 41 60 3200 280 ND ND 1300 220 160 220 98 130 213 NO 180 57 110 31 160 42 100 200 100 590 710 42 120 830 170 279 190 82 120 150 300 220 32 63 ND 100 37 140 140 70 660 200 160 80 580 100 360 230 no 100 150 170 300 41 10 65 121 43 ND 133 ND ND 1105 ND 29 926 130 246 429 80 148 ND 224 0.06 51 94 54 130 36 160 170 96 370 ND 10 62 520 130 ND 520 69 130 150 50 180 60 107 58 152 31 116 98 86 ND 747 ND 10 1016 132 443 285 248 ND 218 ND 222 64 18 88 148 61 214 223 109 ND 1818 ND ND 894 I7S ISO 304 II) 61 136 150 159 39 ND 35 148 303 ND 2710 1220 ND 4600 ND 120 13400 1800 2050 1840 1330 SI2 167 ND 212 10 29 76 16 120 39 140 130 75 290 530 ND 160 610 100 285 280 130 ND 200 ND ND II 38 63 69 100 37 96 131 70 222 ND ND 95 493 113 168 238 6 140 130 160 160 12 42 90 55 112 40 285 285 169 ND ND ND ND 1118 220 754 1080 160 99 197 197 217 A 40 68 68 85 50 130 150 84 280 360 20 50 510 120 180 360 120 160 240 20 240 EPA 1 B 39 73 64 115 51 121 129 83 280 441 ND 76 396 103 344 454 104 113 119 190 189 C ^J 99 17 94 40 120 130 100 200 440 33 190 10 130 190 360 75 130 290 ND 220 D a a a a a 186 180 143 328 461 5 237 722 123 144 462 87 S 231 5 345 e 42 90 II 103 40 152 168 106 220 190 8 345 780 157 262 326 82 117 174 23 340 True Value 80 100 160 150 120 260 200 95 300 500 400 175 600 150 400 350 200 150 200 175 250 * Laboratory ~n- did not analyze the aanple for volatile organic*. b ND - Not detected. Source: Gurka et al., 1982. 83 ------- TABLE 17 ANALYSIS OF CLP PERFORMANCE EVALUATION SAMPLE DATA, 1982 Laboratory No. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Compound Chlorobenzene 1,1,2.2-Tetra- chloroethane Methylene chloride 1.1,2-Trlchloro- e thane Chloroform. 1 ,4-Dlchlorobenzene Napthalene Acenapthalene Hexachlorocyc lo- pentadiene Benzldlne Dibenzanthracene N-Nitroso- dlphenylamine 2-Chloronapthalene 4-Nttrophenol Pentachlorophenol Phenol beta-BHC p,p'-DDD Endosulfan II Endrln 1 46 ND 20 10 41 160 100 40 380 ND 180 350 50 375 210 170 ND 140 ND ND 3 57 110 31 160 42 180 200 110 710 42 120 830 170 270 190 82 120 150 300 200 6 51 94 54 130 36 160 170 58 ND 10 62 520 130 ND 520 69 130 150 50 180 9 39.5 ND 35.1 148 30.3 ND 2710 1220 4600 ND 120 13400 1800 2050 1840 1330 512 167 ND 212 True Value 80 100 160 150 120 260 200 95 500 400 175 600 150 400 360 200 150 200 175 250 Mean3 49.5 75 54.2 116.0 44.3 165 160 96 617 78.3 109 851 143 294 368 122 132 186 179 219 Standard Performance Perfornance Deviation Window Window (S.D.) 0.5T 3T Mean +2 S.D. 17.4 29.6 26.3 42 10.7 53.4 69.5 35.8 450 70.9 74.4 309.0 48 169 237 48 33 50 84 87 40 50 80 75 60 130 100 - 47.5 250 200 87.5 300 75 200 175 100 75 100 87.5 125 - 240 300 480 450 360 780 600 285 1500 1200 525 1800 450 1200 1050 600 450 600 525 750 14.7 15.8 1.6 32.3 22.9 58.4 20.2 26.4 0 0 0 249 47 0 0 26 46 86 11 45 84.3 134.0 - 107.0 - 200.0 - 66.7 - 272.0 - 300.0 170.0 1517 - 220 258 1468 239 632 - 842 218 178 286 247 393 The Hated mean values for compounds No. 1 to 5 are baaed on 16 laboratories. The mean values for compounds No. 6 to 13 are based on 16 laboratories and do not Include values reported by laboratory No. 9. Mean values for compounds No. 14 to 20 are based on 17 laboratories and do not Include values reported by laboratory No. 9. Source: Gurka et al., 1982. 84 ------- TABLE 18 SUMMARY OF INTER-LABORATORY COMPARISON Compound Trichloroethylene Tetrachloroethylene Carbon Tetrachloride 1,1,1 trichloroethane 1,2 dichloroethane Vinyl Chloride Benzene 1,4-dichlorobenzene (as VOC) 1,1 dichloroethylene Results (20 ug/1) 23 + 22 + 20 + 22 + 21 + 20 + 21 + 23 + 23 + 3.0 2.6 2.6 3.0 3.5 11.3 3.5 3.9 6.4 Variation (%) 13 12 13 14 17 57 17 17 28 Source: Adapted from Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985. 85 ------- TABLE 19 SUMMARY OF INTER-IABORATORY COMPARISON Compound 2-Chlorophenol 1, 4-dlchlorobenzene (as extractable) Dimethyl Phthalate Heptachlor PCB-1260 Results (200 ug/1) 156 + 47 144 + 56 13 + 5.6* 41 + 159 171 + 73 136 + 58 Variation (%) 30 39 43 388 43 43 *Results for 20 ug/1. Source: Adapted from Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985. 86 ------- An additional problem is that different equipment may yield different results when analyzing the same samples. Geraghty and Miller, Inc. and American Ecology Services, Inc. (1985) present the data listed in Table 20, comparing the results of an analysis of a soil sample using gas chromatography (GC) and GC coupled with mass spectroscopy (MS). The results show that there can be an order of magnitude difference in the analysis of the same sample using different equipment. Overall laboratory variability in ground water contaminant analysis is summarized in Table 21. As indicated in this table, good precision and accuracy can be achieved in laboratories although the laboratory variability for TCE (one of the most common waste site contaminants) is large. Riggin (1983) notes that one problem with many techniques used to analyze air filter and other samples is that the techniques are destructive in nature. This is important since it implies that samples must be collected in sufficient quantity to allow the sample to be split whenever more than one analysis is to be undertaken using a destructive technique. The list of destructive techniques includes gas chromatography/mass spectroscopy, the principal analytical method used to analyze waste samples for organic contaminants. Numerous other problems are noted by various authors. Kirchmer (1983) notes that there are numerous sources of bias and other problems in laboratory analyses. These include: 87 ------- TABLE 20 COMPARISON OF GAS CHROMATOGRAPHY (GC) AND GAS CHROMATOGRAPHY/MASS SPECTROSCOPY (GC/MS) RESULTS (SOIL SAMPLE - ug/kg) Compound 1, 1-Dichloro ethane t-1 , 2-Dichloroethane 1,1, 1-Trichloroethane Tetrachloroethane GC 32 64 240 27 GC/MS 310 1,900 1,200 140 Source: Adapted from Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985. 88 ------- TABLE 21 MAGNITUDE OF LABORATORY VARIABILITY Component Precision (%) Accuracy (%) Indicators pH, Special Conductivity TOG, TOX TON, TOG, COD, IDS Organics Inorganics Nonmetals Metals ICAP Trichloroethylene 10 5-10 10-50 19-48 5-20 4-6 10-25 50 to 1,000 10 5-20 up to 50 up to 50 0-11 2-7 10 50 to 1,000 Source: Geraghty and Miller, Inc. and American Ecology Services, Inc., 1985. 89 ------- • Sample instability • Interferences • Biased calibrations • Biased blank correction Plumb (1984) identifies the following as being of particular importance; impurities in purge gases, potential for compound outgassing, inter-sample contaminant carry-over, and other interferences. McKown, Schalla, and English (1984) also discuss the problem of interferences and contamination, noting that in one occurrence, the benzene concentration in distilled water to be used in field blanks was 33 ug/1. These authors also identify the problem of possible absorption of contaminants during filtration as a problem of concern. 4.3.4 Interpretation As indicated by Schweitzer (1981), interpretation of hazardous waste site concentration data is more of an art than a science. It is a characteristic of such data that different persons can come to different conclusions upon viewing the same data. This phenomena arises for several reasons. First, the variability in the environment and the potential for error discussed previously make interpretation difficult. Second, it is frequently difficult to differentiate background from site-related contaminant concentration, particularly in a highly varying medium such as the atmosphere. As an example consider the ranges of background contaminant concentrations in urban 90 ------- air reported in Riggin (1983) (Table 22). Detecting site emissions in an urban environment in the presence of other sources is a complex task. The applicability of advanced techniques, such as receptor modeling (see, for example, Core, 1981), of such cases awaits consideration. Similarly, the lack of standards for many contaminants (as noted by Zachowskl and Borgianini (1984) and others) makes the interpretation of the risk from contaminant concentrations difficult. Third, at many sites data are lacking on the local direction of flow of the media during and preceding times of sampling. Lacking such data, the designation of a sample as "background" and another as a "site sample" is subjective at best. Fourth, there are no uniformly acceptable methods for analyzing concentration data. Many statistical methods suffer from reliance on unrealistic assumptions, such as normality, and are thus not generally applicable. Recently developed methods, such as variography and kriging (e.g., Moore and Mclaughlin, 1980 and Flatman, 1984), have also been criticized (e.g., Journel, 1984). Finally, it is unreasonable to expect that a single set of techniques for interpreting concentration data can be developed. There is too much variation between sites, too many gaps in background information, and too many deficiencies in interpretive techniques to allow development of a uniformly applicable collection of such techniques. 91 ------- TABLE 22 RANGES OF SELECTED ORGANIC CONTAMINANT CONCENTRATIONS IN URBAN AIR (ppb) Contaminant Concentration Range Methylene Chloride 0.049 - 9.4 Chloroform 0.019 - 5.1 Carbon Tetrachloride 0.11 - 2.9 Trichloroethylene 0.005 - 2.5 Benzene 0.11 - 37.0 Formaldehyde 6.6 - 41.0 Source: Riggin, 1983. 92 ------- 5.0 COSTS This chapter presents a limited discussion of the costs associated with developing concentration data at uncontrolled waste sites. A discussion of the general problems with estimating data development costs is presented followed by discussions of the principal factors that determine site-specific costs. The chapter concludes with an illustrative example of the magnitude of sampling costs. It would be desirable to estimate the resources, both in terms of time and money, necessary to collect representative concentration data, to the limits provided by current technology and knowledge, within the context of a preliminary assessment (PA) and site inspection (SI). Regrettably for reasons discussed below, this cannot be done generically. This chapter presents what information is available in order to provide an indication of a lower bound on the costs of developing representative data. Based on this information, a considerable increase in resources would be needed to collect representative concentration data at all waste sites for all media. Even a ten-fold increase in the current average per-site SI expenditures may not be sufficient. 5.1 Problems in Estimating Costs The first problem in estimating costs for developing representative concentration data is the problem of specifying the necessary degree of representativeness. As indicated in Appendix B, 93 ------- this is a significant problem since representativeness is poorly defined and can only be assessed subjectively. Moreover, the necessary degree of representativeness depends on the objectives of the program the data are to support and the uses to which the data will be put as part of the program. Since the exact objectives of the HRS and the specific role that concentration data are to play within the HRS are still being reviewed by EPA, no clear-cut, unequivocal set of requirements can be stated. For the purposes of this discussion, therefore, the following subjective statement of the representativeness requirements for concentration data will be used: the data will be of sufficient quality to support inferences (either subjectively or through models) of the degree of risk posed by current and near-term releases of contaminants from the sites and resulting exposures. In order to meet this requirement, three-dimensional profiles of contaminant concentrations will be required in both environmental media (i.e., ground water, surface water, air, soils, and sediments) and wastes. The sampling, handling, and analysis process must be performed according to a comprehensive QA/QC procedure. All sample analyses used in the HRS must achieve the standards for accuracy and precision established for the EPA Contract Laboratory Program. Finally, estimates must be developed for all contaminants of concern, to the extent possible given limitations on the state of sampling and analysis technology. 94 ------- Second, as indicated by numerous authors (including Barcelona et al., 1985; Berg, 1982; Claassen, 1982; deVera et al., 1980; Ford, Turina, and Seeley, 1984; Ford and Turina, 1985; Gibb, Schuller, and Griffin, 1981; Gosse et al., 1986; Hanisch and McDevitt, 1984; JRB Associates, 1985; iMason, 1983; Nacht, 1983; Plumb, 1984; Popkin, 1983; Porcella, 1983; Riggin, 1983; Scalf et al., 1981; Sisk, 1981; Turpin, 1983; and U.S. Environmental Protection Agency, 1977, 1985a, and 1985b) numerous site-specific factors play critical roles in determining many of the components of a sampling plan and thus would affect the costs associated with a sampling effort. A partial list of these factors would include: • Types of contaminants present at the site. • Degree of heterogeneity in the environment surrounding the site. • Site characteristics, including location of wastes and release characteristics. • Size of the site and the surrounding potentially affected area. • Demographics of the surrounding population. • Relative importance of various transport and exposure pathways. This problem would not be critical if, in general, there tended to be similarities among uncontrolled waste sites, in terms of these critical factors. Even after a cursory review of the sites on the National Priorities List, one is struck by the wide variety of sites. Sites range from traditional waste disposal sites (e.g., landfills, 95 ------- surface impoundments, piles, tanks, containers, and landfarms) to contaminated sediments, well fields, roads and soil, to identify just a few of the variations encountered during preliminary assessments and site inspections. There have been almost 500 different contaminants identified as being present at the 888 sites proposed or listed on the NPL through Update 5. Sites are located in both urban and rural areas, in both fairly homogeneous and heterogeneous areas. There have been fairly small sites (Kin-Buc Landfill is about 20 acres) and very large sites (BKK Landfill is nearly 300 acres and there are even larger sites measured in terms of square miles). Nearly any setting in the United States may contain a CERCLA waste site. In total, it is not possible to define a reasonably small number of generic "sites" and to thus estimate costs for different cases. However, certain components of total costs, as well as other factors that affect costs, can be evaluated. The following sections address some of these costs and factors with regard to: • Media • Contaminants • Sampling locations and numbers of samples • Unit sampling and analysis costs 5.2 Media The cost of any particular sampling effort depends on the environmental media and waste to be addressed. Total costs for any 96 ------- particular site would not be simply equal to the sum of costs incurred as a result of sampling each applicable media, due to economies of scale in manpower, mobilization, and other cost components. Soil and air sampling could be performed concurrently rather than on separate trips, for example. Based on a subjective assessment of the difficulties to be encountered in developing representative data (as indicated in Sections 2 through 4), as well as the limited data available in reports cited above, an attempt has been made to provide an approximate ranking of the media of concern in terms of the relative costs to collect representative concentration data in each medium. Ground water is probably the most expensive medium in which to sample. Costs to install wells are high, and the background data requirements necessary to ensure development of representative samples are extensive. Unit installation costs are high, and it would appear that in the best of situations a minimum of four wells are needed to obtain valid concentration data (U.S. Environmental Protection Agency, 1977 and 1985b). Further, several wells may have to be installed at each location, each screened in a different part of the aquifer(s) of concern to develop data in all three dimensions. Also, at least three parameters that have been mentioned as prerequisites for sampling (gradient, transmissivity, and conductivity) are expensive to develop on a site-specific basis (see Gerstein, 1986). It is problematic whether regional estimates 97 ------- are sufficiently accurate to be used instead. Overall, the difficulties inherent in ground water sampling and the resulting high unit costs indicate that it would be the most expensive medium from which to develop representative concentration data. Waste sampling is probably the second most expensive type of sampling due to extreme spatial variability, safety considerations, and potentially high unit costs of sampling. Air is probably less expensive, even though it is the most variable medium. Air sampling equipment is fairly well developed for both vapors and particulates. Air sampling to ensure investigator safety is routinely performed during all site investigations (U.S. Environmental Protection Agency, undated) so unit costs should not be too extreme. Finally, it is likely that soil and surface water are the least costly media to sample. Despite its high degree of spatial variability, soil sampling costs are probably relatively low. The high spatial variability would indicate the need for many sampling locations but this could be offset by low unit sampling costs and the potential for compositing samples (see Mason, 1983). Similarly, the high temporal variability and potential for spatial variability in large water bodies would be offset by the low unit sampling costs. Overall, handling and analysis costs should be roughly comparable for each media. These conclusions are nearly consistent with the ordering of costs indicated by JRB Associates (1985) and presented in Table 23. 98 ------- TABLE 23 SUMMARY OF SAMPLING COSTS* Nominal Complex Hydrogeologic Investigation** Case Case Develop plan, select contractors 4,000 8,000 Perform tasks (tasks undefined) 1,000+ 3,000+ Sample wells 5,600+ 10,000 Analyze samples variable variable Report preparation 8,000 16,000 TOTAL (exclusive of analysis costs) 18,600+ 37,000+ Onsite waste sampling Lagoons 1,540+ 12,850+ Drums and barrels 7,040+ 23,400+ Surface water, leachate and sediment, sampling and analysis 6,100+ 9,800+ Air quality sampling and analysis 1,520+ 1,660+ *Exact coverage of costs is unknown. **Note: For comparison, the reader should note the results of a recent (January 1987) EPA Region 1 analysis of data gathering costs which indicates that a current site investigation requires 300-400 hours of technical level of effort hours (including analytical) at a cost of $27,000 to $51,000. Source: JRB Associates, 1985. 99 ------- The validity of the JRB Associates cost data, however, could not be verified as the report provides little, consistent documentation concerning their underlying assumptions or derivation. 5.3 Contaminants One of the principal determinants of the cost to develop representative concentration data at a site is the list of contaminants whose presence is suspected at or near the site. This list includes, for any given site, not only the contaminants known to have been deposited on the site, but also any of their transformation products that might pose a risk as well. Analysis of additional contaminants may also be required to support advanced interpretive techniques (e.g., receptor modeling). As discussed in Section 2, in many cases special monitoring instruments are required to measure the concentration levels of many of these contaminants. Also, it is important to note in this context that there are over 700 substances that are considered hazardous under CERCLA. Gosse et al. (1986) present a partial list of these contaminants and the principal media of concern for each (see Table 24). The EPA Contract Laboratory Program analyzes for only 130 organic contaminants plus 27 metals and cyanide as part of their routine analysis of water and soil samples. Special analytical services to address additional contaminants (e.g., PCB or TCDD) are also available on a special request basis. 100 ------- TABLE 24 RECOMMENDED MEDIA IN WHICH TO SAMPLE RCRA APPENDIX VIII HAZARDOUS CONSTITUENTS Ground water acenaphthalene acenaphthene acetaldehyde acetonitrile acetophenone 2-acetylaminof luorene acetyl chloride acrolein acrylonitrile aldrin allyl alcohol alpha-BHC aluminum phosphide 4-aminobiphenyl aniline anthracene antimony (total) aramite aroclor 1016 aroclor 1221 aroclor 1232 aroclor 1242 aroclor 1248 aroclor 1254 aroclor 1260 arsenic (total) arsenic acid arsenic pentoxide arsenic trioxide asbestos barium (total) barium cyanide benz(a)anthracene benzene benzene, dichloromethyl benzenethiol benzidine benzo(a)pyrene benzo( b ) f luoranthene benzo(ghi)perylene benzo(k) fluoranthene p-benzoquinone X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated Subsurface soil gas Air X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Source: Gosse et al., 1986. 101 ------- TABLE 24 (Continued) Ground water benzot rich lor ide benzylchloride beryllium (total) beta-BHC bromodichlorome thane b romome t hane 4-bromophenyl phenyl ether 2-butanone peroxide butyl benzyl phthalate 2-sec-butyl-4,6- dinitrophenol cadmium (total) calcium chromate calcium cyanide carbon disulfide carbon oxyfluoride carbon tetrachloride chloral chlordane chloroacetaldehyde p-c hlo roan i line chlorobenzene chlorobenzilate 2-chloro-l , 3-butadiene p-chloro-m-cresol chlorodibromome thane chloroethane b is ( 2-c h loroethoxy ) methane bis(2-chloroethyl) ether 2-chloroethyvinyl ether l-chloro-2 , 3-epoxypropene chloroform bis(2-chloroisoprpyl ) ether chlorome thane bis(chloromethyl ) ether chloromethyl methyl ether 2-chloronapthalene 2-chlorophenol 3-chloropropene X X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Subsurface gas Air X X X X X X X X X X X Source: Gosse et al., 1986. 102 ------- TABLE 24 (Continued) Ground water 3-chloropropionitri le chromium (total) chrysene copper (total) copper cyanide crotonaldehyde creosol cumene cyanide cyanogen cyanogen bromide cyanogen chloride ODD DDE DDT delta-BHC deno(l ,2, 3-cd)pyrene di-n-butyl-phthalate di-n-octyl phthalate di-n-propylnitrosamine dibenzo(a,e)pyrene dibenzo(a.h) anthracene dibenzo(a,h)pyrene dibenzo(a, i)pyrene 1 , 2-dibromo-3-chloro- propane dibromome thane 1 , 2-dibromoethane tris (2 , 3-dibromopropyl ) phosphate m-dichlorobenzene o-dichlorobenzene p-dichlorobenzene 3, 3 '-dichlorobenzidine trans-l,4-dichloro- 2-butene dichlorodif luoro- me thane 1, 1-dichloroethane 1 ,2-dichloroethane trans-1 ,2-dichloroethene 1 , 1-dichloroethylene 1 , 2-dichloroethylene X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Subsurface gas Air X X X X X X X X X X X X Source: Gosse et al., 1986. 103 ------- TABLE 24 (Continued) Ground water die h lor ome thane 2 ,4-dichlorophenol 2 ,6-dichlorophenol 2 ,4-dichlorophenoxy- acetic acid 1 , 2-dichloropropane cis-1 ,3-dichloropropane trans-l,3-dichloro- propene dieldrin o,o-diethyl o-2-parazinyl phosphor othionate o,o-diethyl phosphoric acid, o-p-nitrophenyl ester diethyl phthalate diisopropylf luoro- phosphate 3, 3'-dimethoxybenzidine dimethoate p-dimethylaminoazo- benzene 7, 12-dimethylbenz(a) anthracene dimethyl benzene 3,3'-dimethylbenzidine dimethylcarbatnoyl chloride 1 , 1-diraethylhydrazine 1 , 2-dimethylhydrazine , -dimethylphenethyl- amine 2,4-dimethylphenol dimethyl phthalate dimethyl sulfate m-dinit robenzene 4, 6-dinitro-o-cresol 2,4-dinitro phenol 2, 4-dinitro toluene 2,6-dinitrotoluene 1 ,4-dioxane diphenylamine 1 , 2-diphenylhydraz ine X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated Subsurface soil gas Air X XX X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Source: Gosse et al., 1986, 104 ------- TABLE 24 (Continued) Ground water disulfoton endosulfan I endosulfan II endrin endrin aldehyde ethyl benzene ethyl cyanide bis(2-ethylhexyl) phthlate ethyl methacrylate ethyl methanesulfonate ethylene oxide ethyleneimine famphur f lourene fluoride fluorine fluouranthene formaldehyde garama-BHC g lye idyl aldehyde heptachlor heptachlor epoxide hexachlorobenzene hexachlorobutadiene hexachlorocyclo- pentadiene hexachlorodibenzo-p- dioxins hexachlorodibenzofurans hexachloroe thane hexachlorophene hexachloropropene hexaethyltetraphosphate hydrocyanic acid hydroflouric acid hydrogen sulfide icocyanic acid, methyl ester iodome thane isobutyl alcohol isodrin X X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated Subsurface soil gas Air X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Source: Gosse et al., 1986. 105 ------- TABLE 24 (Continued) Ground water kepone lead (total) lead acetate lead phosphate maleic anhydride malonitrile mercury (total) methacrylonitrile methane met hapyri line methoxychlor 3-methycholanthrene methyl acetate 2-methylactonitril 4)4'-methylene bis (2-chloroaniline) methyl ethyl ketone methyl hydrazine methyl methacrylate methyl tnethanesulfonate methyl parathion mustard gas napthalene 1 ,4-napthoquinone 1-napthylamine 2-napthylamine nickel (total) nickel cyanide 4-nitophenol nitric oxide p-nitroaniline nitrobenzene nitrogen dioxide nitrogen mustard and hydrochloride salt n-nitrosodi-n- butylamine n-nitroso diethylatnine n-nitrosodimethylamine n-nitrosodiohenyl- amine n-nitroso raethy lethyl- amine X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Subsurface gas Air X X X X X X X X X Source: Gosse et al., 1986. 106 ------- TABLE 24 (Continued) Ground water n-nitrosomorpholine n-nitrosopi peri dine n-nitrosopyrrolidine 5-nitro-o-toluidine ortho cresol osmium (total) osmium tetroxide para cresol paradelyhe parathion pentachlorobenzene pent achlo rod ibenzo-p dioxins pentachlorodibenzo- furans pen tachloroe thane pentachloronitrobenzene pentachlorophenol phenacetin phenanthrene phenol phorate phosgene phthalic anhydride 2-picoline potassium cyanide potassium silver cyanide pronamide 1,3-propane sultone propylene oxide 2-propyn-l-o pyrene pyridine resorcinol safrole selenium (total) selenium sulfide seleniuos acid silver (total) silver cyanide silvex X X X X X X X X X X X X X X X X X X X X X X X X X X X X Surface water X X X X X X X X X X X X X X X X X X X X X X X X X X X X Saturated soil X X X X X X X X X X X X X X X X X X X X X X X X X X X X Unsaturated Subsurface soil gas Air X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Source: Gosse et al., 1986. 107 ------- TABLE 24 (Continued) Ground Surface Saturated Unaaturated water water soil soil sodium cyanide strontium sulfide sulfide 2,4,5-T 1,2,4, 5-tet rach loro- benzene 2,3,7, 8-tetrachloro- dibenzo-p-dioxin tetrachlorodibenzo-p- dioxins tetrachlorodibenzo- furans tetrachloroethene 1,1,1, 2-tetrachloro- ethane 1,1,2, 2-tetrachloro- ethane 2,3,4,6-tetrachloride tetraethyldithio- pyro phosphate tetraethylpyrophosphate t e t ran i t rome t hane thallic oxide thallium (I) acetate thallium (I) carbonate thallium (I) chloride thallium (I) sulfate thallium (total) thallium selenite t hioacetamide toluene toluene diisocyanate toxaphene t ribromome thane 1 ,2 ,4-t rich lor obenzene t richloroethene 1,1, 1-t rich loroe thane 1,1,2-trichloroethane trichlorome thane thiol t rich lor omonof luoro- methane 2,4, 5— t rich lor ophenol X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Subsurface gas Air X X X X X X X X X X X X Source: Gosse et al., 1986. 108 ------- TABLE 24 (Concluded) Ground Surface Saturated Unsaturated Subsurface water water soil soil gas Air 2,4,6-trichlorophenol 1,2, 3-t rich loropro pane vanadic acid, ammonium salt vanadium (total) vanadium pentoxide vinyl chloride xylenes zinc (total) zinc cyanide zinc phosphide X X X X X X X X X X X X X X X X X X X X X X X X X X X Source: Personal correspondence with Robert April (EPA-OSW-LDB). "Guidance on Issuing Permits to Facilities Required to Analyze Ground Water for Appendix VIII Constituents." Source: Gosse et al., 1986. 109 ------- 5.4 Number of Sampling Locations The required number of sampling locations (in three dimensions) needed to achieve representative samples depends heavily on site and waste specific conditions. The two most critical site specific factors are the size of the potentially affected area and the size of the zones of homogeneity at the site. A zone of homogeneity (in three dimensions) is a volume of space in which it can be assumed that the distribution of contaminant, in the medium in question is homogeneous. Since each zone of homogeneity must be sampled in at least one location, the number of sampling locations must generally exceed the ratio of these two sizes. Moreover, multiple samples should be taken within each zone of homogeneity to account for sampling and other random errors. Statistical sampling theory provides some approaches for estimating the number of samples needed within each zone, depending on the desired level of confidence. However, most of these approaches depend on assumptions that are, at best, unlikely to be true about contaminant concentrations at uncontrolled waste sites (e.g., normality of the contaminant distribution). Further, they also require some knowledge about the parameters of the distribution such as the coefficient of variation which is almost always unknown. Overall, there is no objective set of approaches that can be employed routinely to estimate the number of sampling locations needed at a given waste site. Judgment is required. 110 ------- As an example of the number of sampling locations that might be required to sample ground water, the draft RCRA Ground-Watej: Monitoring Technical Enforcement Guidance Document of August 1985 (U.S. Environmental Protection Agency, 1985b) indicates that a minimum of four wells are required (one upgradient, three downgradient) while a spacing of one well each 150 feet (or less) is required whenever, for example, liquid wastes are present. This density of wells is required to support a detection monitoring system, i.e., one that would detect a release, but not necessarily characterize the concentrations of that release from the site. In general, more wells would be needed to assess the extent and concentrations of a release. The installation of even four wells would be expensive in terms of current site inspection costs at many sites (see Gerstein, 1986). As another example, Hanisch and McDevitt (1984) present a method for estimating the number of sampling locations required in a zone of homogeneity of area A (in square meters). In their equation, the 1/2 number of locations must exceed 6 + 0.1A . Thus, the number of 2 sampling points in a homogeneous zone of size 10,000 m in a surface impoundment of area must exceed 16. 5.5 Number of Samples Per Location There are three aspects to consider in determining the number of samples to be taken at each sampling location: frequency, duration, and replication. The first two are determined by the 111 ------- temporal variability of the contaminant concentrations in the potentially affected area and the type of health (and other) effects expected as a release of the release (e.g., acute or chronic). For example, assessments of chronic effects risks might require long-term average concentrations requiring possibly less frequent samples over a long period of time, while assessments of acute effects risks may require that a great many samples be taken in a short period of time. In between, the assessment of risks of subchronic effects may require fairly frequent sampling over a relatively long period of time. Replication, the third aspect to the number of samples, addresses the need take multiple samples to account for uncertainty brought on by random sampling errors. With the exception of replication, there are again no objective approaches to assessing the frequency or duration of sampling. However, representative sampling would, in principle, require a fairly large number of samples at each location, if for no other reason than to account for random errors. Provost (1984) presents a table that is useful in estimating the sampling frequency needed to achieve specified confidence intervals about a mean as a function of a known coefficient of variation and an assumption about the underlying distribution (see Table 25). As indicated in this table, for example, 24 samples from a normally distributed process with a coefficient of variation of 50 percent would yield a 95 percent confidence interval about the 112 ------- TABLE 25 EXPECTED CONFIDENCE INTERVALS FOR A PARAMETER MEAN AS A FUNCTION OF NUMBER OF SAMPLES Expected Confidence Intervals for a Parameter Mean aa a Function of Number of Samples (Measurements) Expected Variability Measurement (Coefficient of Variation 51 10Z 25Z 50Z 100Z 200Z 500Z 1000Z 10000Z of 95Z Confidence Interval About the Mean Estimate ( percent )b Distribution n - 4 )a (Model) (Quarterly)c Normal Model Lognormal Model Normal Model Lognormal Model Normal Model Lognormal Model Normal Model Lognormal Model Normal Model Lognormal Model Lognormal Model Lognormal Model Lognormal Model Lognormal Model +8.0 +8.1, -7. 5 +15 +17, -15 +40 +48, -32 +80 +110, -53 +160 +280, -73 +650, -87 +1700, -94 +3000, -96 +13000. -99 n - 6 n - 12 (Bl-monthly)c (Monthly)0 +5.2 +5.4", -5.1 +11 +11, -9. 9 +26 +2 9, -23 +52 +62, -39 +110 +104, -58 +280, -74 +570-85 +900-90 +2300, -96 L _ _- +3.2 +3. 2, -3.0 +6.4 +6. 5, -6.1 +16 +17, -14 +32 +35, -26 +64 +70, -41 +124.-55 +220, -68 +300, -7 5 +590, -85 n - 24 n - 52 (Seml-monthly)c (Weekly)c +2.1 +2.1, -2.0 +4.2 +4. 3, -4.1 +11 +1 1 , -9 . 9 +21 +22, -18 +42 +42, -30 +71, -42 +120, -53 +150, -60 +260, -7 2 +1.4 +1.4 +2.8 +2. 8, -2. 7 +6.9 +7.1,6.6 +14 +14, -12 +28 +26, -21 +43, -30 +65, -40 +82, -4 5 +130. -57 n - 365 (Dally)c +0.5 +0.5 +1.0 +1.0 +2.6 +2. 6, -2. 5 +5.2 +5.0, -4. 8 +11 +9.0, -8. 2 +14, -12 +20, -17 +24, -20 +37, -27 value for the coefficient la assumed In this table. If the coefficient of variation Is greaterthan 100Z, the normal model Is not realistic. bn - number of samples or data points. cMonltorlng frequencies required for the specific value of n If the duration of study was one year. Source: Provost, 1984. ------- mean of about 21 percent. This means that in practice if semi- monthly samples were taken at a sampling location that experienced temporal variations of 50 percent (expressed as the coefficient of variation), then one would be 95 percent confident that the true average lay within 21 percent of the sample average. 5.6 Unit Sampling, Handling, and Analysis Costs The development of generic cost estimates is also hampered by a lack of data on unit costs for background information collection, sampling, handling, and analysis in many of the media and under the conditions applicable to uncontrolled waste sites. The compilation of such a unit cost data set is beyond the scope of this report. However, some unit costs estimates were identified as part of this review. Additional unit cost information concerning ground water sampling can be found in Gerstein, 1986. Few cost data concerning background information collection could be collected. The only indication of the magnitude of these costs is the current cost of Preliminary Assessments. These assessments currently cost approximately $1,200 per site. It is likely that the cost of background information to support representative data development (e.g., ground water flow direction) would be substantially higher. Some very limited information is available on sampling, handling, and analysis costs. As discussed previously, Table 23 presents cost data derived from JRB Associates, 1985. The quality 114 ------- of these data is unknown, given the lack of adequate documentation. Further, based on the limited documentation provided in that report, some of the estimates (e.g., the estimates for air sampling) appear to be unreasonably low when compared with the requirements of representative data development. It should be stressed, however, that the JRB Associates report is a draft report. Table 26 presents an example of the costs to establish a ground water sampling well field consisting of 10 wells drilled to a depth of 100 feet each (adapted from Gerstein, 1986). A representative mobilization cost (including plan development, contracting, and other administrative costs) is estimated to be about £6,000. A representative cost to install each well is estimated to be $4,000 (or about $40 per foot). Unit costs cited in the literature ranged from $30 per foot to $100 per foot (JRB Associates, 1985 and U.S. Environmental Protection Agency, 1985c). A representative cost to determine hydraulic gradient by potentiometric mapping (a necessary prerequisite to sampling) is estimated as $4,500. A representative cost to determine hydraulic conductivity (a second necessary prerequisite) by either a bailing test or a slug test is estimated to be ijl,500 per well, or $15,000 overall. These costs do not include costs for site security or disposal of drilling waste (a potentially hazardous waste regulated under RCRA), nor do they include any increased costs that might result from additional concerns for worker safety over and above normal drilling risks. 115 ------- TABLE 26 EXAMPLE REPRESENTATIVE PRE-SAMPLING COSTS TEN-WELL SAMPLING FIELD Cost Component Costs ($)* Mobilization Well installation (10, 4-inch diameter wells, 100 feet deep) Potentiometric Mapping Conductivity Tests (10 wells at $1500/well, slug or bail test Total 6,000** 40,000 4,500 15,000 65,500 *Costs do not include site security, disposal of drill spoils, or additional costs associated with worker safety. **Note: EPA Region 1 currently (January 1987) experiences a $55,000 mobilization fee for a ten-well drilling program, in addition to costs of drilling and installation of wells. Source: Gerstein, 1986. 116 ------- EPA Region 1 currently experiences a $55,000 mobilization fee for a 10-well drilling program, in addition to the cost of drilling and installation of wells. Consistent unit cost information for collecting ground water samples is not available. JRB Associates (1985) listed costs ranging from $300 to $400 per well. The average costs for RCRA Interim Status facilities is estimated to be $200 per well (U.S. Environmental Protection Agency, 1985c). The assumptions concerning the number of samples taken and the cost component (e.g., manpower) included in both these estimates are unknown. In contrast, consistent information was available on the cost of analyzing water and soil samples using the CLP (Kolb, 1986). The current average analytical cost for the standard organic and inorganic analyses are about $960 and $140, respectively. The costs for special analytical services are variable. Finally, little information was available on the cost of QA/QC programs, although Schweitzer (1981) states that quality assurance costs range from 0 to 20 percent of monitoring costs. 5.7 Illustrative Example To put this information into perspective, consider as an example the 10-well field discussed above. If the ground water were subject to a temporal variation of 10 percent (expressed as the coefficient of variation) during the period of concern and a 95 percent confidence interval of +15 percent were desired, then, under a 117 ------- normality assumption, 4 samples would be required at each well (see Table 25). Thus, a total of 40 samples would be required at an expected analysis cost of J>44,000. Assuming (probably conservatively) that the sampling costs for these samples was $200 per well, a cost of $2,000 would also be incurred. Thus, assuming the 10 wells provided spacially representative data, the total cost to develop representative concentration data under this scenario (for ground water only) would exceed itllO,000, exclusive of handling, QA/QC, interpretation, and administrative costs. Average total costs to develop representative data over all media can only be inferred, at best, from this limited information. 118 ------- 6.0 SUMMARY OF PRECEDING DISCUSSIONS AND IMPLICATION FOR THE HRS Representative data is necessary to have a high degree of confidence in decisions made based on the results of analyses on that data. The lower the degree of representativeness (i.e., the lower the quality), the higher the uncertainty in the results and the lower the confidence in the decisions. The point at which the degree of representativeness of the data becomes too low to support the decisions to be made is determined by the decision-maker. Thus, it is EPA's responsibility to determine if the concentration data developed as part of PA/SIs is of sufficient quality to support particular uses of that data in the HRS to aid in deciding whether a site is placed on the NPL. However, as indicated previously, truly representative data may be very expensive to develop at some sites and may be beyond the capabilities of the program to develop routinely. Many factors act to limit the quality of PA/SI concentration data, thereby increasing its uncertainty. Some factors are inherent in the nature of concentration data; such data alone cannot indicate future conditions, the data rarely reflect actual exposure concentrations, and there is always a chance that actual concentrations are significantly higher or lower. Other factors are programmatic in nature. They arise from constraints on time and resources, variations and limitations in the level of experience of those evaluating sites, and from any gaps in a comprehensive QA/QC 119 ------- program. Still others are technological in that there are gaps in sampling equipment and standard analytical techniques for some field situations and contaminants. A fourth set of factors arise from difficulties in the acquisition, handling, analysis, and interpretation of samples and sample data. There are numerous opportunities for introducing error into the development of concentration data. Undetected temporal and spatial variation in environmental processes induce potentially undetected variation in environmental concentrations. The lack of information on these processes at each site increases the uncertainty associated with concentration data developed for that site. Further, without careful management, it is likely that samples will not be representative of in-situ conditions and that they will become contaminated. These problems of sampling management arise in all areas except the interpretation component of the data development process. Uncertainty in results is further increased by the necessary assumptions that must be made in order to analyze sampling results. The degree to which these assumptions diverge from reality, increases the uncertainty still further. Overall, there are numerous reasons to question the representativeness of even the best concentration data set, i.e., those data sets that have been carefully developed and analyzed subject to an extensive QA/QC program. Data developed without such QA/QC can, at best, be considered suspect. 120 ------- This discussion indicates that the role that concentration data play in the HRS and in NPL decision-making should not be too extensive, even if a good QA/QC program were to be implemented as part of the PA/SI program. Concentration data should be only one of many factors considered in evaluating the risk posed by a site at this stage of the assessment process. Further, the limitations in the data that could reasonably be developed from a site inspection program on a routine basis indicate that any concentration data factors should not be weighted heavily in the HRS. 121 ------- 7.0 OPTIONS FOR EMPLOYING CONCENTRATION DATA This chapter presents several options for using concentration- based factors in the HRS. These factors are designed to improve the accuracy of the HRS in evaluating risk without exceeding the limitations in concentration data discussed in the previous chapters. The discussion also identifies changes in the site inspection program that should be implemented if the options are incorporated into the HRS. Without these programmatic changes, the uncertainty in the concentration data would be very high and the use of these concentration data in the factors presented would be questionable. 7.1 Basic Philosophy A combination of factors determined the basic philosophy towards employing concentration data that is reflected in the options discussed below. These factors include the possible objectives of the HRS, the wide variation in the characteristics of uncontrolled waste sites and the limitations in concentration data discussed previously. The objective of the HRS is assumed to be to expeditiously identify sites for possible response action based on their relative risks (U.S. House of Representatives, 1986). The objective requires that the HRS be applicable to all potential CERCLA sites. This, in turn, requires that any concentration factors be applicable to all sites as well. In the interest of maintaining simplicity in the HRS, no special options were developed to assist in evaluating the occasional sites with extensive 123 ------- concentration and other environmental data. Rather, the options and factors discussed below employ data that could be collected at any site within the constraints of a reasonable site inspection. The basic approach embodied in all of the options is to assign additional points to sites with current problems, as indicated by concentration data, without putting at a disadvantage those sites that appear to lack current problems (as indicated by available concentration data). There are several reasons for adopting this type of approach. First, as discussed previously, sampling by its nature is retrospective. It indicates past problems only. The data can be used to infer present or future problems only by the use of either implicit or explicit environmental models. Alone, concentration data tell nothing about future problems. Second, environmental concentration data can only be employed when they also demonstrate an observed release. Concentrations that do not exceed background levels cannot be reliably associated with the site in question. Thus, the risk posed by these concentrations cannot be associated with the site and should not be included in the evaluation of the risk posed by the site being evaluated. Third, it is a characteristic of any statistical analysis that many low values do not completely rule out the existence of high values. This is embodied by the statement that "lack of evidence is not evidence of lack". Fourth, the data collected during site investigations can rarely be considered as representative in all media. The cost and 124 ------- time requirements associated with developing concentration data that is representative of environmental concentrations in both space and time across the five media of concern are likely to be excessive. Finally, the uncertainty in the environmental concentration data developed during site inspections is such that the measured data indicate at best the lower limit of the maximum possible exposure concentrations, even considering possible dilution and mass removal effects. If a particular contaminant concentration is measured in the environment then the potential clearly exists for someone to become exposed to that concentration either at the time the measurement was taken or at some time in the future. Thus, for a given contaminant, the maximum detected concentration determines a "worst-known-case" of potential exposure. Moreover, the uncertainty in the data generally indicate that the possibility exists for true environmental concentrations to exceed detected concentrations either at the same location (due to sampling, handling and analysis uncertainty), at some other location (due to spatial variation), or at some other time (due to temporal variation). It is unlikely that sampling will find the true maximum concentration. For similar reasons, the maximum detected waste concentration indicates a lower bound on the maximum possible waste concentration. These considerations taken together indicate that little reliance should be placed on low concentration values determined during site inspections in determining that little risk exists from 125 ------- the site. However, the existence of high concentration values does indicate that some risk may exist. Thus, the approach taken in these options is that sites with "high" observed contaminant concentrations should be assigned extra points while those with "low" contaminant concentrations should not be overly penalized. The definitions of "high" and "low" concentrations require the determination of benchmarks against which to assess the measured concentration values. 7.2 Benchmarks Benchmarks determine whether an observed concentration of a contaminant can be considered to be "high" or "low" (or "medium," etc.). Benchmarks establish a metric to gauge the relative magnitude of observed concentrations. For example, a concentration of 3 4,000 mg/m of sulfur hexafluoride in a workplace might be 3 considered low while a concentration of 500 mg/m of trichloro- ethylene in the same workplace would be considered high. In the former case the concentration is below the threshold limit value (TLV) of 6,000 mg/m3 of sulfur hexafluoride while the latter 3 concentration exceeds the trichloroethylene TLV of 270 mg/m (American Conference of Governmental Industrial Hygienists, 1985). Thus, within the context of employing concentration data within the HRS, risk-related benchmarks have to be determined. These benchmarks need to be determined for each chemical of interest in a consistent fashion. Further, since the HRS employs separate 126 ------- migration pathways (and to a lesser degree exposure pathways in evaluating toxicity) and since the risk posed by an exposure to a given concentration of a contaminant frequently differs depending on whether the contaminant is ingested or inhaled, separate pathway specific benchmarks have to be developed. Additionally, since the HRS addresses both human health and environmental risks, separate benchmarks reflecting these two types of risk may have to be developed for each contaminant and pathway. The feasibility of developing a collection of suitable benchmarks for use in the HRS is problematic and remains an important outstanding issue in the use of concentration data in the HRS. The options discussed below assume that an acceptable set of benchmarks can be developed. The development of such benchmarks is beyond the scope of this paper. 7.3 Options Options for employing concentration data in the HRS were developed in each of the three evaluation categories: release, waste characteristics, and targets. The options were developed so as to be employable in any of the HRS migration pathways. No special ground water, surface water, or air options were developed. The options are discussed, by HRS factor category, in the following sections. 7.3.1 Options in the HRS Release Category The HRS currently employs concentration data in determining whether an observed release has occurred. The benchmark in this 127 ------- case is the background contaminant concentration. A release category value of 45 is assigned whenever the observed site concentration significantly exceeds the background concentration in the medium being examined, else, the site is evaluated based on its potential to release. The maximum potential to release value is also 45. An alternate approach of similar structure can be readily defined employing a risk based benchmark as well as the background benchmark, as follows. If the observed concentration of any contaminant in the environment* significantly exceeds the background concentration for that contaminant (i.e., constitutes an observed release) and also exceeds a benchmark concentration for that contaminant and pathway, then a maximum observed release value of, for example, 45 would be assigned. If the observed concentration significantly exceeds the background concentration but is lower than the benchmark, then a lower value of, for example, 40 would be assigned. If the observed concentration does not significantly exceed the background concentration, then the site would be evaluated based on its potential to release since no observed release can be attributed to the site. The maximum potential to release value might be set equal to the value for an observed release that does not exceed the benchmark or it might be set equal to the maximum observed release value. Either variation is reasonable. *Waste concentrations cannot be used to evaluate the release category. 128 ------- Table 27 illustrates this scoring approach. At both Sites 1 and 2, the observed site concentrations significantly exceed background and exceed the benchmark as well. Thus, a release category value of 45 is assigned to both the sites. At Sites 3 and 4, the observed concentrations exceed background, but do not exceed the benchmark. Thus, these sites are assigned values of 40. At Sites 5 and 6, the observed concentrations do not significantly exceed background and hence the sites are assigned values of 0 regardless of whether the observed concentrations exceed the benchmark. (It is noted that a background level above the benchmark would presumably trigger an investigation to identify an alternate source.) A shortcoming of this approach is evident in comparing the last two hypothetical sites (7 and 8). At both sites, the observed site concentration of the contaminant in question significantly exceeds the background concentration. Thus, observed releases have occurred at both sites. Also, the observed concentration at Site 7 significantly exceeds the benchmark while at Site 8 it only slightly exceeds the benchmark. Therefore, Site 7 poses a much greater risk than Site 8, in principle, due to the presumably higher concentrations to which the people around the site will be exposed, all other factors being the same. Thus, Site 7 should receive a higher value, in principle, than Site 8. However, due to the structure of this option both sites would receive the same release category value (45) and site pathway scores, all other factors being the same. This consideration argues for a 129 ------- TABLE 27 HYPOTHETICAL EXAMPLES OF RELEASE CATEGORY OPTION Site 1 2 3 4 5 6 7 8 Benchmark Concentration 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Background Concentration 0.1 1.0 0.01 0.01 5.0 0.1 1.1 0.1 Site Concentration 2.0 10.0 0.5 0.1 5.0 0.1 11.0 1.1 Assigned HRS Value 45 45 40 40 0 0 45 45 130 ------- more refined evaluation approach employing varying levels relative to the benchmark with associated levels of valuation (e.g., one-tenth of the benchmark could be assigned one-tenth of the value, i.e., 4.5). However, such an option is not presented here since it would place too great a reliance on the concentration data in determining scores. Using data of debatable validity in such an important fashion would be questionable. One should note that the adoption of this option would change somewhat the role that the release category plays in the HRS. Currently, the release category reflects the likelihood that the site has, is, or will release a significant quantity of contaminants into the environment. By establishing two levels of release values, an implicit evaluation of the magnitude of the release is made current, detected releases above benchmarks are evaluated higher than potential future releases or undetected, current releases that may or may not exceed benchmarks. Thus, the release category would address the probabilistic aspects of risk as well as a component of the hazard aspects. 7.3.2 Options in the HRS Waste Characteristics Category Two options for reflecting concentration data in the waste characteristics category were developed. The first envisions a separate concentration factor, the value of which could be added to the toxicity and waste quantity factor values to determine the overall waste characteristics value. As in the previous options, 131 ------- this factor would be evaluated based on environmental concentration data, not waste constituent concentration data. The second envisions modifying the waste quantity factor, changing it to reflect the quantity of hazardous constituents found at the site rather than the quantity of wastes containing hazardous substances. This latter option uses waste concentration data. A third option for incorporating concentration data in the toxicity factor is also discussed. This option is presented as an example of a potential approach that requires strict confidence in the representativeness of the concentration data. In the first option, the maximum detected environmental concentration of each contaminant in an observed release would be compared with both the background concentration for that contaminant and the benchmark concentration. Those concentrations that do not significantly exceed background (and thus are ilot "observed releases") would be rejected from further consideration in evaluating factors related to environmental concentrations. If all concentration data are rejected or if no concentration data are available, then the concentration factor is assigned a value of 0. For each remaining concentration datum, the ratio of the datum to the benchmark is calculated and the contaminant with the highest ratio chosen. The concentration factor would then be evaluated based on the calculated ratio for that contaminant using a factor table such as is illustrated in Table 28. This option is designed 132 ------- TABLE 28 ILLUSTRATIVE CONCENTRATION FACTOR TABLE* Ratio (0/B) Factor Value Greater than 1 5 0.1 - 1.0 4 Less than 0.1 0 *Values are provided for illustrative purposes only. B: Benchmark concentration. 0: Observed site concentration. 133 ------- to be used as an addition to the toxicity factor. An example of the approach is given in Table 29. The concentration of three contaminants in Table 29 (contaminants 1, 2, and 3) significantly exceed background and can be used in evaluating the concentration factor under this option. Since the maximum site concentrations of contaminants 4 and 5 do not significantly exceed background, these concentrations cannot be attributed to the site and hence would be rejected from further consideration in evaluating the concentration factor. This rejection is indicated despite the high site to benchmark concentration associated with contaminant 4. There is probably a risk at the site due to high environmental concentrations of contaminant 4, yet it cannot be unquestionably associated with the site. Given the high background concentrations, it is equally probable that the risk arises from other contaminant sources. The ratios of the concentrations of the three contaminants are calculated and the contaminant with the largest ratio is identified (contaminant 2, ratio 20). Using the illustrative factor table presented on Table 28, the concentration factor score for this site would be 5. Although the values listed in Table 28 are illustrative and subject to change, two relationships embodied in the example table are important and should be maintained if the option is adopted. First, the maximum score (5) is smaller than the current maximum 134 ------- TABLE 29 HYPOTHETICAL EXAMPLES OF CONCENTRATION FACTOR OPTION* Contaminant 1 2 3 4*** 5*** Benchmark Concentration 1.0 0.5 0.1 1.0 1.0 Background Concentration 0.1 1.0 0.01 45.0 0.1 Maximum Site Concentration 2.0 10.0 0.1 40.0 0.1 Ratio** 2 20 1 40 1 *Environmental sample. **Rejected since detected concentrations do not demonstrate an observed release. ***Ratio of maximum site concentration to benchmark concentration. 135 ------- scores for the toxicity factor (18) and the waste quantity factor (8). This embodies the conclusion that due to the uncertainty associated with concentration data and the associated inferences about current and future risk, this factor is less important than the others in determining the site pathway score. Also, it minimizes the disadvantage associated with sites that lack observed releases. Second, a relatively small ratio (e.g., at least one-tenth of the benchmark) is needed to receive nearly the maximum value for the factor. This reflects a belief that the uncertainty in concentration data is high and that concentration measurements near the benchmark (i.e., within one-tenth of the benchmark) indicates the probable presence of an exposure situation of concern. These relationships are consistent with the basic philosophy discussed previously. In the second option, the waste quantity factor would be evaluated based on either the total quantity of wastes containing hazardous substances at the site or the total quantity of hazardous substances found in the wastes at the site. The former approach is that currently used in the HRS. It would be employed whenever detailed, complete, representative data on waste constituent concentrations are lacking at the site. The latter approach could be taken only if such data were available. Distributions of the concentrations of the waste constituents would be developed from the waste analyses. The mean (or some other measure of tendency such as the median, the mode, or the 95th percentile) of the distribution of 130 ------- each substance would then be calculated and multiplied by the total waste quantity to yield the quantity of that substance present at the site. The sum of the quantities of each substance would then be calculated and used to evaluate the waste quantity factor.* The principal difficulty with this approach is the data requirement. Such analyses are rarely available as they are difficult and hazardous to perform, as discussed in Section 4. An alternate approach would be to use the highest concentration of each hazardous constituent detected in the waste instead of some parameter of the distribution. These concentrations would then be multiplied by the total quantity of wastes present to yield the quantity of each substance present. These quantities would then be summed to form an estimate of the total quantity of hazardous substances present. This approach has the advantage of relying on the highest concentration and would, in principle, tend to be conservative (i.e., over estimate the quantity and thus the risk). However, unless a sufficient number of samples have been taken at a sufficient number of locations, there is no guarantee that the highest detected concentration is greater than the actual average concentration. Further, both approaches rely on the completeness of the analyses, i.e., chemical analyses *It should be noted that this approach is potentially inconsistent with the current definition of the HRS waste quantity factor. The HRS currently evaluates waste quantity on an "as received" basis. This may differ significantly due to temporal factors from the waste quantity indicate as being present at the time of sampling. 137 ------- must be performed for each CERCLA hazardous substance. This would prove difficult in those cases where acceptable methods of analysis do not exist. A final difficulty in these approaches lies in the definition of the factor evaluation table. One approach would be to transform the existing hazardous waste quantity table (47 FR 31180, 12 July 1982) into a hazardous substance quantity table. The availability of information required to do this translation is examined in Wusterbarth, 1986. The possibility of employing other approaches needs to be examined. As stated previously, a third option for incorporating concentration data into a toxicity factor was examined. In this option, the toxicity factor would be evaluated in terms of a concentration factor and a severity factor, as follows. Each contaminant would be assigned a pathway-specific toxicity benchmark and a severity index. The benchmark would be defined as discussed previously while the severity index would reflect the severity of the effects associated with exceedances of the toxicity benchmark for any single contaminant (evaluated, for example, on a scale of 0 to 3). For each contaminant at the site, the ratio of the maximum detected contaminant concentration to the benchmark concentration would be determined as in the previously discussed concentration factor. The concentration factor would then be evaluated using this ratio as indicated in Table 30 (for example). The overall toxicity 138 ------- TABLE 30 ILLUSTRATIVE CONCENTRATION FACTOR* Ratio (0/B) Factor Value Greater than 10 5 1.0 - 9.99 4 0.1 - 0.99 3 0.01 - 0.099 2 0.001 - 0.0099 1 Less than 0.001 0 *Values are provided for illustrative purposes only. B: Benchmark concentration. 0: Observed site concentration. 139 ------- factor value for each contaminant would then be determined for each contaminant using Table 31 (for example). The highest calculated toxlcity factor value for any single contaminant present in an observed release would be used as the site toxicity factor value (as in the current HRS toxicity factor). For sites lacking observed releases, a presumptive concentration factor value of, for example, three could be used as a default and the toxicity factor evaluated as indicated. There are several potential problems with this approach that makes its implementation unreasonable. First, it may not be possible to develop acceptable toxicity benchmarks for all CERCLA substances. This problem affects the previously discussed options, as well, although it is even more important in this option as the toxicity factor is the major determinant of the waste characteristics value. Problems in defining these benchmarks include differing benchmarks for different effects from exposures to the same contaminants, treatment of threshold versus nonthreshold contaminant/ effect pairings, establishment of de facto acceptable risk levels for carcinogens, and treatment of contaminants/effects pairings with nonlinear dose response relationships. Second, the feasibility of defining a system for evaluating the severity of effects given benchmark exceedances is also questionable. The development of such a system would encounter the difficult problems of effectively establishing the relative worth of different types of effects, for 140 ------- TABLE 31 ILLUSTRATIVE TOXICITY FACTOR MATRIX Concentration Factor Value Severity Index 0 1 2 3 0 0 0 0 0 1 0 1 2 3 2 0 2 4 6 3 0 3 6 9 4 0 4 8 12 5 0 5 10 15 141 ------- example, losing ones eyesight as compared with contracting cancer. Finally, this option would place too great an emphasis on the concentration data. This approach relies heavily on the representativeness of the concentration data; the weakest aspect of the data. No provision would be Bade for reflecting the risks associated with possibly every toxic contaminants found at the site that were not detected in an observed release. Further, as with the waste quantity factor, there would be no guarantee that the highest detected concentration even exceeds the current, average exposure concentration unless the data were truly representative. In such circumstances, the toxicity factor value would probably understate the risks to both maximum and "average" exposed individuals. Additionally, as discussed previously, the present detected concentrations aay not reflect future conditions and thus could understate (or overstate) the risk from the site. In total, these considerations make the adoption of this, otherwise attractive option, scientifically questionable. 7.3.3 Options in the Targets Category Two options for reflecting concentration data in the targets category were developed. The first is fairly simple. All of the current target factor tables reflect the distance from the site to the exposed population. One option for incorporating concentration data would be to give added emphasis to those people who are known to be exposed to contaminant concentrations that exceed background or benchmarks by adjusting the values in the current MRS target distance 142 ------- factor value matrix (as illustrated in Table 32 for the ground water pathway). An alternate, more complex approach is described below. A two- tiered approach could be adopted in evaluating the value for exposed population. First, the number of people within a specified distance of each sampling location with a concentration exceeding background and benchmarks would be evaluated using a "currently exposed" population factor table. The remaining people within another, greater specified distance of the site would be evaluated using a second, "potentially exposed" population factor table. The effective, per-person value would be lower in the second table than in the first table. The resulting "currently exposed" and "potentially exposed" values would be added to form the population factor value. If the sum exceeds the maximum for the factor (e.g., 30), the maximum factor value would be used. An illustrative table for this option, using the air pathway, is presented in Table 33. Using this example, if 350 people were exposed to above benchmark contaminant concentrations arising from the site, then a "currently exposed" population value of 24 would be assigned. If an additional 15,000 people were potentially exposed within a radius of 4 miles, then a "potentially exposed" population value of 21 would be assigned. The sum of the exposed population values (45) exceeds the maximum value (30) and therefore, a population factor value of 30 would be assigned to the site. 143 ------- TABLE 32 ILLUSTRATIVE TABLE FOR EVALUATING POPULATION (GROUND WATER PATHWAY) Population Served 0 1-100 101-1,000 1,001-3,000 3,001-10,000 10,000+ 0 0 30 35 40 40 40 2,000' 0 10 20 30 35 40 Distance 1 mile 0 8 16 24 32 35 to Nearest Well 1 mile 0 6 12 18 24 30 2-3 mile 0 4 8 12 16 20 3 mile 0 0 0 0 0 0 Adapted from 47 FR 31231 (July 16, 1982). 144 ------- TABLE 33 ILLUSTRATIVE TABLES FOR EVALUATING POPULATION (AIR PATHWAY) Currently Exposed Population Population within 1/2 mile* Value 0 0 1-10 15 11-100 18 101-300 21 301-500 24 501-1,000 27 1,000+ 30 Potentially Exposed Population Distance to Population from Hazardous Substance 0-4 miles 0 9 12 15 18 21 0-1 mile 0 12 15 18 21 24 0-1/2 mile 0 15 18 21 24 27 0-1/4 mile 0 18 21 24 27 30 Population 0 1-100 101-1,000 1,001-3,000 3,001-10,000 10,000+ *Total number of people residiag within 1/2 mile of any critical location as well as transients such as workers in factories, offices, restaurants, motels, or students. Critical locations are those locations at which measured contaminant concentrations exceed benchmarks and significantly exceed background. 145 ------- 8.0 OVERALL CONCLUSIONS AND RECOMMENDATIONS Several conclusions can be drawn from the previous discussion. Concerning the quality of concentration data, the data currently developed as part of site inspections is not of uniform quality and is not generally of sufficient quality to support its expanded use in the HRS. Further, within the constraints of a preliminary assessment (PA) and site inspection (SI) program, it is unlikely that concentration data that is representative in space and time could be developed for most sites. The difficulties in developing representative concentration data combine with resource and time constraints to make development of such data infeasible at many sites. Thus, in some cases, the concentration data developed during site inspections would be of questionable scientific validity overall. While it is possible to ensure that each individual datum is scientifically valid, generally an insufficient number of samples will be taken to ensure overall representativeness. Despite these considerations, it is possible to employ concentration data in an expanded fashion in the HRS. However, the limitations of the data must be recognized and, thus, the uses of the data must be limited accordingly. The options discussed previously illustrate several appropriately limited methods for using concentration data to more accurately reflect site risks within the framework of the HRS. 147 ------- The adoption of any of these options would require changes in the PA/SI program to ensure that the concentration data at all sites across all media meet minimum quality standards. These changes would include the development and distribution of uniform guidance for preliminary assessments and site inspections. Such guidance should include not only guidance on site sampling, sample handling, sample analysis, and data interpretation but should also include guidance on the development of background information necessary to develop a valid sampling plan. The development of such plans should be required for all, nonemergency, site inspections. Selected references that could be employed in developing such guidance are provided in Table 34. In order to ensure that the guidance is followed and quality standards are maintained, a vigorous quality assurance (QA) and quality control (QC) program should be implemented, particularly in regard to site inspections not performed by EPA. Such a program would encompass not only laboratory QA and the ongoing EPA Headquarters QA of site documentation packages, but would also include QA/QC of: • Preliminary assessment and background site information. • Site sampling plans and their execution. * Sampling and handling procedures. Without such a program, the concentration data developed will be of varying quality and will too often be of insufficient quality to warrant its use. 148 ------- TABLE 34 GUIDANCE ON CONCENTRATION DATA DEVELOPMENT: SELECTIONS FROM THE LITERATURE Multi-Media Berg, Edward L., Handbook for Sampling and Sample Preservation of Water and Wastewaters, (EPA-600/4-82-029), U.S. Environmental Protection Agency, Cincinnati, OH, September 1982. Ford, Patrick J., Paul J. Turina, and Douglas E. Seeley, Characterization of Hazardous Waste Sites - A Methods Manual - Volume II; Available Sampling Methods, Second Edition, (EPA-600/4-84-076), U.S. Environmental Protection Agency, Las Vegas, NV, December 1984. Ford, Patrick and Paul Turina, Characterization of Hazardous Waste Sites - A Methods Manual - Volume I; Site Investigations, (EPA-600/4-84-075), U.S. Environmental Protection Agency, Las Vegas, NV, April 1985. Gosse, Michelle et al., Continuing Releases at RCRA Facilities Preliminary Draft, Remedial Investigation Guidance, (WR4818), GCA Corporation, Bedford, MA, April 1986. U.S. Environmental Protection Agency, Test Methods for Evaluating Solid Waste; Physical/Chemical Methods, (SW-846), U.S. Environmental Protection Agency, Washington, DC, May 1980. U.S. Environmental Protection Agency, Guidance on Remedial Investigations Under CERCLA, (EPA-540/G-85-002), U.S. Environmental Protection Agency, Washington, DC, June 1985. Groundwater Barcelona, M. J. et al., Practical Guide for Ground-Water Sampling, (EPA-600/2-85-104), U.S. Environmental Protection Agency, Ada, OK, September 1985. Claassen, Hans C., Guidelines and Techniques for Obtaining Water Samples that Accurately Represent the Water Chemistry of an Aquifer, (Open File Report 82-1024), U.S. Geological Survey, Lakewood, CO, 1982. Gibb, James P., Rudolph M. Schuller, and Robert A. Griffin, Procedures for the Collection of Representative Water Quality Data from Monitoring Wells, (ISWS/COOP-7/81), Illinois State Water Survey. Champaign, IL, 1981. ------- TABLE 34 (Continued) Groundwater (Concluded) Nacht, S. J., "Monitoring Sampling Protocols," Ground Water Monitoring Review, Vol. 3, No. 3, Summer, 1983, pp. 23-29. Popkin, Barney P., "Guidelines for Ground-Water Quality Assessments for Hazardous Waste Facilities," Ground Water Monitoring Review, Vol. 3, No. 2, Spring 1983, pp. 65-70. Scalf, Marion R. et al., Manual of Ground-Water Quality Sampling Procedures, (EPA-600/2-81-160), U.S. Environmental Protection Agency, Ada, OK, September 1981. Sisk, Steven W., NEIC Manual for Groundwater/Subsurface Investigations at Hazardous Waste Sites, (EPA-330/9-81-Q02), U.S. Environmental Protection Agency, Denver, CO, July 1981. U.S. Environmental Protection Agency, Procedure Manual for Ground Water Monitoring at Solid Waste Disposal Facilities, (SW-611), U.S. Environmental Protection Agency, Washington, DC, 1977. U.S. Environmental Protection Agency, RCRA Ground-Water Monitoring Technical Enforcement Guidance Document, (Draft), (EPA-600/4-84-076), U.S. Environmental Protection Agency, Washington, DC, August 1985. Air Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic OrganicTompounds in Ambient Air, (EPA-600/4-83-027), U.S. Environmental Protection Agency, Research Triangle Park, NC, June 1983. Turpin, Rodney D., "ERT's Air Monitoring Guides for Uncontrolled Hazardous Waste Sites," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31- November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 82-84. U.S. Environmental Protection Agency, Field Standard Operating Procedure for Air Surveillance, (F.S.O.P. 8), U.S. Environmental Protection Agency, Washington, DC, undated. Soil Mason, Benjamin J., Preparation of Soil Sampling Protocol; Techniques and Strategies, (EPA-600/4-83-020), U.S. Environmental Protection Agency, Las Vegas, NV, May 1983. 150 ------- TABLE 34 (Concluded) Wastes deVera, Emil R. et al., Samplers and Sampling Procedures for Hazardous Waste Streams, (EPA-600/2-80-018), U.S. Environmental Protection Agency, Cincinnati, OH, January 1980. Hanisch, R. C. and M. A. McDevitt, Protocols for Sampling and Analysis of Surface Impoundments and Land Treatment/Disposal Sites for VOCs, (DCN 84-222-078-11-12), Radian Corporation, Austin, TX, September 28, 1984. Laboratory Plumb, Russel H., Jr., Characterization of Hazardous Waste Sites - A Methods Manual - Volume III; Available Laboratory Analytical Methods, (EPA-600/4-84-038), U.S. Environmental Protection Agency, Las Vegas, NV, May 1984. B ioassessment Porcella, D. B., Protocol for Bioassessment of Hazardous Waste Sites, (EPA-600/2-83-054), U.S. Environmental Protection Agency, Corvallis, OR, July 1983. 151 ------- 9.0 REFERENCES AND BIBLIOGRAPHY Absalon, John R. and Robert C. Starr, "Practical Aspects of Ground Water Monitoring at Existing Disposal Sites," Proceedings of the First National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 15-17, 1980 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1980, pp. 53-58. Adams, William M., Stephen W. Wheatcraft, and John W. Hess, "Downhole Sensing Equipment for Hazardous Waste Site Investigations,' Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 108-113. Aller, Linda et al., DRASTIC; A Standardized System for Evaluating Ground Water Pollution Potential Using Hydrogeologic Settings, (EPA-600/2-85-018), U.S. Environmental Protection Agency, Ada, OK, May 1985. American Conference of Governmental Industrial Hygienists, Threshold Limit Values and Biological Indices for 1985-1986, American Conference of Governmental Industrial Hygienists, Cincinnati, OH, 1985. Amster, Michael B., Nasrat Hijazi, and Rosalind Chan, "Real Time Monitoring of Low Level Air Contaminants for Hazardous Waste Sites," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 98-99. Astle, Alice D., Richard A. Duffee, and Alexander R. Stankunas, "Estimating Vapor and Odor Emission Rates from Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29- December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 326-330. Baker, Lynton W., An Evaluation of Screening Models for Assessing Toxic Air Pollution Downwind of Hazardous Waste Landfills, Masters Thesis, Office of Graduate Studies and Research, San Jose State University, San Jose, CA, May 1985. 153 ------- Balfour, W. David, Bart M. Elkund, and Shelly J. Williamson, "Measurement of Volatile Organic Emissions from Subsurface Contaminants," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 77-80. Barcelona, M.J. et al., Practical Guide for Ground-Water Sampling, (EPA-60U/2-85-104), U.S. Environmental Protection Agency, Ada, OK, September 1985. Barcelona, Michael J., "Chemical Problems in Ground-Water Monitoring Programs," Proceedings of the 3rd National Symposium on Aquifer Restoration and Ground Water Monitoring, Held on May 25-27, 1983 in Columbus, OH, D. M. Nielsen, ed., Water Well Journal Publishing Company, Worthington, OH, 1983, pp. 263-271. Ben-Hur, David, James S. Smith, and Michael J. Urban, "Application of Mobile MS/MS to Hazardous Waste Site Investigation," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 53-58. Benson, Richard C. and Robert A. Glaccum, "Site Assessment: Improving Confidence Levels with Surface Remote Sensing," Proceedings of the First National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 15-17, 1980 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1980, pp. 59-65. Benson, Richard C., Charles M. Thomas, and Lynn Yuhr, "An Approach to Long-Term Groundwater Monitoring," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 112-115. Benson, Richard, Robert Glaccum, and Paul Beam, "Minimizing Cost and Risk in Hazardous Waste Site Investigations Using Geophysics," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30,1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 84-88. Berg, Edward L., Handbook for Sampling and Sample Preservation of Water and Wastewa'ters, (EPA-600/4-82-029), U.S. Environmental Protection Agency, Cincinnati, OH, September 1982. 154 ------- Berhardt, David E., Richard 0. Gilbert, and Paul B. Hahn, "Comparison of Soil-Sampling Techniques for Plutonium at Rocky Flats," TRAN-STAT Statistics for Environmental Studies, Number 22, (PNL-SA-11034, DE83005561), Richard 0. Gilbert, coordinator, Batelle Memorial Institute Pacific Northwest Laboratory, Richland, WA, January 1983. Blackman, William C. et al., "Chemical Composition of Drum Samples from Hazardous Waste Sites," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 39-44. Bruck, John M., Eugene W. Koesters, and William R. Parker, "Air Monitoring at a Major Hazardous Waste Cleanup Site: Objectives/ Strategy/Results," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 72-76. Bruehl, Donald H., Neville K. Chung, and Warren F. Diesl, "Geologic Studies of Industrially-Related Contamination: Soil and Ground Water Investigations," Proceedings of the First National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 15-17, 1980 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1980, pp. 78-84. Bryan, Robert J., "Ambient Air Quality Surveillance," Air Pollution, Third Edition Volume III Measuring, Monitoring, and Surveillance of Air Pollution, Arthur C. Stern, ed., Academic Press, New York, NY, 1976, pp. 343-392. Burger, Carol J. and Lawrence M. Kushner, Hazard Ranking System Issue Analysis; An Assessment of the HRS Target Distance Limit for Surface Water, (MTR-86W84), The MITRE Corporation, McLean, VA, October 1986. Caldwell, Steven, U.S. Environmental Protection Agency, Washington, DC, personal communications to Thomas Wolfinger, The MITRE Corporation, 1986. California Department of Health Services, California Air Resources Board, and South Coast Air Quality Management District, Ambient Air Monitoring and Health Risk Assessment for Suspect Human Carcinogens Around the BKK Landfill in West Covina, California Department of Health Services, March 1983. 155 ------- Chang, Ruth and Robert D. Stephens, "The Application of Mass Selective Detector for the Screening of Environmental Pollutants in Toxic Waste," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 102-106. Claassen, Hans C., Guidelines and Techniques for Obtaining Water Samples that Accurately Represent the Water Chemistry of an Aquifer, (Open File Report 82-1024), U.S. Geological Survey, Lakewood, CO, 1982. Clay, Paul F. and Thomas M. Spittler, "The Use of Portable Instruments in Hazardous Waste Site Characterizations," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 40-44. Cook, David K., "Selection of Monitoring Well Locations in East and North Woburn, Massachusetts," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 63-69. Core, John E., Receptor Modeling Technical Series, Volume 1; Overview of Receptor Model Application to Particulate Source Apportionment, (EPA-450/4-81-016a), U.S. Environmental Protection Agency, Research Triangle Park, NC, July 1981. Cox, Robert D., Kenneth J. Baughman, and Ronald F. Earp, "A Generalized Screening and Analysis Procedure for Organic Emissions from Hazardous Waste Disposal Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 58-62. Crawley, W. W., R. L. Shiver, and D. C. Anderson, "In Situ Sampling of Hazardous Waste Surface Impoundments," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-5, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 80-83. Cullis, C. F. and J. G. Firth, Detection and Measurement of Hazardous Gases, Heinemann, London, 1981. 156 ------- Dawson, Gaynor W., Jill M. Meuser, and Mary C. Lilga, Dioxin Transport form Contaminated Sites to Exposure Locations; A Methodology for Calculating Conversion Factors, (EPA-600/8-85-012), U.S. Environmental Protection Agency, Washington, DC, June 1985. deVera, Emil R. et al., Samplers and Sampling Procedures for Hazardous Waste Steams, (EPA-600/2-80-018), U.S. Environmental Protection Agency, Cincinnati, OH, January 1980. Devary, Joseph L. and Ronald Schalla, "Improved Methods of Flow System Characterization," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 117-122. Di Nitto, Richard G., William R. Norman, and M. Margret Hanley, "An Approach to Investigating Groundwater Contaminant Movement in Bedrock Aquifers: Case Histories," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 111-117. Driscoll, Fletcher G., Groundwater and Wells Second Edition, Johnson Division, St. Paul, MN, 1986. Driscoll, J. N., A. G. Wilshire, and I. W. Bodenrader, "New Continuous Monitoring Systems for Measurement of Hazardous Pollutants," Proceedings; National Symposium on Recent Advances in Pollutant Monitoring of Ambient Air and Stationary Sources, (EPA-600/ 9-84-019), Held on May 8-10, 1984 in Raleigh, NC, U.S. Environmental Protection Agency, Research Triangle Park, NC, November 1984, pp. 91-95. Duvel, William A., "Practical Interpretation of Groundwater Monitoring Results," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 86-90. Ehrenfeld, John and Jeffery Bass, Handbook for Evaluating Remedial Action Technology Plans, (EPA-600/2-83-076), U.S. Environmental Protection Agency, Washington, DC, August 1983. 157 ------- Engels, J. L. et al., "Survey of Mobile Laboratory Capabilities and Configurations," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 45-48. Evans, R. B., R. C. Benson, and J. Rizzo, "Systematic Hazardous Waste Site Assessments," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 17-22. Everett, L. G. et al., Monitoring Groundwater Quality; Methods and Costs, (EPA-600/4-76-023), U.S. Environmental Protection Agency, Las Vegas, NV, May 1976. Everett, L. G. et al., "Vadose Zone Monitoring Concepts at Landfills, Impoundments, and Land Treatment Disposal Areas," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 100-106. Everett, L. G., L. G. Wilson, and E. W. Hoylman, Vadose Zone Monitoring for Hazardous Waste Sites, (EPA-600/X-83-064), U.S. Environmental Protection Agency, Las Vegas, NV, October, 1983. Everett, Lome, Groundwater Monitoring, General Electric Company, Schenectady, NY, 1980. Everett, Lorne G., "Monitoring in the Zone of Saturation," Ground Water Monitoring Review, Vol. 1, No. 1, Spring 1981, pp. 38-41. Farthing, William E., "Particle Sampling and Measurement," Environmental Science and Technology, Vol. 16, No. 4, April 1982, pp. 237A-244A. Fellows, Charles R. and James H. Sullivan, "Refined Strategies for Abandoned Site Discovery and Assessment," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 37-42. Fetter, C. W., "Potential Sources of Contamination in Ground-Water Monitoring," Ground Water Monitoring Review, Vol. 3, No. 2, Spring 1983, pp. 60-64. 158 ------- Fitzgerald, Jerry M., Hazard Ranking System Issue Analysis: Laboratory Limits of Detection, (MTR-86W77), The MITRE Corporation, McLean, VA, July 1986. Flatman, George T., "Using Geostatistics in Assessing Lead Contamination Near Smelters," Environmental Sampling for Hazardous Wastes, (ACS Symposium Series 267), Glenn E. Schweitzer and John A. Santolucito, eds., American Chemical Society, Washington, DC, 1984, pp. 43-52. Ford, Karl and Paul Gurba, "Health Risk Assessments for Contaminated Soils," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 230-231. Ford, Patrick J., Paul J. Turina, and Douglas E. Seeley, Characterization of Hazardous Waste Sites - A Methods Manual - Volume II; Available Sampling Methods, Second Edition, (EPA-600/ 4-84-076), U.S. Environmental Protection Agency, Las Vegas, NV, December 1984. Ford, Patrick and Paul Turina, Characterization of Hazardous Waste Sites - A Methods Manual - Volume I: Site Investigations, (EPA-600/ 4-84-075), U.S. Environmental Protection Agency, Las Vegas, NV, April 1985. Friedman, Paul H. and Duane Geuder, "Quality Control Attributes of Process Analytical Data," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 29-34. Furst, George A., Valerie Tillinghast, and Thomas Spittler, "Screening for Metals at Hazardous Waste Sites: A Rapid Cost- Effective Technique Using X-Ray Fluorescence," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 93-96. GCA Corporation, Guidelines for Air Quality Maintenance and Analysis. Volume 11; Air Quality Monitoring and Data Analysis, (EPA-450/4-74-012), U.S. Environmental Protection Agency, Research Triangle Park, NC, September 1974. 159 ------- Geraghty and Miller, Inc. and American Ecology Services, Inc., The Fundamentals of Ground-Water Contamination, Geraghty and Miller, Inc., Tampa, FL, 1985. Gerstein, Robert E., Hazard Ranking System Issue Analysis; Geohydrology, (MTR-86W62), The MITRE Corporation, McLean, VA, October 1986. Gibb, James P., Rudolph M. Schuller, and Robert A. Griffin, Procedures for the Collection of Representative Water Quality Data from Monitoring Wells, (ISWS/COOP-7/81), Illinois State Water Survey, Champaign, IL, 1981. Gilbert, Richard 0., "Field Sampling Designs, Simple Random and Stratified Random Sampling," IRAN-STAT Statistics for Environmental Studies, Number 24, (PNL-SA-11551, DE83016826), Richard 0. Gilbert, coordinator, Batelle Memorial Institute Pacific Northwest Laboratory, Richland, WA, August 1983. Gilbert, Richard 0., "Field Sampling Designs: Systematic Sampling," TRAN-STAT Statistics for Environmental Studies, Number 26, (PNL-SA-12180, DE84-008651), Richard 0. Gilbert, coordinator, Batelle Memorial Institute Pacific Northwest Laboratory, Richland, WA, April 1984. Gillham, R. W. et al., Groundwater Monitoring and Sample Bias, (API Publication 4367), American Petroleum Institute, Washington, DC, June 1983. Gilkeson, Robert H. and Keros Cartwright, "The Application of Surface Electrical and Shallow Geothermic Methods in Monitoring Network Design," Ground Water Monitoring Review, Vol. 3, No. 3, Summer 1983, pp. 30-42. Glaccum, Robert A., Richard C. Benson, and Michael R. Noel, "Improving Accuracy and Cost-Effectiveness of Hazardous Waste Site Investigations," Ground Water Monitoring Review, Vol. 2, No. 3, Summer 1982, pp. 36-40. Gleit, Alan, "Estimation for Small Normal Data Sets with Detection Limits," Environmental Science and Technology, Vol. 19, No. 12, December 1985, pp. 1201-1206. Gosse, Michelle et al., Continuing Releases at RCRA Facilities Preliminary Draft, Remedial Investigation Guidance, (WR4818), GCA Corporation, Bedford, MA, April 1986. 160 ------- Gruenfeld, Michael et al., "Management of Analytical Laboratory Support at Uncontrolled Hazardous Waste Sites," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 96-102. Gurka, D. F. et al., "Analytical and Quality Control Procedures for the Uncontrolled Hazardous Waste Sites Contract Program," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 45-51. Hagger, Christopher and Paul F. Clay, "Hydrogeological Investigation of an Uncontrolled Hazardous Waste Site," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 45-51. Hanisch, R. C. and M. A. McDevitt, Protocols for Sampling and Analysis of Surface Impoundments and Land Treatment/Disposal Sites for VOCs, (DCN 84-222-078-11-12), Radian Corporation, Austin, TX, September 28, 1984. Harman, H. Dan, Jr., "Detailed Stratigraphic and Structural Control: The Keys to Complete and Successful Geophysical Surveys of Hazardous Waste Sites," Proceedings of the National Conference on Hazardous Wastes and Hazardous Materials, Held on March 4-6, 1986 in Atlanta, GA, Hazardous Materials Control Research Institute, Silver Spring, MD, 1986, pp. 19-21. Harman, H. Dan, Jr. and Shane Hitchcock, "Cost Effective Preliminary Leachate Monitoring at an Uncontrolled Hazardous Waste Site," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 97-99. Harrison, Roy M., Recent Advances in Air Pollution Analysis, University of Lancaster, Lancaster, England, undated. Hatayama, Howard K., "Special Sampling Techniques Used for Investigating Uncontrolled Waste Sites in California," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington. DC. Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 149-153. 161 ------- Ho, J. S-Y, "Effect of Sampling Variables on Recovery of Volatile Organics in Water," Journal of the American Water Works Association, December 1983, pp. 583-586. Holdren, M. W., D. L. Smith, and R. N. Smith, Comparison of Ambient Air Sampling Techniques for Volatile Organic Compounds,(EPA-600/ 4-85-067), U.S. Environmental Protection Agency, Research Triangle Park, NC, October 1985. Hwang, Jack C. et al., "Feasibility Studies of Groundwater Pollution Source Identification from Actual Field Monitoring Well Data," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 1-5. Hwang, Seong T., "Statistical Considerations in Groundwater Monitoring," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 346-349. laccarino, T. et al., "A Superfund Site Atmospheric Study: Application to Remedial Response Decision-Making," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 66-67. Isaacson, Peter J., William P. Eckel, and John F. Fisk, "Low Occurrence Compounds: Analytical Problem or Environmental Process?," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 130-135. Jacot, Brian J., "OVA Screening at a Hazardous Waste Site," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 76-78. Janisz, Amelia A. and W. Scott Butterfield, "Biological Sampling at Abandoned Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 52-56. 162 ------- Johnson, Michael G., "The Stratified Sample Thief - A Device for Sampling Unknown Fluids," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 154-157. Journel, Andre G., "New Ways of Assessing Spatial Distributions of Pollutants," Environmental Sampling for Hazardous Wastes, (ACS Symposium Series 267), Schweitzer, Glenn E. and John A. Santolucito, eds., American Chemical Society, Washington, DC, 1984, pp. 109-118. JRB Associates, Remedial Action Costing Procedures Manual, (Draft), U.S. Environmental Protection Agency, Cincinnati, OH, September 1985. K. B. Brown and Associates, Inc., Hazardous Waste Land Treatment, (SW-874), U.S. Environmental Protection Agency, Washington, DC, September 1980. Kaczmar, Swiatoslav, Edwin C. Tifft, Jr., Cornelius B. Murphy, Jr., "Site Assessment Under CERCLA: 'The Importance of Distinguishing Hazard from Risk'," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 221-225. Katz, Morris, "Advances in the Analysis of Air Contaminants," Journal of the Air Pollution Control Association, Vol. 30, No. 5, May 1980, pp. 528-557. Kazmann, R. G., "An Introduction to Ground-Water Monitoring," Ground Water Monitoring Review, Vol. 1, No. 1, Spring 1981, pp. 28-29. Keith, Lawrence H. et al., "Principles of Environmental Analysis, Analytical Chemistry, Vol. 55, 1983, pp. 2210-2218. Keith, Susan J. et al., "Dealing with the Problem of Obtaining Accurate Ground-Water Quality Analytical Results," Proceedings of the 3rd National Symposium on Aquifer Restoration and Ground Water Monitoring, Held on May 25-27, 1983, in Columbus, OH, D. M. Nielsen, ed., Water Well Journal Publishing Company, Worthington, OH, 1983a, pp. 272-283. Keith, Susan J. et al., "Sources of Spatial-Temporal Variability in Ground Water Quality Data and Methods of Control," Ground Water Monitoring Review, Vol. 3, No. 2, Spring 1983b, pp. 21-32. 163 ------- Kerfoot, H. B., J. A. Kohout, and E. N. Amick, "Detection and Measurement of Groundwater Contamination by Soil-Gas Analysis," Proceedings of the National Conference on Hazardous Wastes and Hazardous Materials, Held on March 4-6, 1986 in Atlanta, GA, Hazardous Materials Control Research Institute, Silver Spring, MD, 1986, pp. 22-26. Kirchmer, Cliff J., "Quality Control in Water Analyses," Environmental Science and Technology, Vol. 17, No. 4, 1983, pp. 174A-181A. Kirchmer, Cliff J., Margaret C. Winter, and Barbara A. Kelly, "Factors Affecting the Accuracy of Quantitative Analyses of Priority Pollutants Using GC/MS," Environmental Science and Technology, Vol. 17, No. 7, 1983, pp. 396-4U1. Kolb, Sean, U.S. Environmental Protection Agency, Washington, DC, personal communication to Thomas Wolfinger, The MITRE Corporation, September 1986. Kolybe, Albert C., Jr., "The Need for Accuracy in a Regulatory Agency," Accuracy in Trace Analysis: Sampling, Sample Handling, Analysis - Volumes I and II, (NBS Special Publication 422), D. Philip LaFleur, ed., National Bureau of Standards, Gaithersburg, MD, 1974, pp. 3-8. LaFleur, Philip D., ed., Accuracy in Trace Analysis; Sampling, Sample Handling, Analysis - Volumes I and II, (NBS Special Publication 422), Proceedings of the 7th Material Research Symposium, Held on October 7-11, 1987 in Gaithersburg, MD, National Bureau of Standards, Gaithersburg, MD, 1974. Lappala, Eric G. and Glenn M. Thompson, "Detection of Groundwater Contamination by Shallow Soil Gas Sampling in the Vadose Zone Theory and Applications, " Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 20-28. Liggett, Walter, "Detecting Elevated Contamination by Comparisons with Background," Environmental Sampling for Hazardous Wastes, (ACS Symposium Series 267), Glenn E. Schweitzer and John A. Santolucito, eds., American Chemical Society, Washington, DC, 1984, pp. 119-128. Lipsky, David and Brian Jacot, "Hazardous Emissions from Sanitary Landfills," Proceedings for the 78th Annual Meeting of the Air Polluation Control Association, Held on June 16-21, 1985 in Detroit, MI, Air Pollution Control Association, Pittsburgh, PA, 1985. 164 ------- Liu, M. K. and J. Arvin, Methodology for the Design of an Optimal Air Quality Monitoring Network, (EPA-600/4-81-002), U.S. Environmental alogy V-600/ Protection Agency, Las Vegas, NV, February 1981. Liu, M. K. et al., "Methodology for Designing Air Quality Networks: I Theoretical Aspects," Environmental Monitoring and Assessment, Vol. 6, 1986, pp. 1-11. Lodge, James P., Jr., "Accuracy in Air Sampling," Accuracy in Trace Analysis; Sampling, Sample Handling, Analysis - Volumes I and II, (NBS Special Publication 422), Philip D. LaFleur, ed., National Bureau of Standards, Gaithersburg, MD, 1974, pp. 311-320. Mack, James P. and Thomas J. Morahan, "Equipment for Data Collection at Hazardous Waste Sites - An Overview for Environmental Management Professionals," Proceedings of the National Conference on Hazardous Wastes and Hazardous Materials, Held on March 4-6, 1986 in Atlanta, GA, Hazardous Materials Control Research Institute, Silver Spring, MD, 1986, pp. 1-7. Mason, Benjamin J., Preparation of Soil Sampling Protocol; Techniques and Strategies, (EPA-600/4-83-020), U.S. Environmental Protection Agency, Las Vegas, NV, May 1983. McKee, C. R. and A. C. Bumb, "The Importance of Unsaturated Flow Parameters in Designing a Monitoring System for a Hazardous Waste Site," Proceedings of the National Conference on Hazardous Wastes and Environmental Emergencies, Held on March 12-14, 1984 in Houston, TX, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 50-58. McKown, Gary L., Ronald Schalla, and C. Joseph English, "Effects of Uncertainties of Data Collection on Risk Assessment," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 283-286. Mernitz, Scott, Roger Olsen, and Ken Staible, "Use of a Portable X-Ray Analyzer and Geostatistical Methods to Detect and Evaluate Hazardous Metals in Mine/Mill Tailings," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 107-111. 165 ------- Mooney, Gregory A. and Russell W. Bartley, "Characterization of Organic Wastes for Evaluation of Remedial Action Alternatives," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 35-38. Moore, Stephen F. and Dennis B. Mclaughlin, "Mapping Contaminated Soil Plumes by Kriging," Proceedings of the First National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 15-17, 1980 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1980, pp. 66-70. Moss, M. E. and G. D. Tasker, "Progress in the Design of Hydrologic- Data Networks," Reviews of Geophysics and Space Physics, Vol. 17, No. 6, September 1979, pp. 1298-1307. Morin, Joanne O'Neill, "Development and Application of an Analytical Screening Program to Superfund Activities," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 97-101. Moylan, Craig A., "Hazardous Materials Training for First Responders: Concepts and Future Needs," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 71-73. Myers, Jeffrey C., "Objective Quantification of Sampling Adequacy and Soil Contamination Levels Around Point Sources Using Geostatistics," Proceedings of the National Conference on Hazardous Wastes and Hazardous Materials, Held on March 4-6, 1986 in Atlanta, GA, Hazardous Materials Control Research Institute, Silver Spring, MD, 1986, pp. 92-97. Nacht, S. J., "Monitoring Sampling Protocols," Ground Water Monitoring Review, Vol. 3, No. 3, Summer 1983, pp. 23-29. Nadeau, Royal J. et al., "Measuring Soil Vapors for Defining Subsurface Contaminant Plumes," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Contro1 Research Institute, Silver Spring, MD, 1985, pp. 128-129. 166 ------- Nazar, Andrzej, James Prieur, and Daniel Threlfall, "An Integrated Ground Water Monitoring Program Using Multilevel Gas-Driven Sampler and Conventional Monitoring Wells," Ground Water Monitoring Review, Vol. 4, No. 4, Fall 1984, pp. 43-47. Nelson, James D. and Robert C. Ward, "Statistical Considerations and Sampling Techniques for Ground-Water Quality Monitoring, Ground Water, Vol. 19, No. 6, November-December 1981, pp. 617-625. Oppenheimer, J. A., A. D. Eaton, and L. Y. C. Leong, Multielement Analytical Techniques for Hazardous Waste Analysis; The State-of- the Art. (EPA-600/4-64-028), U.S. Environmental Protection Agency. Las Vegas, NV, April 1984. Pellizzari, Edo D., Measurement of Carcinogenic Vapors in Ambient Atmospheres, (EPA-600/7-78-062), U.S. Environmental Protection Agency, Research Triangle Park, NC, April 1978. Perazzo, James A., Richard C. Dorrler, and James P. Mack, "Long-Term Confidence in Ground Water Monitoring Systems," Ground Water Monitoring Review, Vol. 4, No. 4, Fall 1984, pp. 119-123. Peters, James A., Keith M. Tackett, and Edward C. Eimutis, "Measurement of Fugitive Hydrocarbon Emissions from a Chemical Waste Disposal Site," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 123-128. Plumb, Russel H., Jr., Characterization of Hazardous Waste Sites - A Methods Manual - Volume III: Available Laboratory Analytical Methods, (EPA-60Q/4-84-U38J, U.S. Environmental Protection Agency, Las Vegas, NV, May 1984. Popkin, Barney P., "Guidelines for Ground-Water Quality Assessments for Hazardous Waste Facilities," Ground Water Monitoring Review, Vol. 3, No. 2, Spring 1983, pp. 65-70. Porcella, D. B., Protocol for Bioassessment of Hazardous Waste Sites, (EPA-600/2-83-054), U.S. Environmental Protection Agency, Corvallis, OR, July 1983. Possin, Boyd N., "Groundwater Systems and Hazardous Wastes Sites - A Basic Conceptual Framework," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 114-116. 167 ------- Powell, David H. et al., "Use of Detector Ratios for Contaminant Screening by High-Pressure Liquid Chromatography," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 86-93. Priznar, Francis J. and Lucy P. Sibold, "Site Inspection Sampling Strategy to Support the Hazard Ranking System Scoring," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 74-79. Provost, Lloyd P., "Statistical Methods in Environmental Sampling," Environmental Sampling for Hazardous Wastes, (ACS Symposium Series 267), Gleen E. Schweitzer and John A. Santolucito, eds., American Chemical Society, Washington, DC, 1984, pp. 79-96. Quimby, Jay M., Robert W. Cibulskis, and Michael Gruenfeld, "Evaluation and Use of a Portable Gas Chromatograph for Monitoring Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 36-39. Quinn, Kenneth J., Steven G. Wittmann, and R. Damon Lee, "Use of Soil Gas Sampling Techniques for Assessment of Groundwater Contamination," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 157-163. Rhodes, Raymond C. and E. Gardner Evans, Precision and Accuracy Assessments for State and Local Air Monitoring Networks, (EPA-600/ 4-86-012), U.S. Environmental Protection Agency, Research Triangle Park, NC, February 1986. Riggin, R. M., Technical Assistance Document for Sampling and Analysis of Toxic Organic Compounds in Ambient Air,(EPA-600/ 4-83-027), U.S. Environmental Protection Agency, Research Triangle Park, NC, June 1983. Ritzert, C. John, "Sampling Plan Design for Hazardous Wastes," Proceedings of the National Conference on Hazardous Wastes and Environmental Emergencies, Held on March 12-14, 1984 in Houston, TX, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 141-145. 168 ------- Rogoff, Marc J., Summary of EPA Symposium on Land Disposal of Hazardous Waste, (WP-81W406), The MITRE Corporation, McLean, VA, July 31, 1981. Russell, Sue, National Priorities List Quality Assurance Team, The MITRE Corporation, McLean, VA, personal communications to Thomas Wolfinger, The MITRE Corporation, 1986. Ryan, Robert M., "Texas Experience in Ambient Air Sampling for Toxic Wastes," Proceedings of the Sixth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 4-6, 1985 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1985, pp. 125-127. Sachs, Lothar, Applied Statistics; A Handbook of Techniques, Springer-Verlag, New York, NY, 1982. Sayers, William T. and Wayne R. Ott, "Use and Interpretation of Water Quality Data," Accuracy in Trace Analysis; Sampling, Sample Handling, Analysis - Volumes I and II, (NBS Special Publication 422), Philip D. LaFleur, ed., National Bureau of Standards, Gaithersburg, MD, 1974, pp. 91-107- Scalf, Marion R. et al., Manual of Ground-Water Quality Sampling Procedures, (EPA-600/2-81-160), U.S. Environmental Protection Agency, Ada, OK, September 1981. Schmidt, Charles E., W. David Balfour, and Robert D. Cox, "Sampling Techniques for Emissions Measurements at Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 334-339. Schmidt, Charles E. and M. W. Eltgroth, "Off-Site Assessment of Air Emissions from Hazardous Waste Disposal Facilities," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 293-295. Schuller, Rudolph M., James P- Gibb, and Robert A. Griffin, "Recommended Sampling Procedures for Monitoring Wells," Ground Water Monitoring Review, Vol. 1, No. 1, Spring 1981, pp. 42-46. 169 ------- Schweitzer, Glenn E., "Risk Assessment Near Uncontrolled Hazardous Waste Sites: Role of Monitoring Data," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 238-247. Schweitzer, Glenn E. and Stuart C. Black, "Monitoring Statistics" Environmental Science and Technology, Vol. 19, No. 11, November 1985, pp. 1026-1030. Schweitzer, Glenn E. and John A. Santolucito, eds., Environmental Sampling for Hazardous Wastes, (ACS Symposium Series 267), American Chemical Society, Washington, DC, 1984. Seanor, Arthur M., Anna L. Pisano, and Larry K. Brannaka, "Quality Assurance to Assure Quality of Field Sampling," Proceedings of the National Conference on Hazardous Wastes and Environmental Emergencies, Held on March 12-14, 1984 in Houston, TX, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 123-128. Seanor, Arthur M. and Larry K. Brannaka, "Influence of Sampling Techniques on Organic Water Quality Analysis," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 143-148. Sgambat, Jeffrey and Jery R. Stedinger, "Confidence in Ground-Water Monitoring, Ground Water Monitoring Review, Vol. 1, No. 1, Spring 1981, pp. 62-69. Sherwani, Jabbar and David H. Moreau, Strategies for Water Quality Monitoring, (UNC-WRRI-75-107), University of North Carolina Water Resources Research Institute, June 1975. Singh, Udai P. et al., "Sampling the Biscayne Aquifer for Toxic Pollutants," Proceedings of the Second Conference on Management of Municipal, Hazardous, and Coal Wastes, (DOE/METC-84-34), Held on December 5, 1983, in Miami, FL, U.S. Department of Energy, Washington, DC, September 1984, pp. 422-431. Sisk, Steven W., NEIC Manual for Groundwater/Subsurface Investigations at Hazardous Waste Sites, (EPA-330/9-81-002), U.S. Environmental Protection Agency, Denver, CO, July 1981. 170 ------- Smart, Glenn R. and David K. Cook, "The Design of Monitoring Well Systems to Meet RCRA Requirements," Proceedings of the National Conference on Hazardous Wastes and Environmental Emergencies, Held on March 12-14, 1984 in Houston, TX, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 68-71. Spear, Richard and Peter Franconeri, "Installing Groundwater Monitoring Wells at a Hazardous Waste Site," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 89-95. Spittler, Thomas M., "Field Measurements of PCB's in Soil and Sediment Using a Portable Gas Chromatograph," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 105-107. Spittler, Thomas M., Richard Siscanaw, and Moira Lataille, "Correlation Between Field GC Measurements of Volatile Organics and Laboratory Confirmation of Collected Field Samples Using the GC/MS Extended Abstract," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, p. 57. Stephens, Robert D., "The Stringfellow Industrial Waste Disposal Site: A Technical Assessment of Environmental Impact," Proceedings of the First National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 15-17, 1980 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1980, pp. 15-20. Stern, Arthur C., ed., Air Pollution, Third Edition Volume III Measuring, Monitoring, and Surveillance of Air Pollution, Academic Press, New York, NY, 1976. Stetter, J. R. et al., "Portable Instrument for the Detection and Identification of Air Pollutants," Proceedings; National Symposium on Recent Advances in Pollutant Monitoring of Ambient Air and Stationary Sources, (EPA-600/9-84-019), Held on May 8-10, 1984 in Raleigh, NC, U.S. Environmental Protection Agency, Research Triangle Park, NC, November 1984, pp. 73-81. 171 ------- Stevens, Robert K., Sampling and Analysis of Atmospheric Aerosols, Presented at the Advanced Research Workshop on Environmental Monitoring of Architectural Conservation, Rome, Italy, June 11-14, 1984. Sullivan, David A. and Jerome B. Strauss, "Air Monitoring of a Hazardous Waste Site," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 136-142. Swaroop, R. and 0. S. Ghuman, "Subsampling of Hazardous Waste," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 90-93. Thibodeaux, Louis J. et al., "Air Emission Monitoring of Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29- December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 70-75. Thomas, John M., "Field Sampling for Monitoring, Migration and Defining the Areal Extent of Chemical Contamination," Proceedings of the Fifth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 7-9, 1984 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1984, pp. 85-89. Tirsch, F. S. and J. W. Male, River Basin Water Quality Monitoring Design, (Water Resources Research Center Publication Number 141), Massachusetts University, Amherst, MA, March 1983. Todd, David K. et al., Monitoring Groundwater Quality; Monitoring Methodology, (EPA-600/4-7b-026), U.S. Environmental Protection Agency, Las Vegas, NV, June 1976. Townsend, Richard W., "Air Monitoring of Hazardous Waste Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 67-69. Tucker, William A. and Carolyn Poppell, "Method for Determining Acceptable Levels of Residual Soil Contamination," Proceedings of the National Conference on Hazardous Wastes and Hazardous Materials, Held on March 4-6, 1986 in Atlanta, GA, Hazardous Materials Control Research Institute, Silver Spring, MD, 1986, pp. 87-91. 172 ------- Turpin, Rodney D., "ERT's Air Monitoring Guides for Uncontrolled Hazardous Waste Sites," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 82-84. Turpin, Rodney D., "On-Site Air Monitoring Classification by Use of the ERT Two-Stage Collection Tube," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 85. U.S. Environmental Protection Agency, Ambient Air Monitoring Guidelines for Prevention of Significant Deterioration (PSD), (EPA-450/4-80-012), U.S. Environmental Protection Agency, Researeh Triangle Park, NC, November 1980a. U.S. Environmental Protection Agency, Enforcement Considerations for Evaluations of Uncontrolled Hazardous Waste Disposal Sites, U.S. Environmental Protection Agency, Denver, CO, April 1980b. U.S. Environmental Protection Agency, Field Standard Operating Procedure for Air Surveillance, (F.S.O.P. 8), U.S. Environmental Protection Agency, Washington, DC, undated. U.S. Environmental Protection Agency, Guidelines; Air Quality Surveillance Networks, (AP-98), U.S. Environmental Protection Agency, Research Triangle Park, NC, May 1971. U.S. Environmental Protection Agency, Guidance for Air Quality Monitoring Network Design and Instrument Siting (Revised), (Draft, OAQPS Number 1.2-012), U.S. Environmental Protection Agency, Research Triangle Park, NC, September 1975. U.S. Environmental Protection Agency, Guidance on Remedial Investigations Under CERCLA, (EPA-540/G-85-002), U.S. Environmental Protection Agency, Washington, DC, June 1985a. U.S. Environmental Protection Agency, Procedure Manual for Ground Water Monitoring at Solid Waste Disposal Facilities, (SW-611), U.S. Environmental Protection Agency, Washington, DC, 1977. 173 ------- U.S. Environmental Protection Agency, Proceedings; National Symposium on Recent Advances in Pollutant Monitoring of Ambient Air and Stationary Sources, (EPA-600/9-84-019), Held on May 8-10, 1984 in Raleigh, NC, U.S. Environmental Protection Agency, Research Triangle Park, NC, November 1984. U.S. Environmental Protection Agency, RCRA Ground-Water Monitoring Technical Enforcement Guidance Document, (Draft), (EPA-600/4-84-076), U.S. Environmental Protection Agency, Washington, DC, August 1985b. U.S. Environmental Protection Agency, Resource Document for the Ground-Water Monitoring Strategy Workshop, U.S. Environmental Protection Agency, Washington, DC, March 1985c. U.S. Environmental Protection Agency, Site Inspection Training Course, U.S. Environmental Protection Agency, Washington, DC, undated. U.S. Environmental Protection Agency, Test Methods for Evaluating Solid Waste; Physical/Chemical Methods, (SW-846), U.S. Environmental Protection Agency, Washington, DC, May 1980c. U.S. Environmental Protection Agency, Third Annual National Symposium on Recent Advances in Pollutant Monitoring of Ambient Air and Stationary Sources Agenda, Abstracts, Attendee List, Held on May 3-6, 1983 in Raleigh, NC, U.S. Environmental Protection Agency, Research Triangle Park, NC, May 1983. U.S. House of Representatives, Superfund Amendments and Reauthorization Act of 1986 Conference Report, (Report 99-962), U.S. House of Representatives, Washington, DC, 1986. Vukovich, Fred M., Walter D. Bach, Jr., and C. Andrew Clayton, Optimum Meteorological and Air Pollution Sampling Network Selection in Cities Volume 1; Theory and Design for St. Louis, (EPA-600/ 4-78-030), U.S. Environmental Protection Agency, Research Triangle Park, NC, June 1978. Vukovich, Fred M., Walter D. Bach, Jr., and C. Andrew Clayton, Optimum Meteorological and Air Pollution Sampling Network Selection in Urban Areas, (NSF/RA-77Q454), National Science Foundation, Washington, DC, December 1977. Wallace, Lance A. et al., "Personal Exposures, Indoor-Outdoor Relationships, and Breath Levels of Toxic Air Pollutants Measured for 355 Persons in New Jersey/1 Atmospheric Environment, Vol. 19, No. 10, 1985, pp. 1651-1661. 174 ------- Walther, Eric G., "Study of Subsurface Contamination with Geophysical Monitoring Methods at Henderson, Nevada," Proceedings of the Fourth National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 31-November 2, 1983 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1983, pp. 28-36. Weber, Dennis D. et al., "Spatial Mapping of Conductive Ground Water Contamination With Electromagnetic Induction," Ground Water Monitoring Review, Vol. 4, No. 4, Fall 1984, pp. 70-77. Weber, Robert C. and Kenneth Mims, Evaluation of the Walkthrough Survey Method for Detection of Volatile Organic Compound Leaks, (EPA 600/2-81-073), U.S. Environmental Protection Agency, Cincinnati, OH, April 1981. Wetzel, Roger et al., "Drum Handling Practices at Abandoned Sites," Land Disposal of Hazardous Waste - Proceedings of the Ninth Annual Research Symposium, (EPA-600/9-83-018), Held on May 2-4, 1983 in Ft. Mitchell, KY, U.S. Environmental Protection Agency, Cincinnati, OH, September, 1983, pp. 414-426. Wetzel, Roger, Kathleen Wagner, and Anthony N. Tafuri, "Drum Handling Practices at Abandoned Sites," Proceedings of the Third National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on November 29-December 1, 1982 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1982, pp. 169-174. Wilson, L. G., Monitoring in the Vadose Zone; A Review of Technical Elements and Methods, (EPA-6QO/7-89-134), U.S. Environmental Protection Agency, Las Vegas, NV, June 1980. Wolfinger, Thomas F., Hazard Ranking System Issue Analysis; Carcinogenic Risk Analysis of the Air Pathway Target Distance Limit, (MTR-86W140), The MITRE Corporation, McLean, VA, October 1986. Wusterbarth, Arlene, Hazard Ranking System Issue Analysis; Relationship Between Waste Quantity and Hazardous Constituent Quantity, (MTR-86W141), The MITRE Corporation, McLean, VA, September 1986. Wyeth, Robert K., "The Use of Laboratory Screening Procedures in the Chemical Evaluation of Uncontrolled Hazardous Waste Sites," Proceedings of the Second National Conference on Management of Uncontrolled Hazardous Waste Sites, Held on October 28-30, 1981 in Washington, DC, Hazardous Materials Control Research Institute, Silver Spring, MD, 1981, pp. 107-109. 175 ------- Zachowskl, Michael S. and Stephen A. Borgianini, "Problems and Pitfalls of Trace Ambient Organic Vapor Sampling at Uncontrolled Hazardous Waste Sites," Proceedings; National Symposium on Recent Advances in Pollutant Monitoring of Ambient Air and Stationary Sources, (EPA-60U/9-84-019J, Held on May 8-10, 1984 in Raleigh, NC, U.S. Environmental Protection Agency, Research Triangle Park, NC, November 1984, pp. 82-90. Zar, Jerrold H., "Power and Statistical Significance in Impact Evaluation," Ground Water Monitoring Review, Vol. 2, No. 3, Summer 1982, pp. 33-3T: 176 ------- APPENDIX A COMMENTS ON THE HRS RELATED TO HAZARDOUS WASTE CONCENTRATIONS Comments on the HRS related to hazardous waste concentrations have been related to the appropriateness and the manner of considering concentration data in the scoring of Superfund sites (Federal Register, 1982). A number of these comments have called for the inclusion of concentration data in at least three factors used in the HRS; however, the comments have not specified how the data should be obtained, analyzed, or incorporated in the HRS. This section briefly describes the current rating factors considered in the HRS, outlines comments addressing the modification of three of these factors to account for concentration data, and summarizes commentors1 suggestions for implementing the modifications. The HRS assigns three scores to a hazardous site, or facility. One of these scores is designed to reflect the potential for harm from substances that can explode or cause fires, and a second is designed to reflect the potential harm from direct contact with hazardous substances at a facility. Since these two scores are used to identify facilities requiring emergency attention, and since the commentors did not indicate that concentration data should be obtained to determine these scores, they will not be considered here. The third score, however, is designed to rank facilities across the nation of possible inclusion on the National Priorities List, which includes those sites slated for further government 177 ------- investigation and possible remedial action (Casler and Ramsey, 1985). This "site migration score" reflects the potential for harm to humans or the environment from migration of a hazardous substance away from the facility by three routes: ground water, surface water, or air. To determine the site migration score, a separate score is first determined for each of the three separate migration routes using a two-step process. First, numerical values are assigned to the factors for each migration route. Second, the values for each site are combined to yield the individual migration route scores, none of which can exceed 100. The site migration score is then determined by combining the three route scores into a single score that also cannot exceed 100 Federal Register, 1982). Comments regarding the incorporation of concentration data in the MRS have focused on the surface water and ground water routes. Both of these routes are scored by considering three major categories of factors: "release" (incorporating the subordinate categories "observed release," route characteristics," and "containment"), "waste characteristics," and "targets". The comments received by the EPA nave concerned observed releases and waste characteristics. (For a detailed explanation of the HRS and the scoring of rating factors, refer to Federal Register, 1982). The HRS considers that observed releases of hazardous substances have occurred if hazardous substances attributable to the site are found in the environment at a "significantly higher level 178 ------- than the background level" (Federal Register, 1982), regardless of regulatory limits (e.g., drinking water standards). If there is direct evidence of an observed release, a value of 45 is assigned to the "observed release" category. If no such evidence exists, a score of 0 is assigned to the factor. (However, in this case, alternative values for "route characteristics" and "containment" are assigned, with a combined maximum value of 45). Commentors have objected to the lack of consideration given to concentration levels in the assignment of the score for observed release, arguing that low concentrations of hazardous substances can be detected in many locales (i.e., not just Superfund sites) and that these low concentrations are not necessarily harmful. One of the commentors, the Chemical Manufacturers' Association, suggested that scores from 0 to 45 be assigned to the "observed release" category according to 6 concentration ranges (Chemical Manufacturers' Association, 1982). No rationale for this suggestion, or the specified ranges, was provided. The HRS also considers waste characteristics, which include the two rating factors, "toxicity/persistence" and "quantity". For both the surface water and ground water routes, the maximum values for these factors are 18 and 8, respectively. The score for the category is derived by summing the two factor values; therefore, the maximum category score is 26. The single toxicity/persistence value is determined by first assigning separate numerical values to the 179 ------- toxicity and the persistence of the hazardous substance using scales of 0 to 3, and then extracting an appropriate value (0 to 18) from a matrix having toxicity and persistence values along its axes. (The numericl values assigned to toxicity and persistence are determined by consulting guidance materials provided by the EPA). The hazardous waste quantity value is determined by assigning a numerical value to the estimated quantity of hazardous waste at the site, using an integer scale from 0 to 8 (Federal Register, 1982). Commentors have objected to the lack of consideration given to concentration data in the assignment of values for toxicity/ persistence and quantity, arguing the toxicity and the actual quantity of hazardous substances in the waste are both functions of concentration. More specifically, these commentors have stated that concentrations of hazardous substances could be within regulatory limits, and thus not pose a substantial hazard to human health (Homestake Mining Company, 1982). Commentors also have stated that estimating waste quantities without consideration of waste concentrations result in incorrect estimates and possible inequities. They indicate that such results are possible since sites are evaluated on the total quantity of waste (e.g., quantity of hazardous compounds and the nonhazardous material with which it was mixed before the mixture was dumped on the site) rather than the "actual" quantity of the hazardous substance (i.e., excluding the nonhazardous material) (American Mining Congress, 1983; Chemical Manufacturers' Association, 1982). 180 ------- No guidance was given by any of the commentors regarding the methods of obtaining appropriate concentration data or incorporating the data in the HRS. Additionally, the commentors did not suggest methods of considering the many substances for which there are no regulatory limits. In summary, the issues raised by commentors regarding the incorporation of concentration data in the HRS reflect concern about observed releases and the "actual" quantity and toxicity of hazardous wastes at Superfund sites. Since concentration data are not used in the HRS, except to identify observed releases, commentors contend that sites with low concentrations of wastes could receive site scores that are inappropriately high. None of the commentors, however, have addressed the issues of how concentration data should be obtained. This is important, as will be "discussed in the following section, since there is great variability in the size, nature, and characteristics of Superfund sites, and since the extent of concentration data required to characterize a site also may vary along a broad continuum. 181 ------- APPENDIX B DATA QUALITY An assessment of the quality of waste site data generally requires the comparison of certain characteristics of the data with specified standards. These standards are designed to ensure that the data are representative of the conditions at the site or in the vicinity of the site, as applicable. A set of concentration data for a particular contaminant from a site would be considered representative if the distribution of the data in time and space, within the data set, matched the temporal and spatial distribution of true concentrations from the site. As has been noted by others (e.g., Barcelona et al., 1985), representativeness must be assessed subjectively, as the true distribution of conditions from the site is not known. There are six aspects of representativeness of a data set that are amenable, to a varying degree, to objective assessment (adapted from Sachs, 1982 and Ford and Turina, 1985): • Specificity • Homogeneity • Accuracy • Precision • Sensitivity • Completeness 183 ------- An individual contaminant concentration measurement would be considered specific if the measurement reflected the level of that particular contaminant in the environment and was free from interferences caused by the presence of other contaminants. In part, a measurement is specific if it reflects what it claims to reflect. Thus, for example, a set of benzene data would be considered specific if the data reflected the levels of benzene, and only benzene, in the environment. Alternately, it would be considered not specific if the data that were labeled as "benzene" actually reflected levels of total aromatic hydrocarbons rather than benzene. It is not always possible to completely rule out interferences and thus ensure that data are specific. However, this should be done to the extent possible. An additional aspect of specificity is related to the concept of homogeneity. A set of data is considered homogeneous if the individual data points are derived from samples that were drawn from the same distribution (i.e., to the extent possible, they have the same characteristics; all controllable factors are the same). Data sets that combine samples from multiple distributions are considered to be nonhomogeneous. As related to specificity, the distribution reflected in a homogeneous data set must be the intended distribution. For example, if two wastes are present on an uncontrolled waste site and a differentiation between the concentrations of contaminants in these wastes is needed, then two 184 ------- distinct, homogeneous data sets should be developed, one reflecting samples of the first waste, the second reflecting samples from the second waste. In this case, a single combined nonhomogeneous data set would be useless in determining concentrations in the individual wastes. Accuracy is related to the statistical concept of bias. An individual measurement is considered accurate if it can be expected that the measured value is the true value. Operationally, a data set is considered sufficiently accurate if the average difference (or ratio) between the measured values and the true value is acceptable based on the intended use of the data. An important characteristic of accurate data is that it tends to be equally distributed above and below the true value. It is free from systematic error; error that causes a generally consistent bias upwards or downwards. Also, data can be accurate even though the individual measurements differ significantly from each other (on average the differences must cancel each other out). An immediately apparent problem with the concept of accuracy is that its assessment requires that the true value be known at the time of measurement. If the true value were available, the average difference between the measured values and the true value could be used as a measure of accuracy. This estimate of the average difference could then be used to determine whether a data set were 185 ------- sufficiently accurate. However, the true value is rarely known, generally only when standard solutions are being used. As an illustration of the concept of accuracy, consider the benzene data set exhibited in Table B-l. Assume these values represent the results of 10 replicate benzene samples taken in surface water at the same place and time. Assume also that the true value of 25 mg/1 was also known. These data would be considered accurate since their average is equal to the true value. Alternately, if their average were actually 24, the data might be considered sufficiently accurate depending on the purpose for which they are intended. Accuracy is typically a relative measure rather than an absolute measure. The concept of precision is frequently confused with that of accuracy as both address the extent to which the measured values deviate from the true values. As noted above, accurate data may exhibit wide variations between individual data points. Precision is a measure of the degree of this variation. It is a measure of the degree of agreement between separate measurements of the same quantity. The most common measure of precision is the square root of the average of the squared deviations of eacn data point from the sample average (i.e., the sample standard deviation of the data). If the estimation method is accurate, then precision can be estimated as the average distance between the individual measurements and the average of the measurements. Precise data is characterized by a 186 ------- TABLE B-l ILLUSTRATIVE EXAMPLE OF BENZENE CONCENTRATION DATA ACCURACY AND PRECISION Sample Number Value (mg/1) 1 17 2 43 3 26 4 9 5 7 6 19 7 31 8 49 9 21 10 28 Average 25 Standard Deviation 13.5 Coefficient of Variation 54% 187 ------- clustering of most of the measurements around the average value. An excellent discussion of the differences between accuracy and precision, using a "bulls-eye" analogy is presented in Kirchmer, 1983. Again referring to the example data set in Table B-l, the estimated precision of this data is 13.5, or as it is often stated, 54 percent of the mean value of 25. Estimation of precision requires multiple measurements at the same point in space and time or an assumption of spatial or temporal stability of the factor being measured. The acquisition of multiple samples may be very difficult or the assumption of stability unacceptable. Sensitivity, as described by Sachs (1982), is a measure of the minimum quantity of a substance that can be differentiated from zero. If the data set contains measurements listed as "not detected" or "not quantified" then the data set cannot be considered to be completely representative of the actual environmental concentrations. The "not detected" or "not quantified" reading may be as low as zero or as high as the detection or quantification limits, respectively. Thus, some error must be introduced in either assuming "not detected" concentrations equal zero or equal the detection limit (the two most common approaches to addressing "not detected" data). Special interpretative techniques that may require additional sampling, analysis, or interpretative assumptions (e.g., knowledge of the 188 ------- conditional distribution of the concentrations below the detection limit) are needed to analyze data containing readings below levels of detection or quantification (Gleit, 1985). The final important aspect of representativeness of a data set is completeness. There are no objective measures of completeness. A complete data set would reflect all significant variations in environmental or waste concentrations that occur in both space and time. Further, the data set would include measurements of all contaminants of concern, across all media of concern. Without complete knowledge about the site, estimates of the degree of completeness of a data set are not determinable. Overall, the principal consideration in determining the quality of concentration data in terms of its intended usefulness in a particular application is the degree to which the data are representative of the actual concentration levels from the site. In assessing the degree of representativeness, several questions must be asked reflecting the five most important aspects of representativeness: • Specificity: Do the data represent the parameters that they should, and, if not, is the difference acceptable? • Homogeneity: Are the data homogeneous, do they come from the same distributions? Were sampling' conditions the same for all samples within each data set? 189 ------- • Accuracy: • Precision: • Sensitivity: • Completeness: Are the data sufficiently accurate? Do we expect the estimated values to be the true values on average? Have systematic errors been eliminated or controlled to an acceptable degree? Are the data reproducible? Do replicate values cluster around the average or are they widely variable? Have all source of unintended variation been eliminated or controlled to an acceptable degree? Are the levels of detection and quantification low enough to show important variations in concentrations? Are all significant variations in concentrations reflected in the data? Have all contaminants of concern been measured? Have all media of concern been sampled? 190 ------- |