Setting information priorities for remediation decisions at a contaminated-groundwater site.

Many sites of contamination due to inappropriate disposal of hazardous materials or wastes have been found. These sites have the potential of damaging the environment and human health and thus need to be evaluated as to whether and what actions should be initiated. In the decision on whether a contaminated site should be subject to management, the knowledge concerning important parameters that would influence the decision will be beneficial to planning of data collection to support the decision. This paper presents a case study of contaminated site located in northern Taiwan, where the groundwater is contaminated by chlorinated hydrocarbons including trichloroethylene (TCE) and tetrachloroethylene (PCE). A site-specific multimedia risk assessment is performed to estimate the total risk resulting from the contamination. In addition, Monte Carlo simulation, rank correlation coefficients, and decision criteria are combined to develop a methodology for assessing the important of parameters in terms of their influence on the decision. It is found that TCE concentration, vegetable yield, deposition interception fraction of vegetables, and plant surface loss constant, are the four parameters important to the decision-making of the case problem.     

Model comparison for risk assessment: a case study of contaminated groundwater

Many environmental multimedia risk assessment models have been developed and widely used along with increasing sophistication of the risk assessment method. Despite of the considerable improvement, uncertainty remains a primary threat to the credibility of and users' confidence in the model-based risk assessments. In particular, it has been indicated that scenario and model uncertainty may affect significantly the assessment outcome. Furthermore, the uncertainty resulting from choosing different models has been shown more important than that caused by parameter uncertainty. Based on the relationship between exposure pathways and estimated risk results, this study develops a screening procedure to compare the relative suitability between potential multimedia models, which would facilitate the reduction of uncertainty due to model selection. MEPAS, MMSOILS, and CalTOX models, combined with Monte Carlo simulation, are applied to a realistic groundwater-contaminated site to demonstrate the process. It is also shown that the identification of important parameters and exposure pathways, and implicitly, the subsequent design of uncertainty reduction and risk management measures, would be better-formed.     

Study of contaminant transport at an open-tipping waste disposal site

Field and laboratory studies were conducted to estimate concentration of potential contaminants from landfill in the underlying groundwater, leachate, and surface water. Samples collected in the vicinity of the landfill were analyzed for physiochemical parameters, organic contaminants, and toxic heavy metals. Water quality results obtained were compared from published data and reports. The results indicate serious groundwater and surface water contamination in and around the waste disposal site. Analysis of the organic samples revealed that the site contains polychlorinated biphenyls and other organo-chlorine chemicals, principally chloro-benzenes. Although the amount of PCB concentration discovered was not extreme, their presence indicates a potentially serious environmental threat. Elevated concentrations of lead, copper, nickel, manganese, cadmium, and cobalt at the downgradient indicate that the contamination plume migrated further from the site, and the distribution of metals and metals containing wastes in the site is nonhomogeneous. These results clearly indicate that materials are poorly contained and are at risk of entering the environment. Therefore, full characterization of the dump contents and the integrity of the site are necessary to evaluate the scope of the problem and to identify suitable remediation options.     

The Use of Electrokinetics for Hazardous Waste Site Remediation

The Superfund Innovative Technology Evaluation (SITE) program was authorized as part of the 1986 amendments to the Superfund legislation. It represents a joint effort between U.S. EPA’s Office of Research and Development and Office of Solid Waste and Emergency Response. The program is designed to assist and encourage the development of waste treatment technologies that would contribute to more solutions to our hazardous waste problems.

Recently, EPA, through the SITE program, issued a work assignment to assess the “stateof- the-art” of electroklnetically enhanced contaminant removal from soils. Prior research efforts, both laboratory and field, have demonstrated that electroosmosis has the potential to be effective In facilitating the removal of certain types of hazardous wastes from soils. Particularly encouraging results have been achieved with inorganics in fine-grained soils where more traditional removal alternatives are less effective.

Although the results of various studies suggest that electrokinetics is a promising technology, further testing Is needed at both the laboratory and field levels to fully develop this technology for site remediation. A conceptual test program Is presented based on best available data which incorporates system design and operating parameters used in previous applications of this technology In the use of electrokinetics treatment as a remediation technique at hazardous waste sites.     

Addressing uncertainty in environmental modelling: a case study of integrated assessment of strategies to combat long-range transboundary air pollution

Model development and testing tend to concentrate on how well models represent “reality” or reproduce measurements. However, there are many sources of uncertainty in modelling atmospheric pollution, and those responsible for decisions on abatement strategies need to use modelled scenarios without fear that inaccuracies and assumptions in the modelling may mislead them. This paper explores how techniques from risk assessment may be used to examine a modelling study systematically. Those assumptions and uncertainties which could have significant consequences, whether arising from data used, the modelling itself, or factors omitted and incompleteness, may be identified using hazard and operability studies. This helps to target supporting studies—possibly using more complex models, or Monte Carlo uncertainty analysis; and to indicate potential implications to the decision makers. As a case study we have used work undertaken on uncertainties with the Abatement Strategies Assessment Model for the task force on integrated assessment modelling under the convention on long-range transboundary air pollution of the UN Economic Commission for Europe.     

Static Leaching of Solidified/Stabilized Hazardous Waste from the Soliditech Process

WILT, ANS 16.1 and TCLP leach tests were performed on solidified/stabilized (s/s) wastes treated by Soliditech, Inc. of Houston, Texas as part of a U.S. EPA SITE demonstration project conducted in December 1988 at the Imperial Oil Company/ Champion Chemical Company Superfund site in Morganville, New Jersey. All three leaching tests performed on the s/s wastes indicated that the primary contaminants of concern (lead and PCBs) were not leachable. The ANS 16.1 static leach test for the s/s wastes provided diffusion coefficients (D_e) for Al, Ca, and Na that were comparable to those obtained from the WILT test. However, plots of the ANS 16.1 data indicated that wetting of the samples confounded the static leaching process. The large column WILT D_e was used to estimate that less than 0.8 μg/cm² lead would leach from a one-cubic yard block of s/s waste in contact with groundwater over a 60-month leaching period. This corresponds to concentrations less than 10 μg/L lead in the water contacting the block of s/s waste.     

Refinery Sludge Treatment/Hazardous Waste Minimization Via Dehydration and Solvent Extraction

Abstract

The patented Carver-Greenfield (C-G) Process®, a combination of dehydration and solvent extraction treatment technologies, has a wide range of uses in separating hydrocarbon solvent-soluble hazardous organic contaminants (indigenous oil) from sludges, soils, and industrial wastes. As a result of this treatment, the products from a C-G Process facility are: ? Clean, dry solids which are typically suitable for disposal in nonhazardous landfills;

? Water which is treatable in an industrial or Publicly Owned Treatment Works (POTW) wastewater treatment facility;

? Extracted indigenous oil containing hydrocarbon soluble contaminants which may be recycled or reused or disposed of at less cost because its volume is smaller than the original waste feed.

The C-G Process was demonstrated on spent oily drilling fluids as part of the U.S. Environmental Protection Agency Superfund Innovative Technology Evaluation (SITE) Program. This paper summarizes the use of the C-G Process for economical treatment and minimization of hazardous refinery wastes, reviews the SITE program results, and describes extending the C-G Process technology to treatment of other wastes. Estimated treatment costs are presented.     

Model selection and evaluation for risk assessment of dioxin-contaminated sites

The general European population has a total intake of dioxins and dioxin-like chemicals near the limit recommended by the European Union, making additional exposure above background levels undesirable. For populations living near dioxin-contaminated sites, additional exposure may occur by intake of locally produced food, inhalation of particles, dermal contact with soils, or other exposure pathways. Risk assessment tools are required to estimate risks associated with contaminated sites and to set priorities for site remediation. Here, we review several multimedia models that can be applied as tools to support risk assessment. We then present a strategy to select, apply, evaluate, and adapt a model to address a specific situation. The case study we consider is a risk assessment of generic background dioxin exposure in Sweden, and we compare the predictions with environmental observations and exposure data from Sweden. Arguments are presented for selecting the CalTOX model for this case study. We demonstrate the application, evaluation, and adaptation of the model and discuss the requirements for extending the analysis to conduct risk assessment for subpopulations living near dioxin-contaminated sites.     

MODELKEY. Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity (5 pp)

BACKGROUND: Triggered by the requirement of Water Framework Directive for a good ecological status for European river systems till 2015 and by still existing lacks in tools for cause identification of insufficient ecological status MODELKEY (http:// www.modelkey.org), an Integrated Project with 26 partners from 14 European countries, was started in 2005. MODELKEY is the acronym for 'Models for assessing and forecasting the impact of environmental key pollutants on freshwater and marine ecosystems and biodiversity'. The project is funded by the European Commission within the Sixth Framework Programme. OBJECTIVES: MODELKEY comprises a multidisciplinary approach aiming at developing interlinked tools for an enhanced understanding of cause-effect-relationships between insufficient ecological status and environmental pollution as causative factor and for the assessment and forecasting of the risks of key pollutants on fresh water and marine ecosystems at a river basin and adjacent marine environment scale. New modelling tools for risk assessment including generic exposure assessment models, mechanistic models of toxic effects in simplified food chains, integrated diagnostic effect models based on community patterns, predictive component effect models applying artificial neural networks and GIS-based analysis of integrated risk indexes will be developed and linked to a user-friendly decision support system for the prioritisation of risks, contamination sources and contaminated sites. APPROACH: Modelling will be closely interlinked with extensive laboratory and field investigations. Early warning strategies on the basis of sub-lethal effects in vitro and in vivo are provided and combined with fractionation and analytical tools for effect-directed analysis of key toxicants. Integrated assessment of exposure and effects on biofilms, invertebrate and fish communities linking chemical analysis in water, sediment and biota with in vitro, in vivo and community level effect analysis is designed to provide data and conceptual understanding for risk arising from key toxicants in aquatic ecosystems and will be used for verification of various modelling approaches. CONCLUSION AND PERSPECTIVE: The developed tools will be verified in case studies representing European key areas including Mediterranean, Western and Central European river basins. An end-user-directed decision support system will be provided for cost-effective tool selection and appropriate risk and site prioritisation.     

Decision-support software tools for integrated risk assessment of hazardous substances in complex terrain

This paper presents the ongoing research at the Swiss Federal Institute of Technology (ETH), Zurich, related to the design and implementation of an IDSS (integrated decision support system) dedicated to integrated risk assessment and safety management with application to the transportation of hazardous substances. One of the goals is to construct advanced models to estimate (a) the optimal routing for transportation of hazardous substances and (b) optimise plans for emergency preparedness and management in case of potential (severe) accidents. As an output of this activity one aims at designing tools to represent risk to the public by using a GIS calculation platform, generically applicable to Switzerland. Though a database of some 700 chemicals is available, epichlorohydrin is the hazardous substance targeted in the first phase.     

Emission and fate assessment of methyl tertiary butyl ether in the Boston area airshed using a simple multimedia box model: comparison with urban air measurements

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 microg/m3 MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 microg/m3 and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (*OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

A model for estimating the potential biomagnification of chemicals in a generic food web: Preliminary development

GOAL, SCOPE AND BACKGROUND: Bioaccumulation and biomagnification of organic pollutants have been increasingly assessed and modeled during the last years. Due to the complexity of these processes and the large variability of food webs, setting generic assessments for these parameters is really difficult. Equilibrium models, based on a compound's lipophylicity, are the main tool in regulatory proposals, such as for identifying Persistent, Bioaccumulative and Toxic Substances (PBTs), although a refinement has been claimed by the scientific community. Toxicokinetic studies offer an alternative for these estimations, where biomagnification is modeled as a succession of bioaccumulation processes, each one regulated by toxicokinetic parameters. METHODS: A review of kinetic models covering species belonging to different trophic levels and with different ecological behavior has been conducted. The results were employed for setting a conceptual model for estimating the biomagnification potential in a generic food web, which was mathematically implemented through system dynamic models developed under data sheet software. Crystal Ball was then employed for allowing Monte Carlo based probabilistic calculations. Bioaccumulation laboratory assays have been performed to estimate toxicokinetic parameters in mussels (Mytilus edulis) with two PAHs (chrysene and benzo[a]pyrene). The contamination was delivered via food. The exposure period lasted more than one month followed then by a depuration phase. The contaminant content was determined on an individual basis on five replicates. RESULTS AND DISCUSSION:. The reviewed information suggested the development of a tiered conceptual biomagnification model, starting with a simplified food chain which can be refined to more realistic and complex models in successive levels. CONCLUSIONS: The mathematical implementation of the conceptual model offers tools for estimating the potential for bioaccumulation and biomagnification of chemicals under very different conditions. The versatility of the model can be used for both comparative estimations and for validating the model. RECOMMENDATIONS AND PERSPECTIVES: Since bioaccumulation and biomagnification processes are crucial elements for a proper risk assessment of chemicals, their estimation by mathematical models has been widely tested. However, inregulatory assessments, too simplistic models are still being used quite often. The biomagnification model presented in this study should be amore accurate alternative to these models. In comparison to other previously published biomagnification models, the present one covers the time variation of bioaccumulation using just a few toxicokinetic parameters.     

Potential Impact on Standards for Toxic Air Contaminants

Since the Bhopal incident, the public has placed pressure on regulatory agencies to set community exposure limits for the dozens of chemicals that may be released by manufacturing facilities. More or less objective limits can be established for the vast majority of these chemicals through the use of risk assessment. However, each step of the risk assessment process (i.e., hazard identification, dose-response assessment, exposure assessment, and risk characterization) contains a number of pitfalls that scientists need to avoid to ensure that valid limits are established. For example, in the hazard identification step there has been little discrimination among animal carcinogens with respect to mechanism of action or the epidemiology experience. In the dose-response portion, rarely is the range of “plausible” estimated risks presented. Physiologically based pharmacokinetic (PB-PK) models should be used to understand the difference between the tissue doses and the administered dose, as well as the difference in target tissue concentrations of the toxicant between rodents and humans. Biologically-based models like the Moolgavkar-Knudson-Venzon (MKV) should be developed and used, when appropriate. The exposure assessment step can be significantly improved by using more sensitive and specific sampling and analytical methods, more accurate exposure parameters, and computer models that can account for complex environmental factors. Whenever possible, model predictions of exposure and uptake should be validated by biological monitoring of exposed persons (urine, blood, adipose) or by field measurements of plants, soil, fish, air, or water. In each portion of an assessment, the weight of evidence approach should be used to identify the most defensible value. In the risk characterization, the best estimate of the potential risk as well as the highest plausible risk should be presented. Future assessments would be much improved if quantitative uncertainty analyses were conducted. Procedures are currently available for making future assessments. By correcting some of these shortcomings in how health risk assessments have been conducted, scientists and risk managers should be better able to identify scientifically appropriate ambient air standards and emission limits.     

Emission and Fate Assessment of Methyl Tertiary Butyl Ether in the Boston Area Airshed Using a Simple Multimedia Box Model: Comparison with Urban Air Measurements

Abstract

Expected urban air concentrations of the gasoline additive methyl tertiary butyl ether (MTBE) were calculated using volatile emissions estimates and screening transport models, and these predictions were compared with Boston, MA, area urban air measurements. The total volatile flux of MTBE into the Boston primary metropolitan statistical area (PMSA) airshed was calculated based on estimated automobile nontailpipe emissions and the Universal Quasi-Chemical Functional-Group Activity Coefficient computed abundance of MTBE in gasoline vapor. The fate of MTBE in the Boston PMSA was assessed using both the European Union System for the Evaluation of Substances, which is a steady-state multimedia box model, and a simple airshed box model. Both models were parameterized based on the meteorological conditions observed during air sampling in the Boston area. Measured average urban air concentrations of 0.1 and 1 [H9262]g/m³ MTBE during February and September of 2000, respectively, were comparable to corresponding model predictions of 0.3 and 1 μg/m³ and could be essentially explained from estimated temperature-dependent volatile emissions rates, observed average wind speed (the airshed flushing rate), and reaction with ambient tropospheric hydroxyl radical (.OH), within model uncertainty. These findings support the proposition that one can estimate gasoline component source fluxes and use simple multimedia models to screen the potential impact of future proposed gasoline additives on urban airsheds.     

The current practice of health risk assessment: potential impact on standards for toxic air contaminants

Since the Bhopal incident, the public has placed pressure on regulatory agencies to set community exposure limits for the dozens of chemicals that may be released by manufacturing facilities. More or less objective limits can be established for the vast majority of these chemicals through the use of risk assessment. However, each step of the risk assessment process (i.e., hazard identification, dose-response assessment, exposure assessment, and risk characterization) contains a number of pitfalls that scientists need to avoid to ensure that valid limits are established. For example, in the hazard identification step there has been little discrimination among animal carcinogens with respect to mechanism of action or the epidemiology experience. In the dose-response portion, rarely is the range of "plausible" estimated risks presented. Physiologically based pharmacokinetic (PB-PK) models should be used to understand the difference between the tissue doses and the administered dose, as well as the difference in target tissue concentrations of the toxicant between rodents and humans. Biologically-based models like the Moolgavkar-Knudson-Venzon (MKV) should be developed and used, when appropriate. The exposure assessment step can be significantly improved by using more sensitive and specific sampling and analytical methods, more accurate exposure parameters, and computer models that can account for complex environmental factors. Whenever possible, model predictions of exposure and uptake should be validated by biological monitoring of exposed persons (urine, blood, adipose) or by field measurements of plants, soil, fish, air, or water. In each portion of an assessment, the weight of evidence approach should be used to identify the most defensible value. In the risk characterization, the best estimate of the potential risk as well as the highest plausible risk should be presented. Future assessments would be much improved if quantitative uncertainty analyses were conducted. Procedures are currently available for making future assessments. By correcting some of these shortcomings in how health risk assessments have been conducted, scientists and risk managers should be better able to identify scientifically appropriate ambient air standards and emission limits.     

Some Heavy-Metal Pollutants in the Air of Naples

ABSTRACT

In this paper, assumptions regarding future land use as a key uncertainty is considered and its impact on risk analysis for contaminated sites is assessed. Risks are assessed for two land use scenarios (current-use industrial and future-use residential) using probabilistic models that incorporate uncertainty and variability in the exposure parameters. Residual risks are calculated for both industrial and residential cleanup standards. A Superfund site in northern California is considered.

In general, for the unremediated case, the future-use residential scenarios produce larger risks (1 to 3 orders of magnitude) than current- (continued) use industrial scenarios. For the Superfund site studied, the residual risks calculated for the remedy selected was not sufficiently protective of future-use residents in that it did not meet .S. Environmental Protection Agency (EPA) risk goals, but was protective of current-use workers, even though the cleanup criteria were based on residential use. Alternative risk management practices, such as deed restrictions, can be used in such cases.     

Thermal Encapsulation of Metals in Superfund Soils

Abstract

Superfund sites frequently contain both heavy metals and organic hazardous waste. If not properly controlled, the metals may be changed to a more leachable form and may also be emitted to the atmosphere via the exhaust stack. This paper documents a batch kiln R&D test program to solve these metal-related problems. It was performed under the U.S. EPA’s SITE (Superfund Innovative Technology Evaluation) Emerging Technology Program. Allis Mineral Systems has developed the Thermal Encapsulation Process. Metals with limits set by EPA’s TCLP (Toxicity Characteristic Leaching Procedure) test and BIF (boiler and industrial furnace) stack emission regulations, such as cadmium, chromium, and lead, are the initial target of this process. This process, while unproven in these areas, may also apply to mixed waste (EPA hazardous waste/low-level radioactive wastes) and may also benefit commercial hazardous waste or Superfund thermal treatment systems. The results of the SITE tests were positive: strong, durable nodules were produced with excellent crush strength and improved resistance to leaching. Feed preparation, particularly control of moisture content, was found to be a key element in initiation of agglomeration. A good correlation was found between decreasing TCLP metals leachate levels and increasing crush strength.     

Setting the most robust effluent level under severe uncertainty: Application of information-gap decision theory to chemical management

Decisions in ecological risk management for chemical substances must be made based on incomplete information due to uncertainties. To protect the ecosystems from the adverse effect of chemicals, a precautionary approach is often taken. The precautionary approach, which is based on conservative assumptions about the risks of chemical substances, can be applied selecting management models and data. This approach can lead to an adequate margin of safety for ecosystems by reducing exposure to harmful substances, either by reducing the use of target chemicals or putting in place strict water quality criteria. However, the reduction of chemical use or effluent concentrations typically entails a financial burden. The cost effectiveness of the precautionary approach may be small. Hence, we need to develop a formulaic methodology in chemical risk management that can sufficiently protect ecosystems in a cost-effective way, even when we do not have sufficient information for chemical management. Information-gap decision theory can provide the formulaic methodology. Information-gap decision theory determines which action is the most robust to uncertainty by guaranteeing an acceptable outcome under the largest degree of uncertainty without requiring information about the extent of parameter uncertainty at the outset. In this paper, we illustrate the application of information-gap decision theory to derive a framework for setting effluent limits of pollutants for point sources under uncertainty. Our application incorporates a cost for reduction in pollutant emission and a cost to wildlife species affected by the pollutant. Our framework enables us to settle upon actions to deal with severe uncertainty in ecological risk management of chemicals.     

The effect of export to the deep sea on the long-range transport potential of persistent organic pollutants

BACKGROUND: Export to the deep sea has been found to be a relevant pathway for highly hydrophobic chemicals. The objective of this study is to investigate the influence of this process on the potential for long-range transport (LRT) of such chemicals. METHODS: The spatial range as a measure of potential for LRT is calculated for seven PCB congeners with the multimedia fate and transport model ChemRange. Spatial ranges for cases with and without deep sea export are compared. RESULTS AND DISCUSSION: Export to the deep sea leads to increased transfer from the air to the surface ocean and, thereby, to lower spatial ranges for PCB congeners whose net deposition rate constant is similar to or greater than the atmospheric degradation rate constant. This is fulfilled for the PCB congeners 101, 153, 180, and 194. The spatial ranges of the congeners 8, 28, and 52, in contrast, are not affected by deep sea export. With export to the deep sea included in the model, the spatial ranges of the heavier congener are similar to those of the lighter ones, while the intermediate congeners 101 and 153 have the highest potential for long-range transport. CONCLUSIONS: Transfer to the deep ocean affects the mass balance and the potential for LRT of highly hydrophobic chemicals and should be included in multimedia fate models containing a compartment for ocean water.     

Application of first-order reliability method to modelling the fate and transport of benzene in groundwater

Parameter uncertainty plays a significant role in decision making regarding groundwater contamination and remediation, especially for non-conservative chemicals. This paper presents a probabilistic screening model to accommodate parameter uncertainty in the aquifer media, and physical–chemical parameters, using the first-order reliability method (FORM). The application of the developed model is illustrated on transport of benzene in groundwater. The results matched those obtained using the Monte Carlo simulation method, with a smaller number of functional evaluations. Parametric studies were conducted to estimate the effect of various parameters on the results.