Process Engineering for Pollution Control and Waste Minimization_12

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Các khái niệm và mô hình của chemodynamics được cung cấp chi tiết đáng kể bởi Thibodeaux (5), và Reible và Choi (6). Theo mục đích của cuộc thảo luận này, nó được giả định rằng các mô hình thích hợp của số phận và vận chuyển chất gây ô nhiễm đối với trường hợp được biết, ước tính, hoặc có sẵn trong một số thời trang.

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Nội dung Text: Process Engineering for Pollution Control and Waste Minimization_12

material and energy balances many be found in a number of chemical engineering texts, such as Felder and Rousseau (4) and others. 3 ADDITION OF CHEMODYNAMICS In order to take LCA beyond its usual scope to assess a waste site remedy, we need not only to include the mass and energy balances for environmental compartments, but also the models and mechanisms of inter- and intramedia transport. The concepts and models of chemodynamics are provided in significant detail by Thibodeaux (5), and by Reible and Choi (6). For the purposes of this discussion, it is assumed that appropriate models of the fate and transport of contaminants for a case are known, estimated, or available in some fashion. Since the objective of the LCA in remediation is to assess the burden being placed on the environment by various remedies, the application of realistic and appropriate models is essential and found in references above (5,6) for certain cases. 4 APPLICATION With the objective being assessment of the environmental (eco- and human health) burden from various remedies in a waste site problem, we may employ, as with LCA, risk assessment in the reverse, following the methodology of Hwang (7) as extended by Constant et al. (8). The exposure is summed from different routes to get total exposure, Et, which, to have an acceptable risk, should not exceed the reference dose level (RL). Exposures are calculated as in any other assessment, based on concentration, time, body weight, etc. Key here is the concentration at the exposure point (receptor), which is a function of the concen- tration in the soil or other medium. This function is the subject of much modeling work as described above, as it is essential to have accurate representations of the fate and transport of the contaminants in and across media under investigation. Thus, one may apply the above exposure method for an acceptable risk, combined with LCA, as follows (8). First, land use or other resource needs are established, followed by assuming a chemical management or remediation scheme or treat- ment train concept. Then, incorporating regulations, laws, and liabilities, chemi- cals are traced from “cradle to grave” throughout the process as in a typical LCA. Next, risk is assessed for the scheme (7) with all material and energy balances incorporated, along with eco-risk as appropriate. With these balances completed including appropriate fate and transport models, economics of the process(es) being considered are established. If the economics are acceptable, then the technology or waste processing is appropriate for the present level of available technology considered (or assumed) in the first step. If the economics are unfavorable, another treatment, manufacturing, or remediation scheme should be Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
applied to this integrated management methodology for comparison to the first attempt. Thus, methods can be evaluated for risk-based remediation or manufac- turing as in LCA for the most economical approach. It should be noted here that technology is on a moving time line, and what is successful and economical today will need to be reassessed several times in the future as chemical fate and transport modeling, our understanding of the environment, technologies, and regulations all change. In this manner, “new” technologies such as monitored natural attenuation (MNA) can be assessed alongside and with active remedies as described in the example below. 5 EXAMPLE OF ASSESSMENT The Petro Processors, Inc. (PPI), site is one of the most significant Superfund sites in the United States. While it is not directly under Superfund, due to agreement among the parties and existing consent decree in the U.S. District Court, Middle District of LA, it provides an excellent example, via hindsight, of the utility of LCA for risk-based remediation methodology as described by Constant et al. (8). Details of the site(s), being named Brooklawn and Scenic, for the nearby roadways, may be found at EPA’s Region VI Web site (9), and are not described here. The site(s) contain approximately 400,000 tons of chlorinated hydrocarbon wastes, including hexachlorobenzene, hexachlorobutadiene, TCE, DCE, lower chlorinated products, and numerous other petrochemical wastes of similar nature. The mixture forms a dense, nonaqueous, viscous phase, which is currently covered and maintained by hydraulic containment of the groundwater and recov- ery of the organic phase (both of which are treated on-site) under strict regulatory requirements. Louisiana State University (LSU) has served as the Court’s Expert for the last 10 years regarding cleanup of this site, with the role being research into advanced technologies and assisting the court in monitoring and assessing the remediation. Just prior to LSU’s involvement, the remedy was to remove the waste, stabilize the material, and place it in a lined 1 × 106 yd3 vault, with some hydraulic containment and recovery of site areas found difficult to remove due to the high water table. However, due to volatile emissions exceeding fence-line limits, the removal method was abandoned. The next remedy to be put in place was active hydraulic containment (expansion of the previous pumping layout), with several hundred wells to remove organics and contaminated water over the long term in order to protect the underlying aquifer and prevent migration. To date, only about 1% of the free-phase material has been removed, but containment appears successful, at the expense of treating millions of gallons of water containing only trace contamination levels. As this pumping method was being installed at Brooklawn, via ongoing research by LSU and site personnel for Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
augmentation of the pumping operation by both passive and active technologies, intrinsic biodegradation and hence natural attenuation was studied and then incorporated into the remedy. The addition of biodegradation, sorption, disper- sion, etc. as required within the lines of evidence of MNA as presented by EPA (10), has had a significant impact on the remedy of the PPI site. It appears at this time that active pumping of significant water volumes may be greatly reduced, while still focusing on source removal (NAPL), with the understanding that significant residuals remain bound in these systems. The MNA component is proposed to contain and reduce the size of contaminated ground- water over time, with acceptable risk. Thus, using the same receptors and risk issues, incorporation of MNA into the PPI remedy promises to reduce signifi- cantly the cost of the remedy, without increasing eco- or human health risk. In a recent comparison, starting with the same source and endpoints, in the same time frame, MNA with limited hydraulic containment (a few source removal wells) was evaluated against active hydraulic containment and recovery (many pumping wells across the site) for the Scenic site of PPI. This assessment included monitoring and other costs associated with these technologies, and a 70% cost savings was found by incorporation of MNA into the remedy. This was due mainly to the reduced number of wells to be installed and the significant reduction in treatment of produced water. While this example case of remedy comparison has occurred during the remediation of PPI, it clearly shows that we have the tools of LCA, risk-based remediation, and MNA at our disposal. When properly integrated, one can provide acceptable waste management schemes prior to initiation of a manufacturing project or site remediation. However, as technology changes, as stated earlier, this assessment must be ongoing. REFERENCES 1. T. E. Graedel, Streamlined Life-Cycle Assessment, pp. 97–98. Englewood Cliffs, NJ: Prentice Hall, 1998. 2. P. C. Schulze (ed.), Measures of Environmental Performance and Ecosystem Condi- tion. Washington, DC: National Academy Press, 1999. 3. R. J. Walter, Practical Compliance with the EPA Risk Management Program. New York: Center for Chemical Process Safety of the AIChE, 1999. 4. R. M. Felder and R. W. Rousseau, Elementary Principles of Chemical Processes, pp. 81–86. New York: Wiley, 1978. 5. L. J. Thibodeaux, Chemodynamics: Environmental Movement of Chemicals in Air, Water and Soil. New York: Wiley, 1979. 6. B. Choy and D. D. Reible, Diffusion Models of Environmental Transport. Boca Raton, FL: Lewis Pub., CRC Press, 2000. 7. S. T. Hwang. J. Environ. Sci. Health, A, vol. A27, no. 3, pp. 843–861, 1992. 8. W. D. Constant, L. J. Thibodeaux, and A. R. Machen, Environmental Chemical Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
Engineering: Part I—Fluxion; Part II—Pathways. Trends Chem. Eng., vol. 2, pp. 525–542, 1994. 9. U.S. Environmental Protection Agency (EPA) Region VI Website, Information on Superfund sites, Louisiana, Petro Processors, Inc., http://www.epa.gov/earth1r6/ 6sf/6sf-la.htm. 10. Robert S. Kerr Environmental Research Center (U.S. EPA), Natural attenuation short course materials, Ada, OK, December 2–4, 1997. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
17 Risk-Based Pollution Control and Waste Minimization Concepts Gilbert J. Gonzales Los Alamos National Laboratory, Los Alamos, New Mexico and New Mexico State University, Las Cruces, New Mexico 1 INTRODUCTION Ecological risk assessment is defined as “the qualitative or quantitative appraisal of impact, potential or real, of one or more stressors (such as pollution) on flora, fauna, or the encompassing ecosystem.” The underlying principles behind risk reduction and integrated decision making that are detailed in U.S. Environmental Protection Agency (EPA) strategic initiatives and guiding principles include pollution prevention (1). Pollution control (PC) and waste minimization (WM) are probably the most effective means of reducing risk to humans and the environment from hazardous and radioactive waste. Pollution control can be defined as any activity that reduces the release to the environment of substances that can cause adverse effects to humans or other biological organisms. This includes pollution prevention and waste minimization. Waste minimization is defined as pollution prevention measures that reduce Resource Conservation and Recovery Act (RCRA) hazardous waste (2). Reduced risk is one benefit of these practices, and it results most directly from lower concentrations of contaminants entering the environment from both planned and accidental releases. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
Although it is difficult to quantify the reductions in the release of contam- inants to the environment that have resulted from reductions in waste, the reductions have most assuredly reduced risk to humans and the environment posed by toxicants. Using examples from Los Alamos National Laboratory (LANL), we will discuss the interrelatedness of pollution prevention/waste min- imization with risk reduction and how risk assessment can be generally applied to the field of pollution prevention and waste minimization. While emphasis in this chapter is on “ecological risk assessment,” the concepts and principles can also be applied to human health risk assessment. For purposes of this chapter, distinction is not made between pollution prevention, waste minimization, re- cycling or other waste management techniques, and other related terms. Rather, emphasis is on source reduction, which includes any practice that reduces the amount of contaminant entering a waste stream or the environment. It is evident that the EPA’s hierarchy of general pollution prevention and waste minimization methods is implicitly related to risk reduction (2). The preferred method, source reduction, results in the greatest reduction in human and ecological risk from contaminants. Source reduction is followed in effectiveness by recycling, treatment, and disposal. While it is possible, depending on the technology used, that recycling and treatment may increase risk to worker health because of increases in contact handling of waste, the prioritized list (source reduction → recycling → treatment → disposal) generally results in a decrease in risk to the public and the environment as one progresses from the least preferred to the most preferred method. The reason for this is simple. The preferred method results in little, if any, release of contaminants into the environ- ment compared to the less preferred methods; with the less preferred methods, not only does the quantity of contaminants potentially released into the environ- ment increase, the potential to release them increases. With this premise, it is then important to realize the magnitude of risk reduction achieved by employing pollution prevention and waste minimization at facilities such as LANL. 2 SITE DESCRIPTION AND CHARACTERIZATION LANL is located in north-central New Mexico, approximately 60 miles northwest of Santa Fe (Figure 1). LANL is a U.S. Department of Energy-owned complex managed by the University of California that was founded in 1943 as part of the Manhattan Project to create the first nuclear weapon. Since then, LANL’s mission to design, develop, and test nuclear weapons has expanded to other areas of nuclear science and energy research. The Laboratory comprises dozens of individual technical areas located on 43 square miles of land area; about 1400 major buildings and other facilities are part of the Laboratory. The Laboratory is situated on the Pajarito Plateau, which consists of a series of fingerlike mesas separated by deep east-to-west–oriented Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
Los Alamos National Laboratory Technical Area boundaries County boundaries ST RE Other political boundaries FO LOS ALAMOS Major paved roads 0 0.5 1 2 mi L A COUNTY N IO RIO ARRIBA COUNTY 0 0.5 1 2 km T LOS ALAMOS COUNTY SANDOVAL COUNTY SANTA FE COUNTY A SANTA FE COUNTY N E SANTA FE F NATIONAL N To A FOREST T Espanola N A 30 S LOS ALAMOS 502 502 502 Pa To ja East rito Jem Santa Fe 4 Ro ez R BANDELIER ad oad 501 NAT. MON. SANDO- VAL CO. SAN ILDEFONSO PUEBLO LANDS 4 WHITE 4 LO ROCK 4 SA LA MO SAN SC DO OU VA NT LC Y BANDELIER OU NT Y NATIONAL MONUMENT e nd ra G io R U. S. A. cARTography by A. Kron 4/5/00 UT CO Tierra Amarilla TAOS AZ OK NM COUNTY RIO ARRIBA COUNTY TX Taos LOS ALAMOS COUNTY Taos Los Alamos Los Alamos ★ Santa Fe Santa Fe Grants Albuquerque SANDOVAL SANTA NEW MEXICO COUNTY FE Bernalillo Socorro COUNTY Albuquerque BERNALILLO Las Cruces COUNTY FIGURE 1 Location of the Los Alamos National Laboratory. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
canyons cut by intermittent streams (Figure 2). Mesa tops range in elevation from approximately 7800 ft on the flanks of the Jemez Mountains to about 6200 ft at their eastern termination above the Rio Grande. Researchers at Los Alamos work on initiatives related to the Laboratory’s central mission of enhancing global security as well as on basic research in a variety of disciplines related to advanced and nuclear materials research, devel- opment, and applications; experimental science and engineering; and theory, modeling, analysis, and computation. As a fully functional institution, LANL also engages in a number of related activities including waste management; infrastruc- ture and central services; facility maintenance and refurbishment; environmental, FIGURE 2 Overhead view of the topography in and around the Los Alamos National Laboratory. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
ecological, cultural, and natural resource management; and environmental resto- ration, including decontamination and decommissioning. As result of the scien- tific and technical work conducted at Los Alamos, the Laboratory generates, treats, and stores hazardous, mixed, and radioactive wastes. About 2120 contaminant potential release sites (PRSs) have been identified at LANL. The LANL PRSs are diverse and include past material disposal areas (landfills), canyons, drain lines, firing sites, outfalls, and other random sites such as spill locations. Categorizing contaminants into three types—organics, metals, and radionuclides—Los Alamos has all three present. The contaminants include volatile and semivolatile organics, polychlorinated biphenyls (PCBs), asbestos, pesticides, herbicides, heavy metals, beryllium, radionuclides, petroleum prod- ucts, and high explosives (3). The primary mechanisms for potential contaminant release from the site is surface-water runoff carrying potentially contaminated sediments and soil erosion exposing buried contaminants. The main pathways by which released contaminants can reach off-site residents are through infiltration into alluvial aquifers, airborne dispersion of particulate matter, and sediment migration from surface-water runoff. Like many other sites, the predominant pathway by which contaminants enter terrestrial biological systems is the inges- tion of soil, intentional or not. Diverse topography, ecology, and other factors make the consideration of issues related to contamination in the LANL environment complex. “Since 1990, LANL’s environmental restoration project has conducted over 100 cleanups. The environmental restoration project has also decommissioned over 30 structures and conducted three RCRA closure actions during this period. Schedules have been published for the planned cleanup of approximately 700 to 750 additional sites. This schedule encompasses a period of about 10 years, beginning with fiscal year 1998. The number of cleanups per year varies from approximately 100 in fiscal year 2002 to 18 in fiscal year 2008. An important and integral part of this pollution prevention technology and of identifying interim protection measures is ecological risk assessment” (3). 3 POLLUTION PREVENTION AND WASTE MINIMIZATION AT LANL The pollution prevention program at the Laboratory has been successful in reducing overall LANL wastes requiring disposal by 30% over the last 5 years. The program is site wide but has facility-specific components, especially for the larger generators of radioactive and hazardous chemical wastes. Past reductions indicate that waste generation in the future should be less than that projected. The Site Pollution Prevention Plan for Los Alamos National Laboratory (4) describes the LANL Pollution Prevention and Waste Minimization Programs, including a general program description, recently implemented actions, specific volume Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
reductions resulting from recent actions, and current development/demonstration efforts that have not yet been implemented. More specifically, LANL has achieved reductions in the generation of hazardous waste, low-level radioactive waste (LLW), and mixed LLW. These and two other waste types are defined as follows: Hazardous waste—Any substance containing waste that is regulated by RCRA, the Toxic Substances Control Act, and New Mexico as a Special Waste. Low-level radioactive waste (LLW)—Radionuclide-containing substances with a radionuclide activity (sometimes referred to as concentration) of less than 100 nCi/g. Mixed LLW—Substances containing both RCRA constituents and LLW. Transuranic radioactive (TRU) waste—Radionuclide-containing substances with a radionuclide activity (concentration) equal to or greater than 100 nCi/g. Mixed TRU waste—Substances containing both RCRA and TRU waste. Estimated reduction rates of chronically generated waste, by waste type, over a 6-year period are (D. Wilburn, personal communication, 2000) Hazardous waste: 11%/yr (65% from 1993 to 1999) LLW: 11%/yr (67% from 1993 to 1999) Mixed LLW: 12%/yr (72% from 1993 to 1999) Production of TRU and mixed TRU waste combined has increased by an average of 38%/yr (228% from 1993 to 1999). The Laboratory has dozens of pollution prevention projects ongoing and planned. Some of the efforts are pollution prevention and waste minimization in the strictest sense and some (e.g., separation of waste types or satellite treatment followed by centralized treatment) are pollution control in the broadest sense, including efforts where cost savings is the primary goal and pollution control is a secondary benefit. Three examples of pollution control/waste minimization at LANL follow. Generator Set-Aside Fee-Funded (GSAF) Plutonium Ingot Storage Cubicle Project. “An aliquot casting and blending technique is under imple- mentation at LANLs Plutonium Facility. The aliquot process allows out-of-specification plutonium to be blended with other plutonium so that the final mixed batch meets specifications and is uniform. This avoids the cost and waste generation related to reprocessing out-of-specification plutonium ingots through the nitric acid line. In addition the more uniform product will reduce the reject rate and will avoid reprocessing and remanufacturing wastes. This project will fabricate a storage system Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
with 20 cubicles. It is expected that 12.5 m3 of TRU waste can be avoided over the 25 year life of the cubicle system. This project has an estimated 100% return on investment when prior investments are included in the base project cost. This project is the final step necessary to achieve aliquot blending. The GSAF program is funding purchase of the storage cubicle and the operating group has programmatic support for installing and qualifying the cubicle.” GSAF Reduction of Acid Waste and Emissions. “The Laboratory’s Analyti- cal Chemistry Sciences Group’s performance of analytical services at one of the Laboratory’s technical areas requires the dissolution of up to 20,000 samples per year. The current process is hot plate digestion which requires large quantities of chemicals, mostly acids, and results in the volatilization and release to the atmosphere of 90% of those chemicals. The yearly consumption of HNO3, HCl, HF, HClO4 and NH4OH is estimated to be 3395 kgs. About 3095 kgs of these chemicals are volatilized and become air emissions from the stacks; the balance is diluted and discharged to the Laboratory’s Radioactive Liquid Waste Treatment Facility via the LLW acid line. The stack emissions constitute about 30% of the Laboratory’s annual hazardous air pollutant discharges. By switching to a microwave and muffle furnace oven process, annual consumption of the chemicals listed above can be reduced to about 370 kgs, an 89% reduction. It is estimated that implementing the new process will reduce the Laboratory’s hazardous air pollution discharges by three tons. The estimated return on investment for this project is 82%.” Waste Minimization and Microconcentric Nebulization for Inductively Cou- pled Plasma-Atomic Emission Spectroscopy. “One of the most popular techniques for multi-element analysis is inductively coupled plasma atomic emission spectroscopy (ICP-AES). The most common method of introducing samples into the ICP torch is pneumatic nebulization. The standard nebulizers, in conjunction with typical spray chambers, exhibit very low transport efficiency. Because of this inefficiency the ICP-AES generates almost a liter per day of rinse water that consists primarily of dilute nitric acid mixed with other contaminants. The other contaminants can be TRU waste, LLW, mixed LLW or hazardous waste depending on the samples analyzed. Under this project an existing microconcentric nebulizer will be deployed with the ICP-AES and optimized for analysis of trace elements in a variety of plutonium-containing matrices. It is expected that using an optimized microconcentric nebulizer will reduce the daily rinse water from the spray chamber drain to about 50 ml. This represents a 95% or 200 l/yr reduction in the volume of waste requiring disposal. A 50 liter per year reduction in LLW plastic sample containers is expected. Reducing the volume of samples in the glovebox will Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
simplify the ICP-AES operation, reducing various risk parameters. The return on investment ranges from 10–50%.” 4 ECOLOGICAL RISK ASSESSMENT Ecological risk assessment is defined as “the qualitative or quantitative appraisal of impact, potential or real, of one or more stressors (such as pollution) on flora, fauna, or the encompassing ecosystem.” The Laboratory is employing the EPA’s iterative and tiered approach to ecological risk assessment whereby less complex assessments with greater conservatism and uncertainty are employed first, fol- lowed by the advancement of potential problem areas and contaminants to progressively more complex and realistic assessments with lower uncertainty. The purpose of this section is not to present ecological risk assessment methods, as there are many excellent sources on this subject (5–8). Rather, the purpose is to introduce concepts in ecological risk assessment that could be considered in designing pollution control and waste minimization programs. 4.1 History at the Los Alamos National Laboratory Ecological risk assessment (“ecorisk”) at the Laboratory is a work in progress. Methods for ecorisk screening and “tier 2” assessments have been in development and implementation since approximately 1993. Most screenings and assessments completed at the Laboratory thus far are based on the U.S. EPA hazard quotient method, whereby hazard quotient values are calculated for receptors for each contaminant by area and may be thought of as a ratio of a receptor’s exposure at the site to a safe limit or benchmark: n ∑ HQij HIi = (1) j=1 where HIi is the hazard index for receptor I to n contaminants of potential concern (COPCs), and exposureij HQij = (2) safe limitij where HQij is the hazard quotient for receptor I to COPC j exposureij is the dose to receptor i for COPC j safe limit is an effects or no effects level, such as a chronic no-observed- adverse-effects level (NOAEL) Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
4.1.1 Screening In 1995 a very conservative method for screening contaminants and contaminated areas was developed (9). The method involved the selection of ecological endpoints that focused on animal feeding guilds, a listing of candidate contami- nants, exposure/dose–response estimation, estimation of food and soil ingestion, and risk characterization. A comparison value or safe limit was based on foraging mode, behaviors, types of food consumed, the amount consumed, and NOAELs or radiation dose limits when available. The safe limits for radionuclides were largely laboratory-derived rat-based values used in human risk assessments. As such, this and the use of other conservative factors or assumptions resulted in a method that likely overestimated potential risk by orders of magnitude, espe- cially for radionuclides. At least one application of the method is known to have occurred (10). Currently at LANL, ecorisk screening encompasses qualitative “scoping evaluation” as the basis of problem formulation and “screening evaluation” to identify contaminants of potential concern (COPCs) by exposure media. The screening evaluation focuses on identifying sites that require further investigation and risk characterization (11). A key component to the screening evaluation, and one of interest to PC/WM, is the ecological screening level (ESL) concept. An ESL is basically a contaminant safe limit, or acceptable effects level, below which measurable effects are not expected. ESLs are most useful in units of contaminant amount per quantity of soil, so that measurements of contaminant levels in soil can be quickly and directly compared. The ESLs are developed for each ecolog- ical receptor of interest, each chemical, and are media specific. They are deter- mined so that if an area has levels of a chemical above the ESL in any medium, then the area is deemed to pose a potentially unacceptable risk to ecological receptors. Calculations of ESLs require toxicity information, including toxicity reference values (TRVs), preferably chronic NOAELs, and knowledge of transfer coefficients including bioconcentration and bioaccumulation factors. Details on this information and on the process for calculating and selecting ESLs are documented in a LANL report (11); however a summary is provided here. Nonradionuclides. “Although soil ESLs are based on exposure of terres- trial receptors—plants, invertebrates (earthworms), and wildlife—they are deter- mined differently for each receptor. The different approaches are required because of the different ways that toxicological experiments are performed for these organisms. For plants, earthworms and other soil-dwelling invertebrates, effects are based on the concentration of a COPC in soil. Therefore, ESL values are directly based on effects concentrations and modeling is not required. For plants and invertebrates the soil ESL was ‘back-calculated’ from No-Observed-Effect- Concentrations. Exposure to wildlife, however, is dependent on exposure of the organism to a chemical constituent from a given medium (such as soil or Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
foodstuff) through direct and indirect means (i.e., ingestion, inhalation, and dermal). Wildlife ESL values were based on the dietary regimen of the receptor, including consumption of plants, invertebrates, and vertebrate flesh, with some incidental soil ingestion (11).” The soil ESL was “back-calculated” as the soil concentration of a COPC resulting from exposure to the NOAEL. Starting with the EPA’s general terrestrial wildlife exposure model (12), inverting to convert soil concentration to dose, relating food intake to soil intake, and solving for COPC- and receptor-specific ESLs, models such as Eq. (3) for omnivores were used to compute ESLs for nonradionuclides: NOAELij ESLij = (3) Ii ⋅ (fsi + fpi ⋅ TFplant,j + fii ⋅ TFinvert,j where ESLij is the soil ESL for omnivore i and COPC j (mg/kg) NOAELij is the NOAEL for omnivore i and COPC j (mg/kg/day) fsi is the fraction of soil ingested by omnivore i, expressed as a fraction of the dietary intake Ii is the normalized daily dietary ingestion rate for omnivore i (kg/kg/day) fpi is the fraction of plants in diet for omnivore i TFplant,j is a unitless transfer factor from soil to plants for COPC j fii is the fraction of invertebrates in diet for omnivore i TFinsect,j is a unitless transfer factor from soil to insects for COPC j For any given COPC, the soil ESL used for initial screening was often the lowest receptor-specific soil ESL value among plants, invertebrates, robin, kestrel, shrew, mouse, cottontail, and fox. Models were developed for sediment and water. More detail can be found in Ref. 11. Radionuclides. Radionuclide dose limits are the equivalent of the NOAELs used to develop nonradionuclide ESLs (11). For screening at LANL, radionuclide ESLs were based on the International Atomic Energy Agency (IAEA)-recommended dose limit of 0.1 rad per day (13). At LANL the radionu- clide dose to terrestrial biota was taken as the sum of the dose from internally deposited radionuclides and external dose from gamma emitting radionuclides in soil [Eq. (4)]. Total acceptable dose = 0.1 (rad/day) = internal dose (4) + external dose Detailed formulas can be found in Ref. 11. Conservative assumptions about the size of the organism, its diet, the geometry of the contaminated source, and the location of the receptor relative to the contaminated source are used by LANL for estimating internal and external doses for screening purposes. The internal dose Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
to wildlife is calculated by multiplying the effective energy of a radionuclide by the body burden of that radionuclide in an organism. The external dose is the dose coefficient for skin exposed to contaminated water or soil. Calculations for estimating internal and external doses from radionuclides in soil can be found in literature by Higley and Kuperman (14). At LANL, ESLs are developed sepa- rately for plants and invertebrates versus wildlife, and decay and metabolic elimination rates are incorporated (11). 4.1.2 Integration with Safety Analyses In 1994 the Laboratory began a pilot project to develop an ecological risk assessment method that could be used to augment hazards and safety analyses (15). Specifically, the Laboratory explored the possiblity of using an ecological risk assessment approach to explicitly incorporate environmental consequence analysis into hazards analyses and probabilistic risk assessment processes. Inves- tigators used a two-phase approach: (a) Using five COPCs, conservative eco- logical screening was interacted with worst-case accident analysis results to determine whether ecological impacts could be excluded from further investiga- tion or would require more detailed assessment; (b) using a dynamic ecological transport model (BIOTRAN), a more detailed and realistic assessment was conducted of the land area that the screening process identified as most suscepti- ble to potential adverse impacts from the five contaminants. BIOTRAN (now BIOTRAN.2) is an ecological transport model used for predicting the flow of organic and inorganic contaminants, including radionuclides, through simulated ecosystems—which can include plant, animal, and human populations—using biomass vectors (16). Twenty-two subroutines include variables of meteorol- ogy, soil physics, hydrology, geology, plant and animal physiology, limnology, radiation biology, ecology, epidemiology, risk analysis, and health physics. “The results of the detailed assessment were consistent with the findings of the screening assessment, thus validating the screening assessment approach in the context of hazards analysis.” 4.1.3 Tier 2 Assessments From 1997 to 1999, Gonzales et al. completed tier 2 preliminary ecological risk assessments of federally protected threatened and endangered species (17–19). Risk assessments of the Mexican spotted owl (Strix occidentalis lucida), the American peregrine falcon (Falco peregrinus), the bald eagle (Haliaeetus leucocephalus), and the Southwestern willow flycatcher (Empidonax traillii extimus) were performed using a custom FORTRAN model, ECORSK.5, and the geographic information system (GIS) (17–19). Using Eq. (5), estimated doses resulting from soil ingestion and food consumption were compared against TRVs for nonradionuclides and radiation dose limits for radionuclides. This generated hazard indices (HIs) that included a measure of additive effects from multi- Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
ple contaminants (radionuclides, metals, and organic chemicals) and included bioaccumulation and biomagnification factors. ncs ncoc If /BW∑ Oi ENHi ∑ [Fs + (1 − Fs) BMFj] Csi,j i=1 j=1 HI = (5) TRV where HI = hazard index, cumulative for all summed COPC hazard quotients If = food consumption, kgdwt/day BW = body weight of organism, kgfwt ncs = total number of nest sites Oi = occupancy factor for the ith feeding site ENHi = enhancement factor for the ith feeding site ncoc = total number of different COPCs found over all nesting sites Fs = % soil in diet BMFj = biomagnification factor via food chain transport for the jth contaminant Csi,j = COPC concentration of soil/sediment, mg/kgdwt, for the ith feeding site and the jth COPC TRVj = toxicity reference value (“safe limit”), mg/kg-body weight/day, for the jth COPC Other terms were sometimes included, such as calculating sediment intake from prey data and inferring BMFs through differential equations. ECORSK.5 was used to integrate environmental contaminant data, species- specific biological, ecological, and toxicological information, and GIS spatial information as depicted in Figure 3. Using ECORSK.5, the risk assessor is able to scale home ranges (HRs) so that a rectangular HR simulates foraging patterns based on natural features such as topography or prey distribution. ECORSK.5 is also coded to allow the option of weighting the simulated foraging process on an exponential basis as based on the distance from randomly selected nest sites such that a species forages more in the vicinity of its nest (or any other focal point) than it does at the extremity of its HR. A second manner in which the simulated foraging process is weighted in the tier 2 process is based on animal distribution and other population data. For example, a GIS elk habitat use model based on positions fed from radio collars via a Global Positioning System was used to create an occupancy scheme whereby the amount of time spent foraging on any one area is specified. Coding schemes identify home ranges, habitat core areas, species, and occupancy weights. ECORSK.5 generates information on risk by specific geographic location for use in management of contaminated areas, species habitat, facility siting, Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
GIS EEU and NEST coordinates FIMAD Contaminant CONVRT location and concentration LOAEL/ MAPCDE.DAT NOAEL toxicology Database development Species- INRSK.DAT specific input EEUINP.DAT OUTRSK.DAT ENTRSK.DAT ECORSK.5 GIS.DAT HQ.DAT HQP.DAT HQPC.DAT HQPO.DAT HABIT.DAT HQPCO.DAT GRIDXY.DAT Select PLTRSK 2-D and 3-D plots FIGURE 3 Schematic respresenting the integration of ecological risk assess- ment parameters by ECORSK.5. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
and/or facility operations in order to maintain risk from contaminants at accept- ably low levels. Several different levels of risk breakdown, from very summarized values to very detailed values, are generated by ECORSK.5. Figure 4 shows one level of breakout, where the risk contribution by Aroclor-1254 from different discrete locations in a HR is presented graphically. Thus, the strength of this custom FORTRAN model is for animals with large individual home ranges or populations with large distributions. ECORSK.5 is documented in an internal report (20). 4.2 Ecorisk Assessments Applied Results of the tier 2 assessments described above indicated a small potential for impact to the peregrine falcon, but the studies concluded no appreciable potential impact was expected to the Mexican spotted owl, the bald eagle, or the South- western willow flycatcher. With all the hazardous substances used at the Labora- tory over the years, including radionuclides, an application of a pesticide unrelated to Laboratory operations 37 years ago resulted in the contaminant that dominated the risk contribution for the peregrine falcon. In 1963, dichlorodiphenyltrichloroethane (DDT) was applied to one-half million acres of forest west of the Rio Grande at an application rate of about 140,000 ppm (21). DDT and dichlorodiphenylethelyne (DDE), a DDT breakdown product, were two of the three top contaminants in several modeling scenarios for the peregrine falcon. Since this is currently a widely diffuse source that largely originated in 1963, PC/WM cannot be applied to this chemical, raising the point that not all risk issues can be addressed in the design of a PC/WM program. Nevertheless, the risk assessments summarized above also provide an example of how risk information can be used to augment PC/WM activities as follows. The top three contaminants, DDT, DDE, and a PCB mixture—Aroclor-1254—contributed a total of 81% of the risk under conditions of one of several modeled foraging scenarios. In part this resulted in a charter at the Laboratory to give added emphasis to PCB pollution control (A. Jackson, personal communication, 2000). The increased effort aims to Adopt a PCB-free program for authorized sources as an institutional sponsored program (consistent with Laboratory policy of zero environ- mental incident) Incorporate into the yearly budgetary exercise a schedule to replace PCB items Place greater division-level organizational emphasis on PCB-free facilities Gain senior management endorsement of an approach to address PCB vulnerabilities based on an ecological-risk concept as a coordinated institutional program, i.e., as a Laboratory taking a leadership and proactive role in working with regulators and the Department of Energy Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
0.5 0.45-0.5 0.4-0.45 0.45 0.35-0.4 0.3-0.35 0.4 0.25-0.3 0.2-0.25 0.35 0.15-0.2 Hazard Quotient 0.3 0.1-0.15 0.05-0.1 0.25 0-0.05 0.2 0.15 0.1 125 0.05 85 70 0 61 Grid cell row 0 30 60 75 50 81 Nesting Habitat 87 93 99 105 111 117 25 129 150 165 191 197 203 209 215 0 221 Grid cell column 227 233 255 285 FIGURE 4 Three-dimensional plot of ecological risk hazard quotient contributions for Aroclor-1254 by discrete location. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.
in arriving at a cost-effective and scientifically sound risk management framework for decision making that meets performance goals and is protective of the environment). Implementing pollution controls such as those listed above is no small task at a sprawling 43-mi2 industrial site, and costs can be substantial. In the example above, risk assessments helped focus field studies such that in the first year following the completion of the assessments approximately $122,000 was saved by targeting specific contaminants and omitting the analysis of those deemed inconsequential from a risk perspective. Thus, the consideration of risk issues in the design of PC/WM programs can improve the effectiveness and efficiency of the programs. As mentioned earlier, the Laboratory is employing the iterative and tiered approach to ecological risk assessment whereby less complex assessments with greater conservatism and uncertainty are employed first, followed by the advance- ment of potential problem areas and COPCs to progressively more complex and realistic assessments with lower uncertainty. 4.3 Risk-Based Prioritization of PC/WM COPC Targets As discussed in the previous section, development of the ecorisk screening method at LANL included the calculation of screening values termed ESLs. Table 1 is a list of soil ESLs by contaminant in decreasing order (22). For each contaminant ESLs were developed for eight terrestrial species. The values in Table 1 are for the species that usually had the most stringent (lowest) ESL. ESL values are still undergoing revision at LANL, but the relative rank is not expected to change much. Ecological screening levels are related directly to toxicity and expo- sure, therefore ranking contaminants on the basis of ESL value gives some indication of the contaminants, which if eliminated or reduced by PC/WM techniques, would most effectively reduce risk to flora and fauna. However, before prioritizing contaminants from a PC/WM perspective, one must also consider other factors, some practical, such as the ubiquity of contaminants in the environment because if a contaminant were quite toxic but was absent or present at very low levels in the environment relative to its ESL, elimination or reduction of the contaminant would gain little in terms of risk reduction. For example, since 2,3,7,8-tetrachlorodibenzodioxin is ranked first in Table 1, thus can be considered relatively very toxic, a large degree of risk reduction could be achieved by PC/WM efforts that minimize emissions or releases of it into the environment. However, its presence in the environmental contaminant database used in the threatened and endangered species assessments discussed above was sparse, therefore it is not likely a good candidate for PC/WM consideration. Copyright 2002 by Marcel Dekker, Inc. All Rights Reserved.

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