Sorption and bioreduction of hexavalent uranium at a military facility by the Chesapeake Bay

Directly adjacent to the Chesapeake Bay lies the Aberdeen Proving Ground, a U.S. Army facility where testing of armor-piercing ammunitions has resulted in the deposition of >70,000 kg of depleted uranium (DU) to local soils and sediments. Results of previous environmental monitoring suggested limited mobilization in the impact area and no transport of DU into the nation's largest estuary. To determine if physical and biological reactions constitute mechanisms involved in limiting contaminant transport, the sorption and biotransformation behavior of the radionuclide was studied using geochemical modeling and laboratory microcosms (500 ppb U(VI) initially). An immediate decline in dissolved U(VI) concentrations was observed under both sterile and non-sterile conditions due to rapid association of U(VI) with natural organic matter in the sediment. Reduction of U(VI) to U(IV) occurred only in non-sterile microcosms. In the non-sterile samples, intrinsic bioreduction of uranium involved bacteria of the order Clostridiales and was only moderately enhanced by the addition of acetate (41% vs. 56% in 121 days). Overall, this study demonstrates that the migration of depleted uranium from the APG site into the Chesapeake Bay may be limited by a combination of processes that include rapid sorption of U(VI) species to natural organic matter, followed by slow, intrinsic bioreduction to U(IV).     

Methodology for conducting screening-level ecological risk assessments for hazardous waste sites. Part III: exposure and effects assessment

The Idaho National Engineering and Environmental Laboratory (INEEL) has implemented a phased approach to ecological risk assessment (ERA). The first step in this process is a screening-level ERA at each facility. Basic to this approach was the development of ecologically based screening levels (EBSLs), defined as concentrations of chemicals in soil (or other media) that are not expected to produce any adverse effects on selected ecological receptors under chronic exposure conditions (analogous to preliminary remediation goals or soil screening levels). EBSLs are calculated by rearrangement of standard exposure equations to solve for soil concentration when chemical intake rate is set at a developed toxicity reference value (TRV). A TRV is defined as a chronic dose that is likely to be without appreciable risk of deleterious effects. This definition was extended to define TRVs and ultimately EBSLs for the functional groups used in the INEEL screening-level ERAS.     

Ecological risk assessments of endocrine disrupting organotin compounds using marine neogastropods in Hong Kong

As active ingredients of anti-fouling paints that are widely used on ship hulls, organotin compounds, in particular tributyltin (TBT), are well-known endocrine disruptors causing sex changes in marine organisms and widespread in coastal waters and sediments worldwide. In this study, a comprehensive ecological risk assessment (ERA) of organotins was conducted in Hong Kong waters through determining the imposex status, sex ratio and tissue burdens of these compounds in the neogastropods, Thais clavigera and Thais luteostoma collected from 29 coastal sites. We also investigated the historical trend of organotin effects on these gastropods, and performed a probabilistic ERA based on tissue burden of TBT in the animals. Our results demonstrated that imposex indices were positively correlated with the body burden of organotins in the gastropods. Across all sites, the sex ratio (female:male) decreased significantly with increasing imposex levels or tissue burden of organotins, implying that such pollutants can result in a male-biased population, potentially leading to local extinction in extreme cases. Based on the ERA, 5.4% of all populations of T. clavigera are at risk due to exposure to TBT; the risks include growth inhibition, impairment of immune functions and reduced fitness. Seriously impacted areas included Aberdeen, Repulse Bay, Butterfly Beach, Mui Wo and Ha Mei Wan. A comparison with historical data revealed that there had been some improvement in the areas with low marine traffic, and distant from the major harbour/port. This could partly be due to the restriction on the use of TBT on small vessels (<25m in length) since 1992. Nevertheless, the organotin contamination still remains severe in areas with high marine traffic or adjacent to large harbours/ports. In particular, the situation in the northeastern waters of Hong Kong has been getting worst since 1996 that is probably associated with the rapid development of the cargo container port at Yantian in China.     

A tiered ecological risk assessment of three chlorophenols in Chinese surface waters

Introduction

The ecological risks posed by three chlorophenols (CPs), 2,4-dichlorophenol (2,4-DCP), 2,4,6-trichlorophenol (2,4,6-TCP), and pentachlorophenol (PCP) in Chinese surface waters were assessed.

Materials and methods

This was achieved by applying a tiered ecological risk assessment (ERA) approach ranging from deterministic methods to probabilistic options to measured concentrations of CPs in surface water of seven major watersheds and three drainage regions in China and the chronic toxicity data for indigenous Chinese species.

Results and discussion

The results show that the risks of three chlorophenols are ranked PCP>2,4-DCP??2,4,6-TCP. PCP posed little ecological risk while 2,4-DCP and 2,4,6-TCP posed negligible or de minimis risk in Chinese surface water. However, the risks varied with different river basins, for example, PCP posed some ecological risk in the Yangtze, Huaihe, and Pearl Rivers. The magnitude of 2,4-DCP and 2,4,6-TCP pollution in North China was more serious than that in South China.

Conclusion

The probabilistic risk assessment approach, which can provide more information for risk managers and decision makers, was favored over the screening-level single-value estimate method. However, the results from all tiers of the ERA methods in the framework were consistent with each other.     

Haloacetic acids in the aquatic environment. Part II: ecological risk assessment

Haloacetic acids (HAAs) are environmental contaminants found in aquatic ecosystems throughout the world as a result of both anthropogenic and natural production. The ecological risk posed by these compounds to organisms in freshwater environments, with a specific focus on aquatic macrophytes, was characterized. The plants evaluated were Lemna gibba, Myriophyllum spicatum and M. sibiricum and the HAAs screened were monochloroacetic acid (MCA), dichloroacetic acid (DCA), trichloroacetic acid (TCA), trifluoroacetic acid (TFA) and chlorodifluoroacetic acid (CDFA). Laboratory toxicity data formed the basis of the risk assessment, but field studies were also utilized. The estimated risk was calculated using hazard quotients (HQ), as well as effect measure distributions (EMD) in a modified probabilistic ecological risk assessment. EMDs were used to estimate HAA thresholds of toxicity for use in HQ assessments. This threshold was found to be a more sensitive measure of low toxicity than the no observed effect concentrations (NOEC) or the effective concentration (EC10). Using both deterministic and probabilistic methods, it was found that HAAs do not pose a significant risk to freshwater macrophytes at current environmental concentrations in Canada, Europe or Africa for both single compound and mixture exposures. Still, HAAs are generally found as mixtures and their potential interactions are not fully understood, rendering this phase of the assessment uncertain and justifying further effects characterization. TCA in some environments poses a slight risk to phytoplankton and future concentrations of TFA and CDFA are likely to increase due to their recalcitrant nature, warranting continued environmental surveillance of HAAs.     

Methodology for conducting screening-level ecological risk assessments for hazardous waste sites. Part I: overview

The Idaho National Engineering and Environmental Laboratory (INEEL) is a Department of Energy (DOE) facility. To assess the impact of the site activities and releases on ecological receptors, the INEEL implemented a phased approach for conducting ecological risk assessments (ERAS). This approach applies an iterative, 'tiered' process, in which conservative preliminary assessments support progressively more refined assessments. The first phase is the screening-level ERA, which is a 'preassessment' performed at the Waste Area Group (WAG) level. This paper will address innovative methods, at the screening level, used to address systematically the complexity of the INEEL site, including adaptations of existing ERA methodologies to accommodate the functional grouping approach.     

Probabilistic risk assessment for personal exposure to carcinogenic polycyclic aromatic hydrocarbons in Taiwanese temples

To assess how the human exposure to airborne carcinogenic polycyclic aromatic hydrocarbons (PAHs) during working in or visiting a typical Taiwanese temple, we present a probabilistic risk model, appraised with reported empirical data. Two approaches are applied, one based on animal-derived benzo[a]pyrene (B[a]P) toxic equivalents (B[a]P(eq)) of individual PAHs and one is assumed that the potency of PAH mixtures is linked to their B[a]P level. The model integrates probabilistic exposure profiles of total-PAH and particle-bound PAH levels inside a temple from a published exploratory study with probabilistic incremental lifetime cancer risk (ILCR) models taking into account inhalation and dermal contact pathways, to quantitatively estimate the exposure risks for three age groups of adult, adolescent, and child. Risk analysis indicates that 90% probability inhalation ILCRs for three age groups have orders of magnitude around 10(-7)--10(-6); whereas for the dermal contact ILCRs ranging from 10(-5) to 10(-4), indicating high potential cancer risk. All 90% probabilities of B[a]P- and B[a]P(eq)-based total ILCRs are larger than 10(-6), indicating unacceptable probability distributions for three age groups. Sensitivity analysis indicates that to increase the accuracy of the results efforts should focus on a better definition of probability distributions for inhalation cancer slope factor, inhalation rates, and particle-bound PAH-to-skin adherence factor. We estimate risk-based visiting frequency advice for adult, adolescent, and child to a temple ranging from 5 to 7, 17 to 23, and 48 to 65 year(-1), respectively, based on an average 3h residence time.     

Towards a renewed research agenda in ecotoxicology

New concerns about biodiversity, ecosystem services and human health triggered several new regulations increasing the need for sound ecotoxicological risk assessment. The PEER network aims to share its view on the research issues that this challenges. PEER scientists call for an improved biologically relevant exposure assessment. They promote comprehensive effect assessment at several biological levels. Biological traits should be used for Environmental risk assessment (ERA) as promising tools to better understand relationships between structure and functioning of ecosystems. The use of modern high throughput methods could also enhance the amount of data for a better risk assessment. Improved models coping with multiple stressors or biological levels are necessary to answer for a more scientifically based risk assessment. Those methods must be embedded within life cycle analysis or economical models for efficient regulations. Joint research programmes involving humanities with ecological sciences should be developed for a sound risk management.     

Screening-level ecological risk assessment of polychlorinated dibenzo-p-dioxins and dibenzofurans in sediments and aquatic biota from the Venice Lagoon, Italy

Recent monitoring data indicate that portions of Italy's Venice Lagoon ecosystem have been degraded due to biological and chemical pollution from a variety of potential sources. Using polychlorinated dibenzo-p-dioxin (PCDD) and dibenzofuran (PCDF) data collected from sediment, fish and shellfish in the Lagoon, a screening-level ecological risk assessment (ERA) was performed to evaluate the risks to representative aquatic biota and wildlife receptors. Risks to aquatic invertebrates posed by PCDD/Fs in sediment were evaluated by comparing measured tissue concentrations in fish and shellfish to appropriate ecotoxicological reference values. For mammalian and avian receptors, risks posed by theoretical exposures to PCDD/Fs through the food chain were calculated using conservative wildlife exposure models. Results of the screening-level approach indicate that the potential for adverse effects to fish and aquatic invertebrate receptors from PCDD/Fs in surficial sediments are unlikely. Adverse effects to wildlife are possible but highly uncertain, and warrants further investigation in a more comprehensive ERA.     

Probabilistic risk assessment of abalone Haliotis diversicolor supertexta exposed to waterborne zinc

This paper describes a risk assessment approach that integrates predicted tissue concentrations of zinc (Zn) with a concentration-response relationship and leads to predictions of survival risk for pond abalone Haliotis diversicolor supertexta as well as to the uncertainties associated with these predictions. The models implemented include a probabilistic bioaccumulation model, which linking biokinetic and consumer-resource models, accounts for Zn exposure profile and a modified Hill model for reconstructing a dose-response profile for abalone exposed to waterborne Zn. The growth risk is assessed by hazard quotients characterized by measured water level and chronic no-observed effect concentration. Our risk analyses for H. diversicolor supertexta reared near Toucheng, Kouhu, and Anping, respectively, in north, central, and south Taiwan region indicate a relatively low likelihood that survival is being affected by waterborne Zn. Expected risks of mortality for abalone were estimated as 0.46 (Toucheng), 0.36 (Kouhu), and 0.29 (Anping). The predicted 90th-percentiles of hazard quotient for potential growth risk were estimated as 1.94 (Toucheng), 0.47 (Kouhu), and 0.51 (Anping). These findings indicate that waterborne Zn exposure poses no significant risk to pond abalone in Kouhu and Anping, yet a relative high growth risk in Toucheng is alarming. Because of a scarcity of toxicity and exposure data, the probabilistic risk assessment was based on very conservative assumptions.     

Role of manganese oxides in the exposure of mute swans (Cygnus olor) to Pb and other elements in the Chesapeake Bay, USA

The aims of this study are to estimate exposure of waterfowl to elements in contaminated sediments in the Chesapeake Bay and to consider the potential role of Mn in influencing bioavailability and exposure. Metal concentrations were measured in livers and digesta taken from mute swans living on the Aberdeen Proving Ground, whose sediment had elevated concentrations of Cu, S, Se, Zn, As, Co, Cr, Hg and Pb. Concentrations of only the first four of these elements were elevated in swan digesta. None of the concentrations detected in the digesta or livers of the swans was considered toxic, although the concentrations of Cu and Se were high compared to concentrations of these elements reported in other waterfowl. Lead was found to be scavenged by Mn and Fe oxides from the water and deposited on the surface of vegetation at a reference site. Under some environmental chemical conditions, this is an important route of exposure to Pb in waterfowl, not previously recognized.     

Use of Probabilistic Methods to Understand the Conservatism in California’s Approach to Assessing Health Risks Posed by Air Contaminants

Many state and federal agencies have prepared risk assessment guidelines, which describe methods for quantifying health risks associated with exposure to vapors and particulates emitted from point and area sources (e.g., California Air Pollution Control Officers Association [CAPCOA] under the Air Toxics “Hot Spots” Act [Assembly Bill 2588] and the U.S. Environmental Protection Agency [EPA] under the Clean Air Act). In general, these guidelines recommend or require the use of upper bound “point” estimates for numerous exposure parameters. This methodology yields a single risk estimate, which is intended not to underestimate the true risk and may significantly overstate it. This paper describes a risk assessment of a facility’s airborne emissions using a probabilistic approach, which presents a range and distribution of risk estimates rather than a single point estimate. The health risks to residents living near a food processing facility, as estimated using techniques recommended by California AB2588, are compared to the results of a probabilistic analysis. Polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) were identified as the emitted chemicals of concern. The point estimate method recommended by CAPCOA resulted in estimates that were greater than the 99.99th percentile risk predicted by the probabilistic analysis. As shown in other assessments of persistent airborne chemicals, secondary or indirect exposure pathways (i.e., ingestion of beef, ingestion of cow’s milk, and ingestion of mother’s milk) rather than inhalation, were the greatest contributors to risk. In this analysis, the probability distributions for the cancer potency factor and ingestion of cow’s milk had the largest impact on the results of the 33 exposure factors considered.     

Fenitrothion, an organophosphate, affects running endurance but not aerobic capacity in fat-tailed dunnarts (Sminthopsis crassicaudata)

We measured aerobic metabolism during cold exposure and exercise performance (run duration and oxygen consumption while running at 1 m s(-1)) in the fat-tailed dunnart Sminthopsis crassicaudata, a dasyurid marsupial, before and after ingestion of 30 mg kg(-1) of fenitrothion, an organophosphate (OP) pesticide. Running endurance of OP-exposed animals was less than half that of control animals over the first 3 days after dosing and 55% of control animal endurance on day 5 post-dose. Despite these declines, peak metabolic rate at this running speed (9.3 times basal metabolic rate; BMR) was unaffected by OP exposure. Peak metabolic rate (PMR) and cumulative oxygen consumption during a 1-h exposure to conditions equivalent to -20 degrees C did not differ between OP-treated and control dunnarts, with PMR averaging 11 times BMR. We conclude that fenitrothion-induced exercise fatigue is not due to limitations in oxygen or substrate delivery to muscle or in their uptake per se, but more likely relates to decreased ability to sustain high-frequency neuromuscular function. The persistence of locomotor impairment following OP exposure in otherwise asymptomatic animals emphasizes the importance of using performance-based measures when characterising sublethal effects of pesticide exposure in an ecological context.     

A probabilistic model for the carry-over of PCDD/Fs from feed to growing pigs

When food producing animals are contaminated with PCDD/F congeners, information on the contaminant’s concentration in the bodies of the animals at time of slaughter is needed for risk management purposes. We have developed a mathematical model for the kinetics of PCDD/Fs in growing pigs in case of contaminated feed fed for a limited duration of time. This model allows the prediction of concentrations in body fat. It considers absorption fractions of PCDD/Fs, clearance by metabolism, dilution by growth and excretion through fecal fat. The model parameters were calibrated by fitting the model to experimental data. On the basis of this toxicokinetic model a probabilistic model has been constructed. The probabilistic model handles the parameters with appropriate probability distributions and Monte-Carlo simulation technique, providing for realistic situations with many animals and a range of contaminations and feeding intervals. We applied the new model to describe the German dioxin incident of winter 2010/2011 and discuss its viability as decision tool. The approach demonstrated here is a showcase how a risk assessment in the case of contaminated feeding can be performed.     

Micro-evolution due to pollution: possible consequences for ecosystem responses to toxic stress

Polluting events can change community structure and ecosystem functioning. Selection of genetically inherited tolerance on exposed populations, here referred as micro-evolution due to pollution, has been recognized as one of the causes of these changes. However, there is a gap between studies addressing this process and those assessing effects at higher levels of biological organization. In this review we attempt to address these evolutionary considerations into the ecological risk assessment (ERA) of polluting events and to trigger the discussion about the consequences of this process for the ecosystem response to toxic stress. We provide clear evidence that pollution drives micro-evolutionary processes in several species. When this process occurs, populations inhabiting environments that become polluted may persist. However, due to the existence of ecological costs derived from the loss of genetic variability, negative pleiotropy with fitness traits and/or from physiological alterations, micro-evolution due to pollution may alter different properties of the affected populations. Despite the existence of empirical evidence showing that safety margins currently applied in the ERA process may account for pollution-induced genetic changes in tolerance, information regarding long-term ecological consequences at higher levels of biological organization due to ecological costs is not explicitly considered in these procedures. In relation to this, we present four testable hypotheses considering that micro-evolution due to pollution acts upon the variability of functional response traits of the exposed populations and generates changes on their functional effect traits, therefore, modifying the way species exploit their ecological niches and participate in the overall ecosystem functioning.     

Does small mammal prey guild affect the exposure of predators to anticoagulant rodenticides?

Ireland has a restricted small mammal prey guild but still includes species most likely to consume anticoagulant rodenticide (AR) baits. This may enhance secondary exposure of predators to ARs. We compared liver AR residues in foxes (Vulpes vulpes) in Northern Ireland (NI) with those in foxes from Great Britain which has a more diverse prey guild but similar agricultural use of ARs. Liver ARs were detected in 84% of NI foxes, more than in a comparable sample of foxes from Scotland and similar to that of suspected AR poisoned animals from England and Wales. High exposure in NI foxes is probably due to greater predation of commensal rodents and non-target species most likely to take AR baits, and may also partly reflect greater exposure to highly persistent brodifacoum and flocoumafen. High exposure is likely to enhance risk and Ireland may be a sentinel for potential effects on predator populations.     

Ecological risk assessment of neem-based pesticides

A tiered process was used to evaluate the risks of pure azadirachtin (AZA) and two neem-based insecticides (Neemix and Bioneem) on six aquatic animals [crayfish (Procambarus clarkii), white shrimp (Penaeus setiferus), grass shrimp (Palaemonetes pugio), blue crabs (Callinectes sapidus), water fleas (Daphnia pulex), and mosquito larvae (Culex quinquefasciatus)] through short term acute toxicity tests. The risk was calculated using the level of concern endpoints (Q values) and relative hazard index (RHI) for acute and chronic exposure scenarios. The Q values of Neemix, Bioneem, and pure AZA derived from acute exposure tests indicated that D. pulex is the only sensitive species to the test pesticides. Furthermore, the RHI values of Neemix and Bioneem for D. pulex were above the critical limit of 10 indicating that these pesticides may pose a moderate hazard to this species and related crustaceans in acute exposure scenarios. The RHI values of the two pesticides and pure AZA were all below the critical limit of 10 for P. clarkii, P. setiferus, P. pugio, C. sapidus, and C. quinquefasciatus. The aquatic risk assessment process showed that the risk values of tested pesticides did not exceed the criteria, and therefore, no ecological hazard is likely to result from their use.     

Ecological risk assessment for aquatic species exposed to contaminants in Keelung River, Taiwan

An ecological risk assessment was conducted for Keelung River in northern Taiwan. The objective of this study was to assess the risk to fish, aquatic insects, and benthic macroinvertebrates associated with chemical-of-potential-concern (COPC) in the river and to rank ecological risk for these chemicals. The protection of at least 95% of the species 90% of the time from acute and chronic COPC exposures was the defined assessment endpoint. Nine inorganic and organic contaminants were selected to evaluate the impact to aquatic community in the Keelung River. The quotient method served as screen level estimation of risk. The Aquatic Ecological Risk Assessment model was used to analyze exposure and ecological effects and to estimate community level risk. The logarithmic regression model between probability and lethal concentration was established. The combined risks of multiple chemicals were evaluated under assumption of additive risk. The results indicated that zinc and copper pose higher risk among metals. Ammonia, copper, and zinc posed virtually all of the risk, while organic COPCs posed a negligible risk. Potential ecological risk from ammonia exposure was greatest. The probability of more than 5% of the species being affected by acute or chronic toxicity of COPCs is about 100%. In average (50% of the time), 99% of the species would be affected by acute toxicity of COPCs, and about all the species would be affected by chronic toxicity of COPCs. Uncertainties in this assessment were associated with variability in ecosystem stressors, exposure data, ecological effect data, and risk characterization.     

A Maximum Entropy Approach to Estimating Emissions

ABSTRACT

A maximum information entropy method of calculating probabilistic estimates of volatile organic compound (VOC) emissions by the wood furniture and fixture coating industry is presented. The maximum entropy approach is used to produce minimally biased probability distributions for number of firms, coating use, and coating emission factors from existing summary statistics. These distributions are combined to estimate VOC emissions. The maximum entropy emissions estimate provides information to support probabilistic modeling of regional air quality, probabilistic assessment of emission reduction strategies, and risk assessments. Accurate estimation of emission distributions produces more informed regulatory decisionmaking, risk comparisons, and regulatory and scientific priority setting.     

Evaluation of a Probabilistic Exposure Model Applied

The probabilistic National Ambient Air Quality Standards (NAAQS) Exposure Model applied to carbon monoxide (pNEM/CO) was developed by the U.S. Environmental Protection Agency (EPA) to estimate frequency distributions of population exposure to carbon monoxide (CO) and the resulting carboxyhemoglobin (COHb) levels. To evaluate pNEM/CO, the model was set up to simulate CO exposure data collected during a Denver Personal Exposure Monitoring Study (PEM) conducted during the winter of 1982-1983.

This paper compares computer-simulated exposure distributions obtained by pNEM/CO with the observed cumulative

relative frequency distributions of population exposure to CO from 779 people in the Denver PEM study. The subjects were disaggregated into two categories depending upon whether they lived in a home with a gas stove or an electric stove. The observed and predicted population exposure frequency distributions were compared in terms of 1-hr daily maximum exposure (1DME) and 8-hr daily maximum moving average exposure (8DME) for people living in homes with gas stove or an electric stove. For 1DME, the computer-simulated results from pNEM/CO agreed most closely within the range of 6-13 ppm, but overestimated occurrences at low exposure (<6 ppm) and underestimated occurrences at high exposure (>13 ppm). For 8DME, the predicted exposures agreed best with observed exposures in the range of CO concentration between 5.5 and 7 ppm, and over-predicted occurrences below 5.5 ppm and under-predicted occurrences above 7 ppm.