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Petroleum refinery effluents (PRE) are wastewaters from industries associated with oil refining. Within Europe, PREs are regulated through local discharge permits and receive substantial treatment before emission. After treatment, PREs can still contain low levels of various pollutants potentially toxic to organisms. Earlier work, including whole-effluent toxicity assessments, has shown that the toxicity of permitted PREs is often limited. However, the extent to which PREs contribute to chemical pollution already present in the receiving environment is unknown. Therefore, our study aimed to assess the contribution of PREs to mixture toxic pressure in the environment, using the multi-substance potentially affected fraction of species (msPAF) as an indicator. Based on measured chemical concentrations, compiled species sensitivity distributions (SSD) and a mechanistic solubility model, msPAF levels were estimated for undiluted effluents at discharge points and diluted effluents downstream in receiving waters. Median msPAF-chronic and msPAF-acute levels of PREs at discharge points were 74% (P50) and 40% (P95), respectively. The calculated msPAF levels were reduced substantially to <5% downstream for most effluents (82%), indicating low to negligible toxicity of PREs in receiving environments beyond the initial mixing zone. Regardless of differences in endpoints and locations, hydrocarbons (mainly total petroleum hydrocarbons) and inorganics (mainly ammonia) explained at least 85% of the mixture toxic pressure. The msPAF levels of PREs were on average 2.5-4.5 orders of magnitude lower than msPAF levels derived from background pollution levels, suggesting that PREs were minor contributors to the toxic pressure in the environment. This study presents a generic methodology for quantifying the potential toxic pressure of PREs in the environment, identifying hotspots where more effective wastewater treatment could be needed. We explicitly discuss the uncertainties for further refinement and development of the method., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Markus Hjort and Yves Verhaegen works for Concawe, which represents the European fuel manufacturing industry, whose members operate the refinery sites included in the study. Concawe is a non-profit scientific organisation established in 1963 to conduct research on environmental issues relevant to the European fuel manufacturing industry. Concawe's operating principles aim to publish all research publicly, either on the Concawe website (https://www.concawe.eu) or as open access papers in scientific journals. Concawe has a long history of publications. Our mechanism to avoid bias is to publish our work, publish our data and methods so that the research community can reproduce and build on our findings. Mathijs G.D. Smit and Aaron D. Redman works for Shell and ExxonMobil, respectively, which are Concawe member companies. As this study was funded by Concawe these co-authors are bound to follow the mission and operating principles of Concawe. Jiaqi Wang, Tom M. Nolte, A. Jan Hendriks are employed by Radboud University and have received research funding from Concawe for conducting this study. Their research group independently carries out studies financed by university, governmental, commercial and other funding that is published in peer review journals., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Preserving human and environmental health requires anthropogenic pollutants to be biologically degradable. Depending on concentration, both nutrients and pollutants induce and activate metabolic capacity in the endemic bacterial consortium, which in turn aids their degradation. Knowledge on such 'acclimation' is rarely implemented in risk assessment cost-effectively. As a result, an accurate description of the mechanisms and kinetics of biodegradation remains problematic. In this study, we defined a yield 'effectivity', comprising the effectiveness at which a pollutant (substrate) enhances its own degradation by inducing (biomass) cofactors involved therein. Our architecture for calculation represents the interplay between concentration and metabolism via both stoichiometric and thermodynamic concepts. The calculus for yield 'effectivity' is biochemically intuitive, implicitly embeds co-metabolism and distinguishes 'endogenic' from 'exogenic' substances' reflecting various phenomena in biodegradation and bio-transformation studies. We combined data on half-lives of pollutants/nutrients in wastewater and surface water with transition-state rate theory to obtain also experimental values for effective yields. These quantify the state of acclimation: the portion of biodegradation kinetics attributable to (contributed by) 'natural metabolism', in view of similarity to natural substances. Calculated and experimental values showed statistically significant correspondence. Particularly, carbohydrate metabolism and nucleic acid metabolism appeared relevant for acclimation (R 2  = 0.11-0.42), affecting rates up to 10 4.9(±0.7) times: under steady-state acclimation, a compound stoichiometrically identical to carbohydrates or nucleic acids, is 10 3.2 to 10 4.9 times faster aerobically degraded than a compound marginally similar. Our new method, simulating (contribution by) the state of acclimation, supplements existing structure-biodegradation and kinetic models for predicting biodegradation in wastewater and surface water. The accuracy of prediction may increase when characterizing nutrients/co-metabolites in terms of, e.g., elemental analysis. We discuss strengths and limitations of our approach by comparison to empirical and mechanism-based methods., (Copyright © 2022 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

We aimed to identify patterns in the internal distribution of persistent organic pollutants (POPs) and assess contributing factors using sea turtles and their offspring as a case study of a long-lived wildlife species. We systematically synthesized 40 years of data and developed a lipid database to test whether lipid-normalized POP concentrations are equal among tissues as expected under steady state for lipophilic compounds. Results supported equal partitioning among tissues with high blood flow or perfusion including the heart, kidney, muscle, and lung. Observed differences in the brain, fat, and blood plasma, however, suggest the physiological influence of the blood-brain barrier, limited perfusion, and protein content, respectively. Polybrominated diphenyl ethers partitioned comparably to legacy POPs. Polycyclic aromatic hydrocarbons, meanwhile, partitioned more into the lung, colon, and muscle compared to the liver under chronic and acute field exposure. Partitioning ratios of individual POPs among tissues were significantly related to the lipophilicity of compounds (as estimated by K ow ) in half of the observed cases, and significant differences between juveniles and adults underscore physiological differences across life stages. The comprehensive tissue partitioning patterns presented here provide a quantitative basis to support comparative assessments of POP pollution derived from biomonitoring among multiple tissues.

Although atmospheric concentrations of many conventional persistent organic pollutants (POPs) have decreased in the Arctic over the past few decades, levels of most POPs and mercury remain high since the 1990s or start to increase again in Arctic areas, especially polar bears. So far, studies generally focused on individual effects of POPs, and do not directly link POP concentrations in prey species to population-specific parameters. In this study we therefore aimed to estimate the effect of legacy POPs and mercury on population growth rate of nineteen polar bear subpopulations. We modelled population development in three scenarios, based on species sensitivity distributions (SSDs) derived for POPs based on ecotoxicity data for endothermic species. In the first scenario, ecotoxicity data for polar bears were based on the HC 50 (the concentration at which 50% of the species is affected). The other two scenarios were based on the HC 5 and HC 95 . Considerable variation in effects of POPs could be observed among the scenarios. In our intermediate scenario, we predicted subpopulation decline for ten out of 15 polar bear subpopulations. The estimated population growth rate was least reduced in Gulf of Boothia and Foxe Basin. On average, PCB concentrations in prey (in μg/g toxic equivalency (TEQ)) posed the largest threat to polar bear subpopulations, with negative modelled population growth rates for the majority of subpopulations. We did not find a correlation between modelled population changes and monitored population trends for the majority of chemical-subpopulation combinations. Modelled population growth rates increased over time, implying a decreasing effect of PCBs, DDTs, and mercury. Polar bear subpopulations are reportedly still declining in four out of the seven subpopulations for which sufficient long-term monitoring data is available, as reported by the IUCN-PBSG. This implies that other emerging pollutants or other anthropogenic stressors may affect polar bear subpopulations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 The Author(s). Published by Elsevier B.V. All rights reserved.)

Ecological risks (ERs) of pollutants are typically assessed using species sensitivity distributions (SSDs), based on effect concentrations obtained from bioassays with unknown representativeness for field conditions. Alternatively, monitoring data relating breeding success in bird populations to egg concentrations may be used. In this study, we developed a procedure to derive SSDs for birds based on field data of egg concentrations and reproductive success. As an example, we derived field-based SSDs for p, p'-DDE and polychlorinated biphenyls (PCBs) exposure to birds. These SSDs were used to calculate ERs for these two chemicals in the American Great Lakes and the Arctic. First, we obtained field data of p, p'-DDE and PCBs egg concentrations and reproductive success from the literature. Second, these field data were used to fit exposure-response curves along the upper boundary (right margin) of the response's distribution (95th quantile), also called quantile regression analysis. The upper boundary is used to account for heterogeneity in reproductive success induced by other external factors. Third, the species-specific EC 10/50 s obtained from the field-based exposure-response curves were used to derive SSDs per chemical. Finally, the SSDs were combined with specific exposure data for both compounds in the two areas to calculate the ER. We found that the ERs of combined exposure to these two chemicals were a factor of 5-35 higher in the Great Lakes compared to Arctic regions. Uncertainty in the species-specific exposure-response curves and related SSDs was mainly caused by the limited number of field exposure-response data for bird species. With sufficient monitoring data, our method can be used to quantify field-based ecological risks for other chemicals, species groups, and regions of interest.

Polar bears (Ursus maritimus) currently receive much attention in the context of global climate change. However, there are other stressors that might threaten the viability of polar bear populations as well, such as exposure to anthropogenic pollutants. Lipophilic organic compounds bio-accumulate and bio-magnify in the food chain, leading to high concentrations at the level of top-predators. In Arctic wildlife, including the polar bear, various adverse health effects have been related to internal concentrations of commercially used anthropogenic chemicals like PCB and DDT. The extent to which these individual health effects are associated to population-level effects is, however, unknown. In this study we assembled data on adipose tissue concentrations of ∑PCB, ∑DDT, dieldrin and ∑PBDE in individual polar bears from peer-reviewed scientific literature. Data were available for 14 out of the 19 subpopulations. We found that internal concentrations of these contaminants exceed threshold values for adverse individual health effects in several subpopulations. In an exploratory regression analysis we identified a clear negative correlation between polar bear population density and sub-population specific contaminant concentrations in adipose tissue. The results suggest that adverse health effects of contaminants in individual polar bears may scale up to population-level consequences. Our study highlights the need to consider contaminant exposure along with other threats in polar bear population viability analyses., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Species sensitivity distributions (SSDs) are used in ecological risk assessment for extrapolation of the results of toxicity tests with single species to a toxicity threshold considered protective of ecosystem structure and functioning. The attention to and importance of the SSD approach has increased in scientific and regulatory communities since the 1990s. Discussion and criticism have been triggered on the concept of the approach as well as its technical aspects (e.g., distribution type, number of toxicity endpoints). Various questions remain unanswered, especially with regard to different endpoints, statistical methods, and protectiveness of threshold levels, for example. In the present literature review (covering the period 2002-2013), case studies are explored in which the SSD approach was applied, as well as how endpoint types, species choice, and data availability affect SSDs. How statistical methods may be used to construct reliable SSDs and whether the lower 5th percentile hazard concentrations (HC5s) from a generic SSD can be protective for a specific local community are also investigated. It is shown that estimated protective concentrations were determined by taxonomic groups rather than the statistical method used to construct the distribution. Based on comparisons between semifield and laboratory-based SSDs, the output from a laboratory SSD was protective of semifield communities in the majority of studies. Environ Toxicol Chem 2016;35:2149-2161. © 2016 SETAC., (© 2016 SETAC.)

Metal accumulation in roots was modelled with WHAM VII using humic acid (HA) as a surrogate for root surface. Metal accumulation was simulated as a function of computed metal binding to HA, with a correction term (E(HA)) to account for the differences in binding site density between HA and root surface. The approach was able to model metal accumulation in roots to within one order of magnitude for 95% of the data points. Total concentrations of Mn in roots of Vigna unguiculata, total concentrations of Ni, Zn, Cu and Cd in roots of Pisum sativum, as well as internalized concentrations of Cd, Ni, Pb and Zn in roots of Lolium perenne, were significantly correlated to the computed metal binding to HA. The method was less successful at modelling metal accumulation at low concentrations and in soil experiments. Measured concentrations of Cu internalized in L. perenne roots were not related to Cu binding to HA modelled and deviated from the predictions by over one order of magnitude. The results indicate that metal uptake by roots may under certain conditions be influenced by conditional physiological processes that cannot simulated by geochemical equilibrium. Processes occurring in chronic exposure of plants grown in soil to metals at low concentrations complicate the relationship between computed metal binding to HA and measured metal accumulation in roots., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Organisms are simultaneously exposed to various stressors, including parasites and pollutants, that may interact with each other. Research on the accumulation of organic compounds in host-parasite systems is scant compared to studies on parasite-metal interactions and mainly focuses on intestinal endoparasites. We reviewed factors that determine the accumulation of persistent organic pollutants (POPs) in host-parasite systems. The wet/dry weight-based concentration of POPs in these parasites is usually lower than that in host tissues because of lower lipid contents in the parasites. However, the fractionation of the pollutants into parasites and their hosts may vary, depending on developmental stages in the life cycle of the parasites. Developmental stages determine the trophic relationship and the taxon of the parasite in the host-parasite systems because of different feeding strategies between the stages. Lipid-corrected concentrations of organic chemicals in the host are usually higher than those in the endoparasites studied. This phenomenon is attributed to a number of physiological and behavioural processes, such as feeding selectivity and strategy and excretion. Moreover, no significant relationship was found between the accumulation factor (i.e. the ratio between the lipid-corrected concentrations in parasites and in their hosts) for polychlorinated biphenyls and either hydrophobicity or molecular size. At the intermediate hydrophobicity, larger and more lipophilic compounds are accumulated at higher levels in both parasites and the host than smaller and less lipophilic compounds. The bioaccumulation of POPs in parasites is affected by some other abiotic, e.g. temperature, and biotic factors, e.g. the number of host species infected by parasites., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Since chemicals' ecotoxic effects depend for most soil species on the dissolved concentration in pore water, the equilibrium partitioning (EP) method is generally used to estimate hazardous concentrations (HC50) in the soil from aquatic toxicity tests. The present study analyzes the statistical uncertainty in terrestrial HC50s derived by the EP-method. For 47 organic chemicals, we compared freshwater HC50s derived from standard aquatic ecotoxicity tests with porewater HC50s derived from terrestrial ecotoxicity tests. Statistical uncertainty in the HC50s due to limited species sample size and in organic carbon-water partitioning coefficients due to predictive error was treated with probability distributions propagated by Monte Carlo simulations. Particularly for specifically acting chemicals, it is very important to base the HC50 on a representative sample of species, composed of both target and non-target species. For most chemical groups, porewater HC50 values were approximately a factor of 3 higher than freshwater HC50 values. The ratio of the porewater HC50/freshwater HC50 was typically 3.0 for narcotic chemicals (2.8 for nonpolar and 3.4 for polar narcotics), 0.8 for reactive chemicals, 2.9 for neurotoxic chemicals (4.3 for AChE agents and 0.1 for the cyclodiene type), and 2.5 for herbicides-fungicides. However, the statistical uncertainty associated with this ratio was large (typically 2.3 orders of magnitude). For 81% of the organic chemicals studied, there was no statistical difference between the hazardous concentration of aquatic and terrestrial species. We conclude that possible systematic deviations between the HC50s of aquatic and terrestrial species appear to be less prominent than the overall statistical uncertainty., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Engineered nanomaterials (ENMs) possess novel properties making them attractive for application in a wide spectrum of fields. These novel properties are not accounted for in the environmental risk assessment methods that the Registration, Evaluation, Authorization, and Restriction of Chemicals (REACH) proposes in their guidance on environmental exposure estimation, although ENMs are already applied in a variety of consumer and industrial products. It is thus necessary to evaluate the guidance document REACH provides on environmental exposure estimation on its applicability to ENMs. This is most urgently the case for engineered nanoparticles (ENPs), as the novel properties are most often only applicable to them. The environmental fate of ENPs was reviewed and compared to the environmental fate of chemicals according to the REACH guidance. Major deviations between the fate of ENPs and predicted fate by REACH were found. They were related to at least 1 of 3 major assumptions made in REACH guidance: 1) in REACH, environmental alteration processes are all thought of as removal processes, whereas alterations of ENPs in the environment may greatly affect their properties, environmental effects, and behavior, 2) in REACH, chemicals are supposed to dissolve instantaneously and completely on release into the environment, whereas ENPs should be treated as nondissolved nanosized solids, and 3) in REACH, partitioning of dissolved chemicals to solid particles in air, water, and soil is estimated with thermodynamic equilibrium coefficients, but in the case of ENPs thermodynamic equilibrium between "dispersed" and "attached" states is generally not expected. The environmental exposure assessment of REACH therefore needs adjustment to cover the specific environmental fate of ENPs. Incorporation of the specific environmental fate processes of ENPs into the environmental risk assessment framework of REACH requires a pragmatic approach., (Copyright © 2013 SETAC.)

Environmental risk assessment requires models for estimating the bioaccumulation of untested compounds. So far, bioaccumulation models have focused on lipophilic compounds, and only a few have included hydrophilic compounds. Our aim was to extend an existing bioaccumulation model to estimate the oral uptake efficiency of pollutants in mammals for compounds over a wide K(ow) range with an emphasis on hydrophilic compounds, i.e. compounds in the lower K(ow) range. Usually, most models use octanol as a single surrogate for the membrane and thus neglect the bilayer structure of the membrane. However, compounds with polar groups can have different affinities for the different membrane regions. Therefore, an existing bioaccumulation model was extended by dividing the diffusion resistance through the membrane into an outer and inner membrane resistance, where the solvents octanol and heptane were used as surrogates for these membrane regions, respectively. The model was calibrated with uptake efficiencies of environmental pollutants measured in different mammals during feeding studies combined with human oral uptake efficiencies of pharmaceuticals. The new model estimated the uptake efficiency of neutral (RMSE=14.6) and dissociating (RMSE=19.5) compounds with logK(ow) ranging from -10 to +8. The inclusion of the K(hw) improved uptake estimation for 33% of the hydrophilic compounds (logK(ow)<0) (r(2)=0.51, RMSE=22.8) compared with the model based on K(ow) only (r(2)=0.05, RMSE=34.9), while hydrophobic compounds (logK(ow)>0) were estimated equally by both model versions with RMSE=15.2 (K(ow)&K(hw)) and RMSE=15.7 (K(ow) only). The model can be used to estimate the oral uptake efficiency for both hydrophilic and hydrophobic compounds., (Copyright © 2012 Elsevier Inc. All rights reserved.)

In current life cycle impact assessment, the focus of ecotoxicity is on cold-blooded species. We developed a method to calculate characterization factors (CFs) for the impact assessment of chemical emissions on warm-blooded predators in freshwater food chains. The method was applied to 329 organic chemicals. The CF for these predators was defined as a multiplication of the fate factor (FF), exposure factor (XF), bioaccumulation factor (BF), and effect factor (EF). Fate factors and XFs were calculated with the model USES-LCA 2.0. Bioaccumulation factors were calculated with the model OMEGA, for chemical uptake via freshwater, food, and air. Effect factors were calculated based on experimental, median lethal doses (LD50). The concentration buildup (CB) of the chemicals (i.e., FF, XF, and BF over the 3 routes of exposure) showed a range of 7 to 9 orders of magnitude, depending on the emission compartment. Effect factors displayed a range of 7 orders of magnitude. Characterization factors ranged 9 orders of magnitude. After emissions to freshwater, the relative contribution of the uptake routes to CB were 1% (90% confidence interval [CI]: 0%-2%) for uptake from air, 43% (11%-50%) for uptake from water, and 56% (50%-87%) for uptake from food. After an emission to agricultural soil, the contribution was 11% (0%-80%) for uptake from air, 39% (5%-50%) for uptake from water, and 50% (11%-83%) for uptake from food. Uptake from air was mainly relevant for emissions to air (on average 42%, 90% CI: 5%-98%). Characterization factors for cold-blooded species were typically 4 orders of magnitude higher than CFs for warm-blooded predators. The correlation between both types of CFs was low, which means that a high relative impact on cold-blooded species does not necessarily indicate a high relative impact on warm-blooded predators. Depending on the weighing method to be considered, the inclusion of impacts on warm-blooded predators can change the relative ranking of toxic chemicals in a life cycle assessment., (Copyright © 2011 SETAC.)

Relative metal-ligand complex stability is predicted by evaluating the relationships between physicochemical properties of metal ions and their experimental biotic and abiotic binding constants, K. Linear regression analysis showed that the softness index (σ(p)) and the covalent index (χ(2)(m) r) were especially useful in model construction for rainbow trout (Oncorhynchus mykiss), fathead minnows (Pimephales promelas) and crustaceansaquatic (Daphnia magna) based on RMSE and F-ratio criterion (F(observed)/F(critical) of ≥4). The absolute value of the log of the first hydrolysis constant |logK(OH)| correlated best with logK values for barley (R(2)=0.74, p=0.02) and earthworm (R(2)=0.82, p=0.01). In contrast, the ionic index Z(2)/r explained most of the variability of logK values for the two clays kaolinite and montmorillonite, while |logK(OH)| was a better predictor of the generic NICA-Donnan parameters for HA and FA (0.67

The objective of this work is to present a critical review of the application of the tissue residue approach (TRA) in ecological risk and/or impact assessment (ERA) of chemical stressors and environmental criteria development. A secondary goal is to develop a framework for integrating the TRA into ecological assessments along with traditional, exposure concentration-based assessment approaches. Although widely recognized for its toxicological appeal, the utility of the TRA in specific applications will depend on numerous factors, such as chemical properties, exposure characteristics, assessment type, availability of tissue residue-response data, and ability to quantify chemical exposure. Therefore, the decision to use the TRA should include an evaluation of the relative strengths, limitations, and uncertainties among exposure and residue-based methods for characterizing toxicological effects. Furthermore, rather than supplanting exposure concentration-based toxicity assessments, the TRA can be highly effective for evaluating and reducing uncertainty when used in a complementary manner (e.g., when evaluating multiple lines of evidence in field studies). To address limitations with the available tissue residue-response data, approaches for extrapolating residue-based toxicity data across species, tissues, and exposure durations are discussed. Some of these approaches rely on predicted residue-response relationships or toxicological models that have an implicit residue-response basis (e.g., biotic ligand model). Because risk to an organism is a function of both its exposure potential and inherent sensitivity (i.e., on a residue basis), bioaccumulation models will be required not only for translating tissue residue criteria into corresponding water and sediment criteria, but also for defining the most vulnerable species in an assemblage (i.e., highly exposed and highly sensitive species). Application of the TRA in ecological assessments and criteria development are summarized for bioaccumulative organic chemicals, TBT, and in situ bioassays using bivalve molluscs., (Copyright © 2010 SETAC.)

Wildlife organisms are exposed to a combination of chemical, biological and physical stressors. Information about the relative impact of each stressor can support management decisions, e.g., by the allocation of resources to counteract those stressors that cause most harm. The present paper introduces Eco-SpaCE; a novel receptor-oriented cumulative exposure model for wildlife species that includes relevant ecological processes such as spatial habitat variation, food web relations, predation, and life history. A case study is presented in which the predicted mortality due to cadmium contamination is compared with the predicted mortality due to flooding, starvation, and predation for three small mammal species (Wood mouse, Common vole, and European mole) and a predator (Little owl) living in a lowland floodplain along the river Rhine in The Netherlands. Results indicated that cadmium is the principal stressor for European mole and Little owl populations. Wood mouse and Common vole population densities were mainly influenced by flooding and food availability. Their estimated population sizes were consistent with numbers reported in literature. Predictions for cadmium accumulation and flooding stress were in agreement with field data. The large uncertainty around cadmium toxicity for wildlife leads to the conclusion that more species-specific ecotoxicological data is required for more realistic risk assessments. The predictions for starvation were subject to the limited quantitative information on biomass obtainable as food for vertebrates. It is concluded that the modelling approach employed in Eco-SpaCE, combining ecology with ecotoxicology, provides a viable option to explore the relative contribution of contamination to the overall stress in an ecosystem. This can help environmental managers to prioritize management options, and to reduce local risks., (Copyright 2009 Elsevier B.V. All rights reserved.)

We evaluated various modeling options for estimating concentrations of PCB-153 in the environment and in biota across Europe, using a nested multimedia fate model coupled with a bioaccumulation model. The most detailed model set up estimates concentrations in air, soil, fresh water sediment and fresh water biota with spatially explicit environmental characteristics and spatially explicit emissions to air and water in the period 1930-2005. Model performance was evaluated with the root mean square error (RMSE(log)), based on the difference between estimated and measured concentrations. The RMSE(log) was 5.4 for air, 5.6-6.3 for sediment and biota, and 5.5 for soil in the most detailed model scenario. Generally, model estimations tended to underestimate observed values for all compartments, except air. The decline in observed concentrations was also slightly underestimated by the model for the period where measurements were available (1989-2002). Applying a generic model setup with averaged emissions and averaged environmental characteristics, the RMSE(log) increased to 21 for air and 49 for sediment. For soil the RMSE(log) decreased to 3.5. We found that including spatial variation in emissions was most relevant for all compartments, except soil, while including spatial variation in environmental characteristics was less influential. For improving predictions of concentrations in sediment and aquatic biota, including emissions to water was found to be relevant as well., (Copyright 2009 Elsevier B.V. All rights reserved.)

Exposure of humans to chemicals in beef or milk is part of almost all risk evaluation procedures carried out to reduce emissions or to remediate sites. Concentrations of substances in these livestock products are often estimated using log-log regressions that relate the biotransfer factor BTF to the octanol-water partition ratio K(ow). However, the correctness of these empirical correlations has been questioned. Here, we compare them to the mechanistic model OMEGA that describes the distribution of substances in organisms by integrating theory on chemical fugacity and biological allometry. OMEGA has been calibrated and validated on thousands of laboratory and field data, reflecting many chemical substances and biological species. Overall fluxes of water, food, tissue (growth), milk and stable substances calculated by OMEGA are within a factor of two from independent data obtained in experiments. Rate constants measured for elimination of individual compounds of a recalcitrant nature vary around the level expected from the model for output to faeces and milk. Both data and model suggest that biotransfer BTF of stable substances to beef and milk is independent of the octanol-water partition ratio K(ow) in the range of 10(3)-10(6). This contradicts empirical regressions including stable and labile compounds. As expected, levels of labile substances vary widely around a tentative indication derived from the model. Transformation and accumulation of labile substances remains highly specific for the chemical and organism concerned but depends weakly on the octanol-water partition ratio K(ow). Several possibilities for additional refinement are identified.

Environmental risk assessment procedures often use bioaccumulation as a criterion for hazard identification of a polluted location. Field studies regarding metal concentrations in food chains, however, have provided widely different information, because accumulation is shown to vary between the extremes of bioreduction and biomagnification. Bioaccumulation models provide insight regarding species-specific uptake and elimination kinetics of metals and assist in the interpretation of field data. Here, we use the bioaccumulation model OMEGA (Optimal Modeling for Ecotoxicological Applications) to estimate cadmium accumulation in herbivorous voles and carnivorous shrews. In addition to model validation, a meta-analysis of cadmium accumulation data is performed, because earlier studies generally have focused on relationships between cadmium concentrations in either specific tissues (kidney and liver) or whole-body concentrations and total soil levels. Additionally, we included the food-small mammal relationship. Our results show that cadmium whole-body concentrations are significantly related to cadmium levels in food items such as earthworms and plants. In addition, a significant relationship is found between cadmium accumulation in the liver and kidney of small mammals and total soil levels. Cadmium concentrations in shrews typically are an order of magnitude higher than metal levels in voles as a result of higher metal accumulation in earthworms compared to plants. Model predictions for both voles and shrews are in good agreement with field observations; deviations generally are within a factor of five. Small mammals prevent cadmium toxicity by binding this metal to metallothionein, which likely results in low elimination rates. Comparison with empirical elimination rates shows that rate constants of loss are accurately predicted assuming that cadmium is only released via growth dilution.

Biota to sediment accumulation factors (BSAFs) are widely used to describe the potential accumulation of organic contaminants in organisms. From field studies it is known that these BSAFs can vary dramatically between sediments of different origin, which is possibly explained by the variation in bioavailability of organic contaminants in sediments. In the present study it is shown that the variability in BSAF values for different sediment samples obtained at two Dutch freshwater sites could largely be explained by the variation in Tenax-extractable concentrations in these sediments. Variations of a factor of about 50 could be explained. The ratio between concentrations in biota and Tenax-extractable concentrations in sediment varied slightly between sediments and contaminant class, but was close to the theoretically expected value of 2. This is a strong indication that Tenax-extractable concentrations of contaminants in sediments are an excellent indicator of available concentrations.

In this study, biotransformation rate constants are estimated for a large set of organic compounds. Biotransformation (km) is considered part of the total elimination, further consisting of physico-chemical elimination to water (kw), depuration by feces (kf) and growth dilution (gamma). Existing models are used to estimate kw and kf, and gamma. The difference between measured elimination rate constants and the sum of predicted elimination rate constants for water, feces and growth indicates the ration of biotransformation in the total elimination. In all examined animal classes, polycyclic aromatic hydrocarbons seem to be metabolized at an intermediate rate. Because of the relative low hydrophobicity of some of the studied compounds, their physico-chemical elimination rate constant is relatively high, and the relative contribution of metabolism to total elimination of these compounds is therefore relatively low. Fish seem to be capable of metabolizing chlorodibenzo-p-dioxins and -furans, DDT, chloroanilines and phenol.

A model was designed and calibrated with accumulation data to calculate the internal concentrations of microcontaminants in organisms as a function of a few constants and variables. The main factors are the exposure time, the external exposure concentration, the partition ratio of the compound, and the size of the taxon concerned. The model was applied to calculate the lethal and sublethal body burdens of several priority compounds and some major taxa. Estimations were generally confirmed at the order of magnitude level by measured residues and applied doses if available. According to the estimations, most priority compounds chosen were critical for most taxa above internal concentrations of 0.1 mmol.kg-1 wet wt. Trichloromethane, 1,2,4-trichlorobenzene, and hexachlorobenzene were lethal above this level only, whereas other organic microcontaminants affected at least some taxa at lower body burdens. The log(Kow) of the organic compounds ranged from 2.0 to 7.0. Keeping in mind that bioconcentration and -magnification ratios for metals may be quite variable, the lowest critical residues estimated were just below the value of 0.1 mmol.kg-1 wet wt. Here, external concentrations encountered in natural habitats seem to be a promising tool for predictive comparative ecotoxicology. The critical body burdens for plants and invertebrates may have been overestimated due to uncertainty about the parameters. Among the different taxa, however, the fish families chosen (Salmonidae and Cyprinidae) seem to be most sensitive to most compounds. Internal response concentrations of the herbicide atrazine were the lowest in micro- and macrophytes, whereas parathion affected invertebrates at low levels. The database that provided the external response concentrations was also consulted to estimate so-called extrapolation or safety factors. On average, long-term no effect concentrations in water are estimated to be about 10-30 times below short-term median lethal levels. In general, short-term versus long-term, lethal versus sublethal, and median versus no response concentration ratios each contributed factors of about 2-3 to this overall ratio. The model for internal concentrations indicated that the ratio between the short-term and the long-term LC50 will be high for large species and high octanol-water partition ratios.