Ecotoxicological environmental risk limits for total petroleum hydrocarbons on the basis of internal lipid concentrations.

A method is described for deriving ecotoxicological environmental risk limits (ERLs) for total petroleum hydrocarbons (TPH). Toxicity data for two oil types (light and heavy) to benthic organisms and corresponding estimated internal lipid concentrations, calculated by equilibrium partitioning, are used as a measure of toxicity by narcosis. It is assumed that uptake by organisms takes place from the aqueous phase, and for partitioning, both oil droplets or coating and organic carbon of sediment are taken into account. To distinguish between the different fractions of TPH, the method used is based on a fraction analysis approach in which aliphatic and aromatic compounds are regarded separately and both are further divided into different fractions. A toxic unit approach is applied to these fractions to take additivity into account. Lethality of the lighter oil type (internal concentration 28-204 mmol/Llipid) was in good agreement with data on internal concentrations retrieved from the literature. For the heavier oil type the observed toxicity was slightly higher and can probably be attributed to physical soiling of the organisms by oil or oxygen depletion due to biodegradation of the oil. For deriving ERLs, chronic endpoints are considered. The most sensitive chronic endpoints appear to be similar for both types of oil. The distribution of estimated total internal concentrations for chronic endpoints (1.38-149 mmol/Llipid) is used as a basis for the ERLs. The resulting ERLs for the mixture of TPH are comparable with ERLs for single compounds.

Environmental exposure scenarios: development, challenges and possible solutions.

Under the new REACH system, companies importing, producing and marketing chemical substances will be obliged to register the single substances and to carry out a safety assessment for all identified uses during the life cycle of the substance. This duty will apply to about 10,000 existing substances in the EU market exceeding an annual production or import volume of 10 t per company. If the substance is already known to be dangerous or turns out to be dangerous(1) during the hazard assessment, the registrant is obliged to carry out an exposure assessment and a risk characterisation for all identified uses. The goal of the safety assessment is to define the conditions of use that allow for adequate control of risk with regard to health and safety at the work place, consumer safety and protection of the environment. Once the registrant has established and documented these conditions in the Chemicals Safety Report (CSR), that information is to be communicated down the supply chain by means of the Extended Safety Data Sheet (eSDS). The ultimate aim of the new legislation is to establish duties and mechanisms that systematically prevent or limit exposure to dangerous industrial chemicals. The current paper explains this concept with regard to environmental exposure and highlights the challenges and possible solutions.

Modeling decreased food chain accumulation of PAHs due to strong sorption to carbonaceous materials and metabolic transformation.

The predictive power of bioaccumulation models may be limited when they do not accountfor strong sorption of organic contaminants to carbonaceous materials (CM) such as black carbon, and when they do not include metabolic transformation. We tested a food web accumulation model, including sorption to CM, on data from a model ecosystem experiment with historically contaminated sediment. In combination with measured CM contents of the sediment, the model gave good fits for the biota that are known not to metabolize PAHs (macrophytes, periphyton, floating algal biomass). The same model was applied to invertebrates and fish but now with optimization of their metabolic transformation rates (k(m)). For fish, these rates correlated empirically with log K(OW): Log k(m) = -0.8 log K(OW) + 4.5 (r2 adj = 0.73). For invertebrates, log k(m) did not correlate with logK(OW). Sensitivity analysis revealed that the model output is highly sensitive to sediment CM content and sorption parameters, moderately sensitive to metabolic transformation rates, and slightly sensitive to lipid fraction of the organism and diet-related parameters. It is concluded that CM-inclusive models yield a better assessment of accumulation than models without sorption to CM. Furthermore, inclusion of CM in a model enables metabolic transformation rates to be calculated from the remaining overestimation in the model results when compared to measured data.

Critical body residues linked to octanol-water partitioning, organism composition, and LC50 QSARs: meta-analysis and model.

To protect thousands of species from thousands of chemicals released in the environment, various risk assessment tools have been developed. Here, we link quantitative structure-activity relationships (QSARs) for response concentrations in water (LC50) to critical concentrations in organisms (C50) by a model for accumulation in lipid or non-lipid phases versus water Kpw. The model indicates that affinity for neutral body components such as storage fat yields steep Kpw-Kow relationships, whereas slopes for accumulation in polar phases such as proteins are gentle. This pattern is confirmed by LC50 QSARs for different modes of action, such as neutral versus polar narcotics and organochlorine versus organophosphor insecticides. LC50 QSARs were all between 0.00002 and 0.2Kow(-1). After calibrating the model with the intercepts and, for the first time also, with the slopes of the LC50 QSARs, critical concentrations in organisms C50 are calculated and compared to an independent validation data set. About 60% of the variability in lethal body burdens C50 is explained by the model. Explanations for differences between estimated and measured levels for 11 modes of action are discussed. In particular, relationships between the critical concentrations in organisms C50 and chemical (Kow) or species (lipid content) characteristics are specified and tested. The analysis combines different models proposed before and provides a substantial extension of the data set in comparison to previous work. Moreover, the concept is applied to species (e.g., plants, lean animals) and substances (e.g., specific modes of action) that were scarcely studied quantitatively so far.

Environmental quality criteria for organic chemicals predicted from internal effect concentrations and a food web model.

Environmental quality criteria (EQC) for hydrophobic organic chemicals were calculated with a model for bioaccumulation in food webs. The model was calibrated and verified using polychlorinated biphenyl concentrations in food webs of shallow lakes. The EQCs in water and sediment were derived based on internal effect concentrations (IECs) for several modes of toxic action. By reverse calculation with the food web model for each organism in the web, a different water or sediment concentration is calculated corresponding to the IEC in each organism. A statistical procedure with an acute-to-chronic value is used to derive chronic EQCs based on bioaccumulation. The model-based chronic EQCs were compared with previously established EQCs. The EQCs calculated with the food web model generally are within an order of magnitude of the previously derived EQCs based on toxicity data on individual chemicals. Some previously derived EQCs are much lower than model predictions and usually based on small samples of toxicity data such as no-observed-effect concentrations (NOECs) with large assessment factors. When faced with data gaps, it is proposed to use model-based chronic EQCs for (polar) narcotic chemicals. Other modes of action require a different model concept to account for receptor-based toxicity.

A freshwater food web model for the combined effects of nutrients and insecticide stress and subsequent recovery.

A microcosm experiment that addressed the interaction between eutrophication processes and contaminants was analyzed using a food web model. Both direct and indirect effects of nutrient additions and a single insecticide application (chlorpyrifos) on biomass dynamics and recovery of functional groups were modeled. Direct toxicant effects on sensitive arthropods could be predicted reasonably well using concentration-response relationships from the laboratory with representative species. Model predictions showed that nutrient additions alone caused only small effects on toxicant fate and effects probably due to the relatively high dissipation rate of chlorpyrifos. Enhancement of eutrophication effects by the insecticide was relatively small and seemed to be additive. The recovery of some affected functional groups was hampered in the indoor microcosms due to their isolation from outdoor seed populations. Introducing recolonization scenarios in the model simulated dose-dependent recovery. Recolonization increased the recovering rate after exposure to the pesticide. Modeling can extend the use of microcosms as a link between laboratory and field as this allows the prediction of effects and recovery of ecosystems for concentrations that have not been experimentally tested.