Risk management of hazardous substances in a circular economy.

The ambitions for a circular economy are high and unambiguous, but day-to-day experience shows that the transition still has many difficulties to overcome. One of the current hurdles is the presence of hazardous substances in waste streams that enter or re-enter into the environment or the technosphere. The key question is: do we have the appropriate risk management tools to control any risks that might arise from the re-using and recycling of materials? We present some recent cases that illustrate current practice and complexity in the risk management of newly-formed circular economy chains. We also highlight how separate legal frameworks are still disconnected from each other in these cases, and how circular economy initiatives interlink with the European REACH regulation. Furthermore, we introduce a novel scheme describing how to decide whether a(n)(additional) risk assessment is necessary with regard to the re-use of materials containing hazardous substances. Finally, we present our initial views on new concepts for the fundamental integration of sustainability and safety aspects. These concepts should be the building blocks for the near future shifts in both policy frameworks and voluntary initiatives that support a sound circular economy transition.

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.

Workgroup report: review of fish bioaccumulation databases used to identify persistent, bioaccumulative, toxic substances.

Chemical management programs strive to protect human health and the environment by accurately identifying persistent, bioaccumulative, toxic substances and restricting their use in commerce. The advance of these programs is challenged by the reality that few empirical data are available for the tens of thousands of commercial substances that require evaluation. Therefore, most preliminary assessments rely on model predictions and data extrapolation. In November 2005, a workshop was held for experts from governments, industry, and academia to examine the availability and quality of in vivo fish bioconcentration and bioaccumulation data, and to propose steps to improve its prediction. The workshop focused on fish data because regulatory assessments predominantly focus on the bioconcentration of substances from water into fish, as measured using in vivo tests or predicted using computer models. In this article we review of the quantity, features, and public availability of bioconcentration, bioaccumulation, and biota-sediment accumulation data. The workshop revealed that there is significant overlap in the data contained within the various fish bioaccumulation data sources reviewed, and further, that no database contained all of the available fish bioaccumulation data. We believe that a majority of the available bioaccumulation data have been used in the development and testing of quantitative structure-activity relationships and computer models currently in use. Workshop recommendations included the publication of guidance on bioconcentration study quality, the combination of data from various sources to permit better access for modelers and assessors, and the review of chemical domains of existing models to identify areas for expansion.

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.

Implementation of bioavailability in standard setting and risk assessment.

Bioavailability is, to an increasing extent, recognised as the key issue linking the increased levels of toxicants to actually occurring adverse effects in ecosystems, whilst taking the modifying effects of the abiotic components of the environment into account. Various factors may affect bioavailability in the field, and these factors are often time and space dependent. This is one of the main reasons why legislators have been reluctant to implement bioavailability in risk assessment procedures. Over the last few years, however, considerable scientific progress has been made with regard to increasing our understanding of the chemical and ecological mechanisms responsible for rendering chemicals available for uptake and toxicity. As a consequence, legislators face the challenge of having to anticipate the scientific progress and to implement bioavailability in legislation. This contribution reports on the possibilities of implementing various methodologies within a maximum time period of three years.

Implementation of bioavailability in standard setting and risk assessment: suggestions based on a workshop with emphasis on metals.

Bioavailability is increasingly recognised as the key issue linking increased levels of toxicants with actually occurring adverse effects in ecosystems, whilst taking the modifying effects of the abiotic components of the environment into account. Various factors may affect bioavailability in the field, and often these factors are time- and space-dependent. This is one of the main reasons why legislators have been reluctant in implementing bioavailability in risk assessment procedures. Over the last few years, however, considerable scientific progress has been made with regard to better understanding of chemical and ecological mechanisms responsible for rendering chemicals available for uptake and toxicity. As a consequence, legislators face the challenge to anticipate the scientific progress and to implement bioavailability in legislation. This paper discusses the possibilities of implementing various methodologies within a maximum period of time of three years.

Mechanism-based testing strategy using in vitro approaches for identification of thyroid hormone disrupting chemicals.

The thyroid hormone (TH) system is involved in several important physiological processes, including regulation of energy metabolism, growth and differentiation, development and maintenance of brain function, thermo-regulation, osmo-regulation, and axis of regulation of other endocrine systems, sexual behaviour and fertility and cardiovascular function. Therefore, concern about TH disruption (THD) has resulted in strategies being developed to identify THD chemicals (THDCs). Information on potential of chemicals causing THD is typically derived from animal studies. For the majority of chemicals, however, this information is either limited or unavailable. It is also unlikely that animal experiments will be performed for all THD relevant chemicals in the near future for ethical, financial and practical reasons. In addition, typical animal experiments often do not provide information on the mechanism of action of THDC, making it harder to extrapolate results across species. Relevant effects may not be identified in animal studies when the effects are delayed, life stage specific, not assessed by the experimental paradigm (e.g., behaviour) or only occur when an organism has to adapt to environmental factors by modulating TH levels. Therefore, in vitro and in silico alternatives to identify THDC and quantify their potency are needed. THDC have many potential mechanisms of action, including altered hormone production, transport, metabolism, receptor activation and disruption of several feed-back mechanisms. In vitro assays are available for many of these endpoints, and the application of modern '-omics' technologies, applicable for in vivo studies can help to reveal relevant and possibly new endpoints for inclusion in a targeted THDC in vitro test battery. Within the framework of the ASAT initiative (Assuring Safety without Animal Testing), an international group consisting of experts in the areas of thyroid endocrinology, toxicology of endocrine disruption, neurotoxicology, high-throughput screening, computational biology, and regulatory affairs has reviewed the state of science for (1) known mechanisms for THD plus examples of THDC; (2) in vitro THD tests currently available or under development related to these mechanisms; and (3) in silico methods for estimating the blood levels of THDC. Based on this scientific review, the panel has recommended a battery of test methods to be able to classify chemicals as of less or high concern for further hazard and risk assessment for THD. In addition, research gaps and needs are identified to be able to optimize and validate the targeted THD in vitro test battery for a mechanism-based strategy for a decision to opt out or to proceed with further testing for THD.

Specific environmental release categories--A tool for improving chemical safety assessment in the EC--report of a multi-stakeholder workshop.

In April 2011, experts from industry and authorities met for a workshop to discuss experience and future developments regarding the use of specific environmental release categories (SPERCs) in chemicals safety assessment (CSA) under the European Chemicals Regulation Registration, Evaluation and Authorization of Chemicals (REACH). This article provides a summary of the workshop. It briefly explains what a SPERC is, why SPERCs are needed, where the challenges of the concept are, and what improvements are needed to make SPERCs a useful tool for assessments under REACH.

Evaluation of the Daphnia magna reproduction test for detecting endocrine disruptors.

The Daphnia 21 d reproduction test is considered as a comprehensive and decisive test in the OECD Conceptual Framework for testing and assessment of endocrine disrupting chemicals (EDCs). However, how to interpret results of the Daphnia 21 d reproduction test for identification, risk assessment and testing strategy of EDCs remains an unsolved issue. This study analysed a total number of 135 published studies encompassing 86 known EDCs and non-EDCs with different modes of action. Our results show that the majority of effects on apical endpoints (survival, molting, growth, time to reproductive maturity, brood size, the number of broods, and the total number of offspring) do not seem to be EDC-specific. In contrast, the endpoint sex ratio is likely specific to juvenile hormones and their mimics. Variability is quantified for three most reported endpoints survival, the total number of offspring and sex ratio. Quantification of the endpoint sensitivity shows that the sensitivity of the sex ratio is lower than that of the total number of offspring. The Daphnia 21 d reproduction test gives insufficient information to conclude if a substance is an EDC or not. EDCs that are potent in assays in vitro may not be potent in the Daphnia 21 d reproduction test. We conclude that the Daphnia 21 d reproduction test is important for deriving No Observed Effect Concentrations for risk assessment but may produce false negatives in identification of EDCs when used on its own. A targeted testing strategy for selection of species, tests, and endpoints is suggested for identifying EDCs.

Evaluation of the fish short term reproduction assay for detecting endocrine disrupters.

In a fish testing strategy, positive results of the fish short term reproduction assay (FSTR), often trigger a definitive test like the fish sexual development test (FSDT) or the fish full life cycle test (FFLC), entailing ethical and economic problems. This study analysed 137 studies encompassing 35 chemicals with different modes of actions (MOAs). Variability is quantified for MOA endpoints vitellogenin (VTG) and secondary sex characteristics (SSCs) as well as for apical endpoints. Two MOA endpoints could indicate estrogenic, anti-estrogenic, androgenic, anti-androgenic and steroidogenesis activities. Great variability, however, has been observed for chemicals with anti-androgenic and steroidogenesis activities, suggesting that TG229/230 may not be sensitive enough to detect these types of chemicals and may produce false negatives. Changes in apical endpoints like fecundity are not limited to endocrine disrupting chemicals (EDCs). Non-EDCs could induce the similar effects on these apical endpoints. If elucidating MOA is needed, targeted in vitro MOA tests are suggested. Positive in vitro MOA results trigger a definitive test, which could be used for confirmation of the MOA in vivo and for deriving a no observed effect concentration (NOEC). Based on positive MOA results of TG229, a definitive test such as the FSDT or the FFLC is still needed, because the current TG229 has limitation on the derivation of a NOEC. An extended TG229 with more power to detect reproduction effects, as recently proposed in the OECD test guideline program, would improve the possibility to derive a NOEC and increase its usefulness in risk assessment.

Guidance for evaluating in vivo fish bioaccumulation data.

Currently, the laboratory-derived fish bioconcentration factor (BCF) serves as one of the primary data sources used to assess the potential for a chemical to bioaccumulate. Consequently, fish BCF values serve a central role in decision making and provide the basis for development of quantitative structure-property relationships (QSPRs) used to predict the bioaccumulation potential of untested compounds. However, practical guidance for critically reviewing experimental BCF studies is limited. This lack of transparent guidance hinders improvement in predictive models and can lead to uninformed chemical management decisions. To address this concern, a multiple-stakeholder workshop of experts from government, industry, and academia was convened by the International Life Sciences Institute Health and Environmental Sciences Institute to examine the data availability and quality issues associated with in vivo fish bioconcentration and bioaccumulation data. This paper provides guidance for evaluating key aspects of study design and conduct that must be considered when judging the reliability and adequacy of reported laboratory bioaccumulation data. Key criteria identified for judging study reliability include 1) clear specification of test substance and fish species investigated, 2) analysis of test substance in both fish tissue and exposure medium, 3) no significant adverse effects on exposed test fish, and 4) a reported test BCF that reflects steady-state conditions with unambiguous units. This guidance is then applied to 2 data-rich chemicals (anthracene and 2,3,7,8-tetrachlorodibenzo-p-dioxin) to illustrate the critical need for applying a systematic data quality assessment process. Use of these guidelines will foster development of more accurate QSPR models, improve the performance and reporting of future laboratory studies, and strengthen the technical basis for bioaccumulation assessment in chemicals management.

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.