Bioavailability Assessment of Metals in Freshwater Environments: A Historical Review.

Many metals (aluminum, cadmium, cobalt, copper, nickel, lead, zinc) are widely studied environmental contaminants because of their ubiquity, potential toxicity to aquatic life, and tendency for toxicity to vary widely as a function of water chemistry. The interactions between metal and water chemistry influence metal "bioavailability," an index of the rate and extent to which the metal reaches the site of toxic action. The implications of metal bioavailability for ecological risk assessment are large, with as much as a 100-fold variability across a range of water chemistries in surface waters. Beginning as early as the 1930s, considerable research effort was expended toward documenting and understanding metal bioavailability as a function of total and dissolved metal, water hardness, natural organic matter, pH, and other water characteristics. The understanding of these factors and improvements in both analytical and computational chemistry led to the development of modeling approaches intended to describe and predict the relationship between water chemistry and metal toxicity, including the free ion activity model, the gill surface interaction model, the biotic ligand model, and additional derivatives and regression models that arose from similar knowledge. The arc of these scientific advances can also be traced through the evolution of the US Environmental Protection Agency's ambient water quality criteria over the last 50 yr, from guidance in the "Green Book" (1968) to metal-specific criteria produced in the last decade. Through time, water quality criteria in many jurisdictions have incorporated increasingly sophisticated means of addressing metal bioavailability. The present review discusses the history of scientific understanding of metal bioavailability and the development and application of models to incorporate this knowledge into regulatory practice. Environ Toxicol Chem 2019;39:48-59. © 2019 SETAC.

Perfluoroalkyl acids in the Canadian environment: multi-media assessment of current status and trends.

In Canada, perfluoroalkyl acids (PFAAs) have been the focus of several monitoring programs and research and surveillance studies. Here, we integrate recent data and perform a multi-media assessment to examine the current status and ongoing trends of PFAAs in Canada. Concentrations of perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), and other long-chain perfluorocarboxylates (PFCAs) in air, water, sediment, fish, and birds across Canada are generally related to urbanization, with elevated concentrations observed around cities, especially in southern Ontario. PFOS levels in water, fish tissue, and bird eggs were below their respective Draft Federal Environmental Quality Guidelines, suggesting there is low potential for adverse effects to the environment/organisms examined. However, PFOS in fish and bird eggs tended to exceed guidelines for the protection of mammalian and avian consumers, suggesting a potential risk to their wildlife predators, although wildlife population health assessments are needed to determine whether negative impacts are actually occurring. Long-term temporal trends of PFOS in suspended sediment, sediment cores, Lake Trout (Salvelinus namaycush), and Herring Gull (Larus argentatus) eggs collected from Lake Ontario increased consistently from the start of data collection until the 1990s. However, after this time, the trends varied by media, with concentrations stabilizing in Lake Trout and Herring Gull eggs, and decreasing and increasing in suspended sediment and the sediment cores, respectively. For PFCAs, concentrations in suspended sediment, sediment cores, and Herring Gulls generally increased from the start of data collection until present and concentrations in Lake Trout increased until the late 1990s and subsequently stabilized. A multimedia comparison of PFAA profiles provided evidence that unexpected patterns in biota of some of the lakes were due to unique source patterns rather than internal lake processes. High concentrations of PFAAs in the leachate and air of landfill sites, in the wastewater influent/effluent, biosolids, and air at wastewater treatment plants, and in indoor air and dust highlight the waste sector and current-use products (used primarily indoors) as ongoing sources of PFAAs to the Canadian environment. The results of this study demonstrate the utility of integrating data from different media. Simultaneous evaluation of spatial and temporal trends in multiple media allows inferences that would be impossible with data on only one medium. As such, more co-ordination among monitoring sites for different media is suggested for future sampling, especially at the northern sites. We emphasize the importance of continued monitoring of multiple-media for determining future responses of environmental PFAA concentrations to voluntary and regulatory actions.

Application of the tissue residue approach in ecological risk assessment.

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.