A Review of Mechanistic Models for Predicting Adverse Effects in Sediment Toxicity Testing.

Since recognizing the importance of bioavailability for understanding the toxicity of chemicals in sediments, mechanistic modeling has advanced over the last 40 years by building better tools for estimating exposure and making predictions of probable adverse effects. Our review provides an up-to-date survey of the status of mechanistic modeling in contaminated sediment toxicity assessments. Relative to exposure, advances have been most substantial for non-ionic organic contaminants (NOCs) and divalent cationic metals, with several equilibrium partitioning-based (Eq-P) models having been developed. This has included the use of Abraham equations to estimate partition coefficients for environmental media. As a result of the complexity of their partitioning behavior, progress has been less substantial for ionic/polar organic contaminants. When the EqP-based estimates of exposure and bioavailability are combined with water-only effects measurements, predictions of sediment toxicity can be successfully made for NOCs and selected metals. Both species sensitivity distributions and toxicokinetic and toxicodynamic models are increasingly being applied to better predict contaminated sediment toxicity. Furthermore, for some classes of contaminants, such as polycyclic aromatic hydrocarbons, adverse effects can be modeled as mixtures, making the models useful in real-world applications, where contaminants seldomly occur individually. Despite the impressive advances in the development and application of mechanistic models to predict sediment toxicity, several critical research needs remain to be addressed. These needs and others represent the next frontier in the continuing development and application of mechanistic models for informing environmental scientists, managers, and decisions makers of the risks associated with contaminated sediments. Environ Toxicol Chem 2023;00:1-17. © 2023 SETAC. This article has been contributed to by U.S. Government employees and their work is in the public domain in the USA.

A Review of the Literature on Potential Effects of Runoff from Refined Coal-Tar-Based Sealant Coating on Aquatic Organisms.

Pavement sealants are frequently applied to parking lots and driveways to improve their appearance and protect the integrity of the underlying asphalt. We performed a comprehensive literature review to summarize the potential impacts of refined coal-tar-based sealant (RCTS) runoff to aquatic organisms and to evaluate the strengths and weaknesses of the lines of evidence presented in the literature. The studies reviewed included both laboratory and field exposures, with and without exposure to UV light, and measured effects on multiple endpoints associated with bacteria, benthic macroinvertebrates, and fish. Several studies demonstrated that constituents in RCTS runoff can affect survival, growth, behavior, development, and molecular responses of aquatic organisms in controlled laboratory settings. However, translating effects observed in the laboratory to field settings, where runoff is diluted and constituents interact with particulate and dissolved stream constituents (e.g., organic matter), has proven difficult. In this review, we identify the strengths and weaknesses of the existing literature and provide recommendations for study designs and methods to fill the most critical data gaps in understanding the risk of this material to aquatic organisms. Our review highlights the need for environmentally relevant study designs that demonstrate cause-effect relationships under field conditions. Integr Environ Assess Manag 2019;00:1-11. © 2019 SETAC.

Development of a Novel Equilibrium Passive Sampling Device for Methylmercury in Sediment and Soil Porewaters.

We explored the concept of equilibrium passive sampling for methylmercury (MeHg) using the strategy developed for hydrophobic organic chemicals. Passive sampling should allow prediction of the concentration of the chemically labile fraction of MeHg in sediment porewaters based on equilibrium partitioning into the sampler, without modeling diffusion rates through the sampler material. Our goals were to identify sampler materials with the potential to mimic MeHg partitioning into animals and sediments and provide reversible sorption in a time frame appropriate for in situ samplers. Candidate materials tested included a range of polymers embedded with suitable sorbents for MeHg. The most promising were activated carbon (AC) embedded in agarose, thiol-self-assembled monolayers on mesoporous supports embedded in agarose, and cysteine-functionalized polyethylene terephthalate, which yielded log sampler-water partition coefficients of 2.8 to 5 for MeHgOH and MeHg complexed with dissolved organic matter (Suwannee River humic acid). Sampler equilibration time in sediments was approximately 1 to 2 wk. Investigation of the MeHg accumulation mechanism by AC embedded in agarose suggested that sampling was kinetically influenced by MeHg interactions with AC particles and not limited by diffusion through the gel for this material. Also, AC exhibited relatively rapid desorption of Hg and MeHg, indicating that this sorbent is capable of reversible, equilibrium measurements. In sediment:water microcosms, porewater concentrations made with isotherm-calibrated passive samplers agreed within a factor of 2 (unamended sediment) or 4 (AC-amended sediment) with directly measured concentrations. The present study demonstrates a potential new approach to passive sampling of MeHg. Environ Toxicol Chem 2020;39:323-334. © 2019 SETAC.

Microplastics as vectors for bioaccumulation of hydrophobic organic chemicals in the marine environment: A state-of-the-science review.

A state-of-the-science review was conducted to examine the potential for microplastics to sorb hydrophobic organic chemicals (HOCs) from the marine environment, for aquatic organisms to take up these HOCs from the microplastics, and for this exposure to result in adverse effects to ecological and human health. Despite concentrations of HOCs associated with microplastics that can be orders of magnitude greater than surrounding seawater, the relative importance of microplastics as a route of exposure is difficult to quantify because aquatic organisms are typically exposed to HOCs from various compartments, including water, sediment, and food. Results of laboratory experiments and modeling studies indicate that HOCs can partition from microplastics to organisms or from organisms to microplastics, depending on experimental conditions. Very little information is available to evaluate ecological or human health effects from this exposure. Most of the available studies measured biomarkers that are more indicative of exposure than effects, and no studies showed effects to ecologically relevant endpoints. Therefore, evidence is weak to support the occurrence of ecologically significant adverse effects on aquatic life as a result of exposure to HOCs sorbed to microplastics or to wildlife populations and humans from secondary exposure via the food chain. More data are needed to fully understand the relative importance of exposure to HOCs from microplastics compared with other exposure pathways. Environ Toxicol Chem 2016;35:1667-1676. © 2016 SETAC.

Passive sampling methods for contaminated sediments: practical guidance for selection, calibration, and implementation.

This article provides practical guidance on the use of passive sampling methods (PSMs) that target the freely dissolved concentration (Cfree ) for improved exposure assessment of hydrophobic organic chemicals in sediments. Primary considerations for selecting a PSM for a specific application include clear delineation of measurement goals for Cfree , whether laboratory-based "ex situ" and/or field-based "in situ" application is desired, and ultimately which PSM is best-suited to fulfill the measurement objectives. Guidelines for proper calibration and validation of PSMs, including use of provisional values for polymer-water partition coefficients, determination of equilibrium status, and confirmation of nondepletive measurement conditions are defined. A hypothetical example is described to illustrate how the measurement of Cfree afforded by PSMs reduces uncertainty in assessing narcotic toxicity for sediments contaminated with polycyclic aromatic hydrocarbons. The article concludes with a discussion of future research that will improve the quality and robustness of Cfree measurements using PSMs, providing a sound scientific basis to support risk assessment and contaminated sediment management decisions.

A framework for using dose as a metric to assess toxicity of fish to PAHs.

The effects of PAHs on fish have been described in the literature, but the ability to assess risk to juvenile and adult fish from exposure to PAHs the field is currently hindered by the lack of a predictive dose-response exposure model. The goal of this paper is to present a framework that can be used to convert concentrations of PAHs in environmental media (e.g., water, food, and sediment) to a dose metric that is predictive of adverse effects. Examples of toxicity studies that can be considered within the framework are presented. Additional toxicity studies are needed to establish the potency and range of toxic responses to mixtures of PAHs that fish encounter in the environment.