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The present study examined the ability of three chemical estimation methods to predict toxicity and nontoxicity of polycyclic aromatic hydrocarbon (PAH) -contaminated sediment to the freshwater benthic amphipod Hyalella azteca for 192 sediment samples from 12 field sites. The first method used bulk sediment concentrations of 34 PAH compounds (PAH34), and fraction of total organic carbon, coupled with equilibrium partitioning theory to predict pore-water concentrations (KOC method). The second method used bulk sediment PAH34 concentrations and the fraction of anthropogenic (black carbon) and natural organic carbon coupled with literature-based black carbon-water and organic carbon-water partition coefficients to estimate pore-water concentrations (KOCKBC method). The final method directly measured pore-water concentrations (pore-water method). The U.S. Environmental Protection Agency's hydrocarbon narcosis model was used to predict sediment toxicity for all three methods using the modeled or measured pore-water concentration as input. The KOC method was unable to predict nontoxicity (83% of nontoxic samples were predicted to be toxic). The KOCKBC method was not able to predict toxicity (57% of toxic samples were predicted to be nontoxic) and, therefore, was not protective of the environment. The pore-water method was able to predict toxicity (correctly predicted 100% of the toxic samples were toxic) and nontoxicity (correctly predicted 71% of the nontoxic samples were nontoxic). This analysis clearly shows that direct pore-water measurement is the most accurate chemical method currently available to estimate PAH-contaminated sediment toxicity to H. azteca.

The evaluation of a chemical substance's persistence is key to understanding its environmental fate, exposure concentration, and, ultimately, environmental risk. Traditional biodegradation test methods were developed many years ago for soluble, nonvolatile, single-constituent test substances, which do not represent the wide range of manufactured chemical substances. In addition, the Organisation for Economic Co-operation and Development (OECD) screening and simulation test methods do not fully reflect the environmental conditions into which substances are released and, therefore, estimates of chemical degradation half-lives can be very uncertain and may misrepresent real environmental processes. In this paper, we address the challenges and limitations facing current test methods and the scientific advances that are helping to both understand and provide solutions to them. Some of these advancements include the following: (1) robust methods that provide a deeper understanding of microbial composition, diversity, and abundance to ensure consistency and/or interpret variability between tests; (2) benchmarking tools and reference substances that aid in persistence evaluations through comparison against substances with well-quantified degradation profiles; (3) analytical methods that allow quantification for parent and metabolites at environmentally relevant concentrations, and inform on test substance bioavailability, biochemical pathways, rates of primary versus overall degradation, and rates of metabolite formation and decay; (4) modeling tools that predict the likelihood of microbial biotransformation, as well as biochemical pathways; and (5) modeling approaches that allow for derivation of more generally applicable biotransformation rate constants, by accounting for physical and/or chemical processes and test system design when evaluating test data. We also identify that, while such advancements could improve the certainty and accuracy of persistence assessments, the mechanisms and processes by which they are translated into regulatory practice and development of new OECD test guidelines need improving and accelerating. Where uncertainty remains, holistic weight of evidence approaches may be required to accurately assess the persistence of chemicals. Integr Environ Assess Manag 2022;1-34.

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