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Only a fraction of the total number of per‐ and polyfluoroalkyl substances (PFAS) are monitored on a routine basis using targeted chemical analyses. We report on an approach toward identifying bioactive substances in environmental samples using effect‐directed analysis by combining toxicity testing, targeted chemical analyses, and suspect screening. PFAS compete with the thyroid hormone thyroxin (T4) for binding to its distributor protein transthyretin (TTR). Therefore, a TTR‐binding bioassay was used to prioritize unknown features for chemical identification in a PFAS‐contaminated sediment sample collected downstream of a factory producing PFAS‐coated paper. First, the TTR‐binding potencies of 31 analytical PFAS standards were determined. Potencies varied between PFAS depending on carbon chain length, functional group, and, for precursors to perfluoroalkyl sulfonic acids (PFSA), the size or number of atoms in the group(s) attached to the nitrogen. The most potent PFAS were the seven‐ and eight‐carbon PFSA, perfluoroheptane sulfonic acid (PFHpS) and perfluorooctane sulfonic acid (PFOS), and the eight‐carbon perfluoroalkyl carboxylic acid (PFCA), perfluorooctanoic acid (PFOA), which showed approximately four‐ and five‐times weaker potencies, respectively, compared with the native ligand T4. For some of the other PFAS tested, TTR‐binding potencies were weak or not observed at all. For the environmental sediment sample, not all of the bioactivity observed in the TTR‐binding assay could be assigned to the PFAS quantified using targeted chemical analyses. Therefore, suspect screening was applied to the retention times corresponding to observed TTR binding, and five candidates were identified. Targeted analyses showed that the sediment was dominated by the di‐substituted phosphate ester of N‐ethyl perfluorooctane sulfonamido ethanol (SAmPAP diester), whereas it was not bioactive in the assay. SAmPAP diester has the potential for (bio)transformation into smaller PFAS, including PFOS. Therefore, when it comes to TTR binding, the hazard associated with this substance is likely through (bio)transformation into more potent transformation products. Environ Toxicol Chem 2024;43:245–258. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC. [ABSTRACT FROM AUTHOR]

Large-scale use of dispersants to remediate oil spills has raised concerns about their toxicity to marine organisms. Of particular concern is oxidative stress and resulting membrane damage due to exposure to surfactants in dispersant mixtures. We investigated the potential of the dispersant Corexit 9500 ® and one of its major components, the anionic surfactant dioctyl sodium sulfosuccinate (DOSS), to induce oxidative stress in larval sheepshead minnows after 24 and 96h exposures, at two sublethal concentrations, the lesser being environmentally realistic for each compound. Corexit exposures elicited only minimal antioxidant responses for most antioxidant components tested, with increased glutathione peroxidase (GPx) and glutathione S-transferase (GST) activities observed only after 96h and at the higher exposure concentration. In contrast, DOSS induced statistically significant increases in the levels of reactive oxygen species (ROS), GPx, and lipid peroxidation, as well as depleted reduced glutathione (GSH) levels at both time points and concentrations. These data indicate that short-term and environmentally realistic exposures to DOSS can impact antioxidant response capabilities, raising concern about its use in oil dispersants and other high volume use products where environmental releases are likely., (Copyright © 2017 Elsevier B.V. All rights reserved.)