Identifying Organic Toxicants in Sediment Using Effect-Directed Analysis: A Combination of Bioaccessibility-Based Extraction and High-Throughput Midge Toxicity Testing

Toxicity identification evaluation (TIE) and effect-directed analysis (EDA) were integrated to diagnose toxicity drivers in a complex system, such as sediment. In TIE manipulation, XAD resin was utilized as an amending agent for characterizing organic toxicants, which also facilitate a large-volume bioaccessibility-based extraction for EDA purposes. Both raw sediments in TIE and extract fractions in EDA were tested with Chironomus dilutus for toxicity using whole-sediment testing and a high-throughput microplate assay. This allowed for a direct link between whole-sediment TIE and EDA, which strongly strengthened the characterization and identification of toxicants. Sediments amended with XAD resin, as part of the TIE, significantly reduced midge mortality compared with unamended sediments, suggesting that organics were one class of main toxicants. On the basis of bioaccessible concentrations in sediment measured by XAD extraction, a group of previously unidentified contaminants, synthetic polycyclic musks (versalide, tonalide, and galaxolide), were found to explain 32–73% of the observed toxicity in test sediments. Meanwhile, three pyrethroids contributed to an additional 17–35% of toxicity. Surprisingly, the toxicity contribution of musks and pyrethroids reached 58–442 and 56–1625%, respectively, based on total sediment concentrations measured by exhaustive extraction. This suggested that total sediment concentrations significantly overestimated toxicity and that bioavailability should be considered in toxicity identification. Identifying nontarget toxicants sheds a light on application of the integrated TIE and EDA method in defining causality in a complex environment.