High-efficiency effect-directed analysis (EDA) advancing toxicant identification in aquatic environments: Latest progress and application status.

Facing the great threats to ecosystems and human health posed by the continuous release of chemicals into aquatic environments, effect-directed analysis (EDA) has emerged as a powerful tool for identifying causative toxicants. However, traditional EDA shows problems of low-coverage, labor-intensive and low-efficiency. Currently, a number of high-efficiency techniques have been integrated into EDA to improve toxicant identification. In this review, the latest progress and current limitations of high-efficiency EDA, comprising high-coverage effect evaluation, high-resolution fractionation, high-coverage chemical analysis, high-automation causative peak extraction and high-efficiency structure elucidation, are summarized. Specifically, high-resolution fractionation, high-automation data processing algorithms and in silico structure elucidation techniques have been well developed to enhance EDA. While high-coverage effect evaluation and chemical analysis should be further emphasized, especially omics tools and data-independent mass acquisition. For the application status in aquatic environments, high-efficiency EDA is widely applied in surface water and wastewater. Estrogenic, androgenic and aryl hydrocarbon receptor-mediated activities are the most concerning, with causative toxicants showing the typical structural features of steroids and benzenoids. A better understanding of the latest progress and application status of EDA would be beneficial to further advance in the field and greatly support aquatic environment monitoring.

Identify organic contaminants of high-concern based on non-targeted toxicity testing and non-targeted LC-HRMS analysis in tap water and source water along the Yangtze River.

Many organic pollutants were detected in tap water (TW) and source water (SW) along the Yangtze River. However, the potential toxic effects and the high-concern organics (HCOs) which drive the effect are still unknown. Here, a non-targeted toxicity testing method based on the concentration-dependent transcriptome and non-targeted LC-HRMS analysis combining tiered filtering were used to reveal the overall biological effects and chemical information. Subsequently, we developed a qualitative pathway-structure relationship (QPSR) model to effectively match the biological and chemical information and successfully identified HCOs in TW and SW along the Yangtze River by potential substructures of HCOs. Non-targeted toxicity testing found that the biological potency of both TW and SW was stronger in the downstream of the Yangtze River, and disruption of the endocrine system and cancer were the main drivers of the effect. In addition, non-targeted LC-HRMS analysis combined with retention time prediction results identified 3220 and 631 high-confidence compound structures in positive and negative ion modes, respectively. Then, QPSR model was further implied and identified a total of 103 HCOs, containing 35 industrial chemicals, 30 PPCPs, 26 pesticides, and 12 hormones in TW and SW, respectively. Among them, the neuroactive and hormonal compounds oxoamide, 8-iso-16-cyclohexyl-tetranor prostaglandin E2, E Keppra, and Tocris-0788 showed the highest frequency of detection, which were identified in more than 1/3 of the samples. The strategy of combining non-targeted toxicity testing and non-targeted LC-HRMS analysis will support comprehensive biological effect assessment, identification of HCOs, and risk control of mixtures.

Deep mining of reported emerging contaminants in China's surface water in the past decade: Exposure, ecological effects and risk assessment.

The identification and management of high-risk contaminants have raised great concern from governments. Facing the growing amount of data on the occurrence of emerging contaminants (ECs) in surface water, a deep mining and quality control strategy was developed to integrate data on all reported ECs in Chinese surface water over the past decade, and an exposure and effect database was further built. In addition, multilevel risk characterization was carried out to prioritize high-risk areas, contaminants and endpoints. A total of 1038 ECs, mainly pharmaceutical and personal care products (PPCPs) and industrial chemicals, were curated, with concentrations ranging from 0.02 pg/L to 533 µg/L. For individual risk, all the provinces had acceptable risks except for Henan, which was characterized with a medium chronic risk. Nine ECs, including 4-nonylphenol and estrone, dominated individual risks. Conversely, for multisubstance risk, 76.20% and 73.87% of aquatic organisms were affected acutely and chronically at the national level, with acute and chronic risks exceeding the safety threshold of 5% in 11 and 19 provinces, respectively. Nineteen ECs, including sitosterol and chyfluthrin, dominated the multisubstance risk. In addition, 9 MoAs mainly inducing electron transfer inhibition, neurotoxicity and narcosis toxicity are high-risk endpoints. The study revealed the ecological risk status and key risk entities of Chinese surface waters, which provided the latest data to support the control of ECs in China.

Identification of high-concern organic pollutants in tap waters from the Yangtze River in China based on combined screening strategies.

Recently, numerous organic pollutants have been detected in water environment. The safety of our drinking water has attracted widespread attention. Effective methods to screen and identify high-concern substances are urgently needed. In this study, the combined workflow for the detection and identification of high-concern organic chemicals was established and applied to tap water samples from the Yangtze River Basin. The solid phase extraction (SPE) sorbents were compared and evaluated and finally the HLB cartridge was selected as the best one for most of the contaminants. Based on target, suspect and non-target analysis, 3023 chemicals/peaks were detected. Thirteen substances such as diundecyl phthalate (DUP), 2-hydroxyatrazine, dioxoaminopyrine and diethyl-2-phenylacetamide were detected in drinking water in the Yangtze River Basin for the very first time. Based on three kinds of prioritization principles, 49 ubiquitous, 103 characteristic chemicals and 13 inefficiently removed chemicals were selected as high-concern substances. Among them, 8, 31, 9, 3, 4 substances overlapped with the toxic, risky or high-concern chemicals lists in China, America, European Union, Japan, Korea, respectively. Specific management and removal strategies were further recommended. The workflow is efficient for identification of key pollutants.

Identification of Glucocorticoid Receptor Antagonistic Activities and Responsible Compounds in House Dust: Bioaccessibility Should Not Be Ignored.

More and more contaminants in dust have been found to be glucocorticoid receptor (GR) disrupting chemicals. However, little is known about the related potency and responsible toxicants, especially for the main bioaccessible ones in dust. An effect-directed analysis (EDA)-based workflow was developed, including solvent-based exhaustive extraction/tenax-assisted bioaccessible extraction (TBE), high-throughput bioassays, suspect and non-target analysis, as well as in silico candidate selection, for a more realistic identification of responsible contaminants in dust. None of the 39 dust samples from 23 cities in China exhibited GR agonistic activity, while GR antagonistic potencies were detected in 34.8% of samples, being significantly different from the high detection frequency of GR agonistic activities in other environmental media. The GR antagonistic potencies of the dust samples were all reduced after bioaccessible extraction. The mean bioaccessibility of GR antagonistic potency compared with the related exhaustive extracts was 36.8%, and the lowest value was 9%. By using in silico candidate selection, greater than 99% candidate chemical structures which were found by a non-target screening strategy were removed. Di-n-butyl phthalate (DnBP), diisobutyl phthalate (DiBP), and nicotine (NIC) were responsible for the activities of the exhaustive extracts of dust, contributing up to 91% potencies. DiBP and DnBP were also responsible for the bioaccessible activities, contributing up to 79% potencies. However, the contribution from NIC decreased significantly and can be ignored because of its low bioaccessibility. This study suggests that the improved workflow combining extraction, reporter gene bioassays, suspect and non-target analysis, as well as in silico candidate selection is useful for EDA analysis in dust samples. In addition, exhaustive extraction may overestimate the risk of contaminants, while bioaccessibility evaluation based on bioaccessible extraction is essential in both effect evaluation and toxicant identification.