De facto Water Reuse: Investigating the Fate and Transport of Chemicals of Emerging Concern from Wastewater Discharge through Drinking Water Treatment Using Non-targeted Analysis and Suspect Screening.

Wastewater is a source for many contaminants of emerging concern (CECs), and surface waters receiving wastewater discharge often serve as source water for downstream drinking water treatment plants. Nontargeted analysis and suspect screening methods were used to characterize chemicals in residence-time-weighted grab samples and companion polar organic chemical integrative samplers (POCIS) collected on three separate hydrologic sampling events along a surface water flow path representative of de facto water reuse. The goal of this work was to examine the fate of CECs along the study flow path as water is transported from wastewater effluent through drinking water treatment. Grab and POCIS samples provided a comparison between residence-time-weighted single-point and integrative sample results. This unique and rigorous study design, coupled with advanced analytical chemistry tools, provided important insights into chemicals found in drinking water and their potential sources, which can be used to help prioritize chemicals for further study. K-means clustering analysis was used to identify patterns in chemical occurrences across both sampling sites and sampling events. Chemical features that occurred frequently or survived drinking water treatment were prioritized for identification, resulting in the probable identification of over 100 CECs in the watershed and 28 CECs in treated drinking water.

Comprehensive assessment of chemical residues in surface and wastewater using passive sampling, chemical, biological, and fish behavioral assays.

Effluents from ten full-scale municipal wastewater treatment plants (WWTPs) that discharge into the Hudson River, surface waters, and wild-caught fish samples were analyzed using liquid chromatography with tandem mass spectrometry (LC/MS/MS) to examine the influence of wastewater discharge on the concentrations of contaminants of emerging concern (CECs) and their ecological impacts on fish. Analysis was based on targeted detection of 41 pharmaceuticals, and non-targeted analysis (suspect screening) of CECs. Biological effects of treated WWTP effluents were assessed using a larval zebrafish (Danio rerio) swimming behavior assay. Concentrations of residues in surface waters were determined in grab samples and polar organic chemical integrative samplers (POCIS). In addition, vitellogenin peptides, used as biomarkers of endocrine disruption, were quantified using LC/MS/MS in the wild-caught fish plasma samples. Overall, 94 chemical residues were identified, including 63 pharmaceuticals, 10 industrial chemicals, and 21 pesticides. Eight targeted pharmaceuticals were detected in 100% of effluent samples with median detections of: bupropion (194 ng/L), carbamazepine (91 ng/L), ciprofloxacin (190 ng/L), citalopram (172 ng/L), desvenlafaxine (667 ng/L), iopamidol (3790 ng/L), primidone (86 ng/L), and venlafaxine (231 ng/L). Over 30 chemical residues were detected in wild-caught fish tissues. Notably, zebrafish larvae exposed to chemical extracts of effluents from 9 of 10 WWTPs, in at least one season, were significantly hyperactive. Vitellogenin expression in male or immature fish occurred 2.8 times more frequently in fish collected from the Hudson River as compared to a reference site receiving no direct effluent input. Due to the low concentrations of pharmaceuticals detected in effluents, it is likely that chemicals other than pharmaceuticals measured are responsible for the behavioral changes observed. The combined use of POCIS and non-target analysis demonstrated significant increase in the chemical coverage for CEC detection, providing a better insight on the impacts of WWTP effluents and agricultural practices on surface water quality.

Increasing accuracy of field-scale studies to investigate plant uptake and soil dissipation of pharmaceuticals.

Pharmaceuticals and personal care products (PPCPs) can enter agricultural fields through wastewater irrigation, biosolid amendments, or urine fertilization. Numerous studies have assessed the risk of PPCP contamination, however there are no standardized methodologies for sample treatment, making the interpretation of results challenging. Various time periods between sampling and analysis have been reported (shipping, storage, etc.), but literature is lacking in the evaluation of PPCP degradation amidst this process. This study assessed the stability of 20 pharmaceuticals (200 µg L-1) in soil and crops stored at -40 °C for 7, 30, and 310 days. After 310 days, caffeine, meprobamate, trimethoprim, primidone, carbamazepine, anhydro-erythromycin and dilantin were found to be stable (≥75% recovery) in all matrices. On the other hand, acetaminophen, amitriptyline, bupropion, lamotrigine, sulfamethoxazole, naproxen, ibuprofen, and paroxetine were unstable after 30 days in at least one of the matrices investigated. Due to variations in analyte stability, fortification with isotopically-labelled surrogates at the point of sample collection was evaluated in comparison to fortification after shipment and storage, immediately prior to extraction. Chromatographic peak areas of stable analytes were found to be reproducible (±15%) in field-fortified samples, indicating that no additional error occurred during sample handling under field conditions despite having a less controlled environment. Unstable analytes revealed notable differences in peak areas between fortification times, suggesting that fortification immediately after sample collection is crucial to account for analyte losses during shipping and storage, resulting in accurate quantification of PPCPs.