Suspect and non-target screening of pesticides and pharmaceuticals transformation products in wastewater using QTOF-MS.

Pesticides and pharmaceuticals are widely used in modern life and are discharged into wastewater after usage. However, a large number of transformation products (TPs) are formed through abiotic (hydrolysis/photolysis, etc.) and biotic (aerobic/anaerobic degradation by micro-organisms) wastewater treatment processes, and the structure and potential risk of TPs are still unclear. In this study, a suspect and non-target screening was performed to monitor these chemicals with HPLC-QTOF-MS. We identified 60 parent compounds by suspect screening in three Chinese wastewater treatment plants with the commercial database of pesticides and pharmaceuticals, and they were confirmed by authentic standards. Then, suspect and non-target screening strategies based on the predicted diagnostic fragment ions were used to screen TPs of the 60 parent compounds. We tentatively identified 50 TPs and confirmed thirteen of them with authentic standards. Among 13 quantified TPs, about 40% of them showed higher concentration than their parent compounds in effluent. Especially, cloquintocet, as a TP of cloquintocet-mexyl, had a concentration ratio TP/parent = 14,809 in effluent. Twenty-five TPs had higher predicted toxicity than the corresponding parent compounds by calculating their LC50 values towards aquatic organisms using toxicity prediction software. Twenty identified TPs were firstly reported in this study. These results indicate the importance of TP analysis in environmental monitoring in wastewater.

Suspect and Nontarget Screening of Per- and Polyfluoroalkyl Substances in Wastewater from a Fluorochemical Manufacturing Park.

Although per- and polyfluoroalkyl substances (PFASs) have always been a key issue in the global environmental field, there are still a lot of undiscovered PFASs in the environment due to new PFAS alternatives developed by manufacturers. Wastewater treatment plants (WWTPs), as one of the sources for PFASs, are an important part of the process of releasing new PFASs into the environment. In this study, suspect screening and PFAS homologue analysis with quadrupole time-of-flight tandem mass spectrometry were used to discover PFASs in wastewater from a WWTP near Yangtze River. Fifteen classes with 90 PFASs were identified, including 12 legacy PFASs (2 classes), 41 previously reported PFASs (7 classes), and 37 new PFASs (6 classes), and 18 of these PFASs were also detected in the nearby Yangtze River. Only 1 PFAS class was removed through the treatment processes (fold change < 1/6). Conversely, 4 PFAS classes increased through the treatment processes (fold change > 6), which could be the transformation products of PFAS precursors. These results implied that most discovered PFASs were not effectively removed in the WWTP. Chlorine-substituted perfluoroalkyl carboxylates (Cl-PFCAs) as the main component of wastewater were detected only in downstream, meaning that Cl-PFCAs in downstream possibly originated from the WWTP.

Non-Target and Suspect Screening of Per- and Polyfluoroalkyl Substances in Airborne Particulate Matter in China.

Airborne particulate matter (APM) has an important role in inhalation exposure, especially in China. The environmental occurrence of conventional and unknown per- and polyfluoroalkyl substances (PFASs) in APM remains unclear. Therefore, in this study, a two-stage experiment was designed to identify potential PFASs and to investigate their distribution in APM. Indoor and outdoor APM samples were collected from five selected cities in China. Through PFAS homologue analysis and suspect screening, 50 peaks were identified with different confidence levels (levels 1-3). Among the identified PFASs, 34 emerging PFASs including p-perfluorous nonenoxybenzenesulfonate, 6:2 polyfluoroalkyl phosphate diester, n:2 fluorotelomer sulfonates, n:2 fluorinated telomer acids, n:2 chlorinated polyfluoroalkyl ether sulfonic acids, 1:n polyfluoroalkyl ether carboxylic acids (1:n PFECAs), perfluoroalkyl dioic acids (PFdiOAs), hydro-substituted perfluoroalkyl dioic acids (H-PFdiOAs), and unsaturated perfluorinated alcohols (UPFAs) were identified in APM. In particular, 1:n PFECAs, PFdiOAs, H-PFdiOAs, and UPFAs were first detected in APM. Although human exposure to perfluorooctanoic acid via inhaled APM was noted to not be a risk (hazard quotient <0.1) in this study, the expansion of the PFASs screened in APM implies that human exposure to PFASs might be much more serious and should be considered in future risk assessments in China.