Unveiling intricate transformation pathways of emerging contaminants during wastewater treatment processes through simplified network analysis.

As the key stage for purifying wastewater, elimination of emerging contaminants (ECs) is found to be fairly low in wastewater treatment plants (WWTPs). However, less knowledge is obtained regarding the transformation pathways between various chemical structures of ECs under different treatment processes. This study unveiled the transformation pathways of ECs with different structures in 15 WWTPs distributed across China by simplified network analysis (SNA) we proposed. After treatment, the molecular weight of the whole component of wastewater decreased and the hydrophilicity increased. There are significant differences in the structure of eliminated, consistent and formed pollutants. Amino acids, peptides, and analogues (AAPAs) were detected most frequently and most removable. Benzenoids were refractory. Triazoles were often produced. The high-frequency reactions in different WWTPs were similar, (de)methylation and dehydration occurred most frequently. Different biological treatment processes performed similarly, while some advanced treatment processes differed, such as a significant increase of -13.976 (2HO reaction) paired mass distances (PMDs) in the chlorine alone process. Further, the common structural transformation was uncovered. 4 anti-hypertensive drugs, including irbesartan, valsartan, olmesartan, and losartan, were identified, along with 22 transformation products (TPs) of them. OH2 and H2O PMDs occurred most frequently and in 80.81 % of the parent-transformation product pairs, the intensity of the product was higher than parent in effluents, whose risk should be considered in future assessment activity. Together our results provide a macrography perspective on the transformation processes of ECs in WWTPs. In the future, selectively adopting wastewater treatment technology according to structures is conductive for eliminating recalcitrant ECs in WWTPs.

SWATH-F: A Novel Nontarget Strategy Based on the SWATH-MS Deconvolution Method Assisting in Annotating PFAS Homologues in Multisample Studies.

In order to identify emerging per- and polyfluoroalkyl substances (PFASs) and their alternatives in the environment or population, we need to perform extensive profiling of PFASs to determine their distribution in samples. The sequential window acquisition of all theoretical fragment-ion spectra (SWATH mode) is capable of obtaining a wide range of MS2 spectra but is difficult for direct identification of PFASs due to its complex MS2 spectra, and the nontarget screening method is difficult to identify due to its lack of a priori information. In this study, we demonstrated the great potential of SWATH-F, a nontarget fragment-based homologue screening method in combination with the SWATH-MS deconvolution, for detecting PFASs. We evaluated the application of SWATH-F to gradient spiked samples and real population serum samples, compared it with nontarget homologue screening in the information-dependent acquisition mode (IDA mode), and obtained better results for SWATH-F with 276% improvement (IDA:17 PFASs, SWATH-F: 64 PFASs) in identification. In addition, we automated the screening and identification process of SWATH-F to facilitate its use by researchers. SWATH-F is freely available on GitHub (https://github.com/njuIrene/SWATH-F) under an MIT license.

Potential effects of Ag ion on the host by changing the structure of its gut microbiota.

Silver (Ag) can change the structure of the gut microbiota (GM), but how such change may affect host health is unknown. In this study, mice were exposed to silver acetate daily for 120 days. During this period, Ag accumulation in the liver was measured, its effects on GM structure were analyzed, and potential metabolic changes in liver and serum were examined. Although Ag accumulation remained unchanged in most treatments, the ratio of Firmicutes to Bacteroidetes at the phylum level increased and changes in the relative abundance of 33 genera were detected, suggesting that Ag altered the energy metabolism of mice via changes in the gut GM. In serum and liver, 34 and 72 differentially expressed metabolites were identified, respectively. The KEGG pathways thus enriched mainly included those involving the metabolism of amino acids, organic acids, lipids, and purine. Strong correlations were found between 33 % of the microorganisms with altered relative abundances and 46 % of the differentially expressed metabolites. The resulting clusters yielded two communities responsible for host inflammation and energy metabolism. Overall, these results demonstrate potential effects of Ag on the host, by changing its GM structure, and the need to consider them when evaluating the health risk of Ag.

The occurrence, tissue distribution, and PBT potential of per- and polyfluoroalkyl substances in the freshwater organisms from the Yangtze river via nontarget analysis.

Numerous emerging per- and polyfluoroalkyl substances (PFASs) occur in the aquatic environment, posing a threat to aquatic ecosystems and human health. In this study, we conducted a nontarget analysis on 3 surface water samples and 92 tissue samples of 16 fish collected from the Yangtze River to investigate the patterns, tissue distribution, and environmental impacts of emerging PFASs. A total of 43 PFASs from 11 classes were identified, including 17 legacy PFASs and 26 emerging PFASs. Among the 43 PFASs, seven PFASs were reported in biota for the first time while five PFASs were reported in the environment for the first time. Chlorine substituted perfluoroalyl ether sulfonic acids were the major emerging PFASs detected in organisms. Our results showed that most emerging PFASs tended to accumulate in the liver whereas perfluorinated sulfonamides tended to accumulate in the blood, and all of the emerging PFASs accumulated less in the muscle. Methods for evaluating the persistence, bioaccumulation, and toxicity (PBT) of PFASs were developed by combining the in-silico methods and experimental methods. Long-chain PFASs were found to have extremely high PBT scores compared to short-chain PFASs. Additionally, most emerging PFASs exhibited comparable PBT characteristics with legacy PFASs, especially Cl-substituted PFASs.

Nontarget Discovery of Antimicrobial Transformation Products in Wastewater Based on Molecular Networks.

Antimicrobial transformation products (ATPs) in the environment have raised extensive concerns in recent years due to their potential health risks. However, only a few ATPs have been investigated, and most of the transformation pathways of antimicrobials have not been completely elucidated. In this study, we developed a nontarget screening strategy based on molecular networks to detect and identify ATPs in pharmaceutical wastewater. We identified 52 antimicrobials and 49 transformation products (TPs) with a confidence level of three or above. Thirty of the TPs had not been previously reported in the environment. We assessed whether TPs could be classified as persistent, mobile, and toxic (PMT) substances based on recent European criteria for industrial substances. Owing to poor experimental data, definitive PMT classifications could not be established for novel ATPs. PMT assessment based on structurally predictive physicochemical properties revealed that 47 TPs were potential PMT substances. These results provide evidence that novel ATPs should be the focus of future research.

Changes in Gut Microbiota Structure: A Potential Pathway for Silver Nanoparticles to Affect the Host Metabolism.

Silver nanoparticles (AgNPs) are one of the most widely used NPs. Their adverse effects on either the host or its gut microbiota (GM) have been examined. Nevertheless, whether the GM plays any role in AgNP toxicity to the host remains unclear. In the present study, AgNPs were administered to mice by oral gavage once a day for 120 days. A significant dose-dependent accumulation of Ag in the liver was observed, with a steady state reached within 21 days. The AgNPs changed the structure of the GM, mainly with respect to microorganisms involved in the metabolism of energy, amino acids, organic acids, and lipids, as predicted in a PICRUST analysis. Effects of the AgNPs on liver metabolism were also demonstrated, as a KEGG pathway analysis showed the enrichment of pathways responsible for the metabolism of amino acids, purines and pyrimidine, lipids, and energy. More interestingly, the changes in GM structure and liver metabolism were highly correlated, evidenced by the correlation between ∼23% of the differential microorganisms at the genus level and ∼60% of the differential metabolites. This implies that the metabolic variations in liver as affected by AgNPs were partly attributable to NP-induced changes of GM structure. Therefore, our results demonstrate the importance of considering the roles of GM in the toxicity of NPs to the host in evaluations of the health risks of NPs.

Comprehensive Exposure Studies of Per- and Polyfluoroalkyl Substances in the General Population: Target, Nontarget Screening, and Toxicity Prediction.

Novel per- and polyfluoroalkyl substances (PFASs) in the environment and populations have received extensive attention; however, their distribution and potential toxic effects in the general population remain unclear. Here, a comprehensive study on PFAS screening was carried out in serum samples of 202 individuals from the general population in four cities in China. A total of 165 suspected PFASs were identified using target and nontarget analysis, including seven identified PFAS homolog series, of which 16 PFASs were validated against standards, and seven PFASs [4:2 chlorinated polyfluorinated ether sulfonate (4:2 Cl-PFESA), 7:2 chlorinated polyfluorinated ether sulfonate (7:2 Cl-PFESA), hydrosubstituted perfluoroheptanoate (H-PFHpA), chlorine-substituted perfluorooctanoate (Cl-PFOA), chlorine-substituted perfluorononanate (Cl-PFNA), chlorine-substituted perfluorodecanoate (Cl-PFDA), and perfluorodecanedioic acid (PFLDCA n = 8)] were reported for the first time in human serum. The Tox21-GCN model (a graph convolutional neural network model based on the Tox21 database) was established to predict the toxicity of the discovered PFASs, revealing that PFASs containing sulfonic acid groups exhibited multiple potential toxic effects, such as estrogenic effects and stress responses. Our study indicated that the general population was exposed to various PFASs, and the toxicity prediction results of individual PFASs suggested potential health risks that could not be ignored.

Classification and identification of polar pollutants on microplastics from freshwater using nontarget screening strategy.

Microplastics (MPs) cause an increased threat to the freshwater environment by adsorbing pollutants on their large surface area. Considering their adsorption characteristics, non-polar pollutants with high distribution coefficients have been studied extensively. However, comprehensive research on the types of polar pollutants adsorbed by MPs is lacking. In this study, a nontarget screening strategy, including classification and identification, was performed to analyze the pollutants adsorbed by MPs in Tai Lake and the Yangtze River. Compared with the pollutants adsorbed or added to raw plastics, more types of polar pollutants were found on MPs from freshwater. The nontarget classification of 4723 features on MPs from freshwater and 680 features from raw plastics were annotated based on the mass spectrometry spectra. Further identification with multiple platforms identified hundreds of pollutants absorbed by MPs in Tai Lake and Yangtze River, including industrial intermediates, medicines, and surfactants, exceeding those adsorbed by raw plastics, showing an enrichment of the pollutants on MPs in freshwater by secondary adsorption. Our study is the first to use nontarget analysis to comprehensively demonstrate MP adsorption and release of pollutants in freshwater environment, providing a significant reference for the research of MPs and the management of the water environment.

[Nontarget Screening and Ecological Risk Assessment of Polar Organic Pollutants in Surface Water on the West Bank of Taihu Lake].

Emerging pollutants occur in the environment, which has become a pressing issue for environmental research. In order to comprehensively screen potential polar organic pollutants in surface water of Wujin and Yixing in the Taihu Lake Basin, nontarget screening was carried out by high performance liquid chromatography(HPLC) and time of flight mass spectrometry(TOF-MS). Screened by accurate mass, isotope distribution, and MS/MS information, 162 organic compounds were identified, including 46 pesticides, 34 drugs, 8 personal care products, and 27 additives; 17 organic synthetic intermediates and 30 metabolites, 45 of which have been verified by reference standards. Through the quantitative analysis of 42 pollutants and ecological risk assessment of 3 trophic model species, it was found that 25 pollutants posed medium risk while 12 pollutants presented high risk. Nontarget screening can be used to identify potential pollutants with no prior information or standards. It is not only fast, accurate, and has high analytical flux, but also provides an important basis for subsequent ecological risk assessment.

Exposure to legacy and novel perfluoroalkyl substance disturbs the metabolic homeostasis in pregnant women and fetuses: A metabolome-wide association study.

BACKGROUND: Perfluoroalkyl substances (PFASs) exist extensively and several of these have been verified to be toxic. Prenatal exposure to PFASs has attracted much attention. Metabolome-wide association analyses can be used to explore the toxicity mechanisms of PFASs by identifying associated biomarkers. OBJECTIVES: To evaluate associations between the metabolites in maternal and cord serum and internal exposure to several common PFASs. METHODS: Paired maternal and cord serum samples were collected from 84 pregnant women who gave birth between 2015 and 2016. Seven legacy and two novel PFASs were measured. A nontarget metabolomic method and an iterative metabolite annotation based on metabolic pathways were applied to characterize the metabolic profiles. Linear regression adjusted with the false discovery rate and covariates was used to indicate the associations. RESULTS: A total of 279 features in maternal serum and 338 features in cord serum were identified as metabolites associated with PFAS exposure. Perfluorooctanoic acid (PFOA) and perfluorohexane sulfonic acid (PFHxS) were two PFASs associated with more metabolites, while the two novel chlorinated polyfluorinated ether sulfonic acids (Cl-PFESAs) showed less relevance to the metabolome. With pathway enrichment analysis, we found that three fatty acid metabolisms and retinol metabolism were correlated with PFAS exposure in maternal blood, and that sterol metabolism showed the correlation in both maternal serum and cord serum. CONCLUSIONS: We identified metabolites and pathways in pregnant women and fetuses associated with the exposure to several PFAS, indicating a promising application for metabolome-wide association studies. Additional research is needed to confirm causation.

[Pollution Characteristics and Risk Assessment of Nitro Polycyclic Aromatic Hydrocarbons in PM2.5 of Nanjing, China].

Nitro polycyclic aromatic hydrocarbons (NPAHs) are important pollutants with carcinogenic effects present in PM2.5. To analyze the pollution characteristics and sources of NPAHs, 14 samples of PM2.5 were collected in Nanjing from November 2017 to March 2018. The results showed that, 2,8-dinitrodibenzothiophene (743 pg·m-3), 2, 7-dinitrofluorene (331 pg·m-3), 9-nitroanthracene (326 pg·m-3), 3-nitrofluoranthene (217 pg·m-3), and 1,8-dinitropyrene (193 pg·m-3) were dominant, and the detection concentrations notably varied between seasons; the highest concentrations occurred in winter (3082 pg·m-3) followed by autumn (1553 pg·m-3) and spring (1218 pg·m-3). The ratio of nitrofluoranthene and 1-nitropyrene concentrations, and 9-nitroanthracene and 1-nitropyrene concentrations, indicated that the main sources of NPAHs in the PM2.5 of Nanjing were photooxidation of polycyclic aromatic hydrocarbons and biomass burning. NPAHs were more typically associated with smaller particles, which further indicated that secondary formation is an important source. The current carcinogenic risk of NPAHs in PM2.5 in Nanjing is controllable, and dinitro-polycyclic aromatic hydrocarbons represent the highest level of risk. The data presented in this study provide important baseline information that can inform the management of risks associated with NPAHs in PM2.5 in Nanjing.

Screening priority indicator pollutants in full-scale wastewater treatment plants by non-target analysis.

Wastewater treatment plants (WWTPs) are the main sources of emerging contaminants (ECs) in aquatic environment. However, the standards for limiting emerging pollutants in effluent are extremely lacking. We investigated the occurrence and removal of emerging pollutants in 16 WWTPs in China using non-target analysis. 568 substances screened out were divided into 9 kinds including 167 pharmaceuticals, 113 natural substances, 85 pesticides, 86 endogenous substances, 64 chemical raw materials, 14 personal care products, 17 food additives, 6 hormones and 16 others. And they were divided into 5 fates. Pesticides and pharmaceutical compounds seemed to be the most notable categories, the kinds detected in each sample is the largest compared with other compounds. Besides, the average removal rate of pesticides and pharmaceuticals in all WWTPs were the lowest, at 9.54% and 23.77%, respectively. Priority pollutants were screened by considering distribution of pollutants with different fates. Pollutants with the same fate especially "consistent" in different WWTPs had attracted attention. 4 potential priority pollutants including metoprolol, carbamazepine, 10, 11-dihydro-10, 11-dihydroxycarbamazepine and irbesartan were proposed. And it was found that the 4 compounds, "consistent suspects" and "consistent non-targets" had similar rankings of removal rate in 16 WWTPs, which can reflect the performance of different WWTPs.

Photodegradation of carbon dots cause cytotoxicity.

Carbon dots (CDs) are photoluminescent nanomaterials with wide-ranging applications. Despite their photoactivity, it remains unknown whether CDs degrade under illumination and whether such photodegradation poses any cytotoxic effects. Here, we show laboratory-synthesized CDs irradiated with light degrade into molecules that are toxic to both normal (HEK-293) and cancerous (HeLa and HepG2) human cells. Eight days of irradiation photolyzes 28.6-59.8% of the CDs to <3 kilo Dalton molecules, 1431 of which are detected by high-throughput, non-target high-performance liquid chromatography-quadrupole time-of-flight mass spectrometry. Molecular network and community analysis further reveal 499 cytotoxicity-related molecules, 212 of which contain polyethylene glycol, glucose, or benzene-related structures. Photo-induced production of hydroxyl and alkyl radicals play important roles in CD degradation as affected by temperature, pH, light intensity and wavelength. Commercial CDs show similar photodegraded products and cytotoxicity profiles, demonstrating that photodegradation-induced cytotoxicity is likely common to CDs regardless of their chemical composition. Our results highlight the importance of light in cytocompatibility studies of CDs.

Non-target and suspect screening of per- and polyfluoroalkyl substances in Chinese municipal wastewater treatment plants.

Wastewater treatment plant (WWTP) is one of the major sources of per- and polyfluoroalkyl substances (PFASs) to the aquatic environment. In this study, wastewater samples were collected from 17 WWTPs in 17 cities of China to investigate emerging PFASs in WWTPs. To comprehensively identify PFASs in the wastewater samples, an integrated suspect screening, homologue-based and fragment-based non-target screening method is proposed. Sixty-three PFASs from 13 classes (25 subclasses) were identified, including 14 legacy and 49 emerging PFASs, and this study is the first to report on 12 of these PFASs. We found that emerging PFASs concentration had a significantly positive correlation with the gross domestic product, indicating more substitution of legacy PFASs in the developed area of China. We also analyzed the removal of the 13 PFAS classes, and found that all discovered PFAS classes were not completely removed after the treatment process, whereas the class of perfluoroalkyl ether alcohols significantly increased. All of these results imply that the release of emerging or unknown PFASs from WWTPs is a universal but not negligible problem in China.

Suspect screening and risk assessment of pollutants in the wastewater from a chemical industry park in China.

Owing to the production and use of chemicals in chemical industry parks (CIPs), these areas are considered to be highly polluted. However, the type of pollutants presents in the wastewater from CIPs and the risk posed to the environment due to the release of these pollutants remains unclear. In this study, suspect screening was combined with traceability analysis to determine the type of pollutants present in wastewaters at 9 chemical enterprises and wastewater treatment plants (WWTPs) in the CIPs. Additionally, the distribution of nine pollutants from the WWTPs' effluent stage and the risk they posed to the surrounding river was examined through target analysis. Upon conducting suspect analysis, the presence of 65 and 64 chemicals in the 9 chemical enterprises' wastewaters and WWTPs, respectively, was tentatively identified. Traceability analysis of the compounds screened in the effluent from the WWTPs determined that 41 substances were identified as characteristic pollutants of the chemical enterprises, indicating that the suspect screening strategy enabled relatively more efficient identification of the characteristic pollutants compared to traditional quantitative analysis. Targeting analysis combined with ecological risk assessment showed that metolachlor, carbendazim, atrazine, diuron, and chlorpyrifos posed relatively higher risks to aquatic organisms in the surrounding river. Therefore, the refined management of the wastewater treatment plant in the CIPs is necessary.

Metabolomic insights into the lasting impacts of early-life exposure to BDE-47 in mice.

Early-life exposure to toxicants may have lasting effects that adversely impact later development. Thus, although the production and use of a toxicant have been banned, the risk to previously exposed individuals may continue. BDE-47, a component of commercial penta-BDEs, is a persistent organic pollutant with demonstrated neurotoxicity. To investigate the persistent effects of BDE-47 and the mechanisms thereof, we employed a metabolomics approach to analyze the brain, blood and urine of mice exposed to BDE-47 for 28 days and then 3 months post-exposure. In the brain, BDE-47 was detectable just after exposure but was below the limit of detection (LOD) 3 months later. However, the metabolomic alterations caused by early-life exposure to BDE-47 persisted. Potential biomarkers related to these alterations included phosphatidylcholine, lysophosphatidylcholine, sphingomyelin and several amino acids and biogenic amines. The metabolic pathways involved in the response to BDE-47 in the brain were mainly those related to glycerophospholipid metabolism, sphingomyelin metabolism and neurotransmitter regulation. Thus, our study demonstrates the utility of metabolomics, as the omics most closely reflecting the phenotype, in exploring the mechanisms underlying the lasting effects induced by early-life BDE-47 exposure.

Nontarget Discovery of Per- and Polyfluoroalkyl Substances in Atmospheric Particulate Matter and Gaseous Phase Using Cryogenic Air Sampler.

Novel per- and polyfluoroalkyl substances (PFASs) have become a key issue in global environmental studies. Although several novel PFASs have been discovered in atmospheric particulate matter through nontarget analysis, information on the environmental occurrence of novel PFASs in atmospheric gaseous phases and conventional sampling techniques is somewhat deficient. Therefore, this Article describes a new type of air sampler, the cryogenic air sampler (CAS), which was used to collect all atmospheric components simultaneously. Nontarget analysis then was performed through PFASs homologue analysis. A total of 117 PFAS homologues (38 classes) were discovered, 48 of which (13 classes) were identified with confidence Level 4 or above. Eleven chlorinated perfluoropolyether alcohols (3 classes) and four chlorinated perfluoropolyether carboxylic acids (2 classes) have been reported for the first time in this Article. This Article is also the first report of 12 hydrosubstituted perfluoroalkyl carboxylates (H-PFCAs) in the atmosphere. H-PFCAs and chlorinated perfluoropolyether carboxylic acids were mainly distributed in the particular phase. These results are evidence that novel chlorinated polyether PFASs should be the focus of future study.

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.

Transplacental Transfer of Per- and Polyfluoroalkyl Substances Identified in Paired Maternal and Cord Sera Using Suspect and Nontarget Screening.

Novel per- and polyfluoroalkyl substances (PFASs) in various environmental media have attracted increasing attention; however, the information regarding PFASs exposure in pregnant women and fetuses is insufficient. In this study, we built and applied suspect and nontarget screening strategies based on the mass difference of the CF2, CF2O, and CH2CF2 units to select potential novel PFASs from 117 paired maternal and cord sera. In total, 10 legacy PFASs and 19 novel PFASs from 10 classes were identified to be above confidence levels 3, among which 14 were not previously reported in human serum. Novel PFASs accounted for a considerable percentage of total PFASs in pregnant women and can be transferred to fetuses at non-negligible concentrations (i.e., 27.9% and 30.3% of total PFAS intensities in maternal and cord sera, respectively). The transplacental transfer efficiency (TTE) of PFASs showed a U-shape trend in the series of perfluoroalkyl carboxylic acids, perfluoroalkyl sulfonic acids, and unsaturated perfluorinated alcohols. The TTE of novel PFASs is suggested to be structure-dependent, based on a flexible docking experiment. This study provides comprehensive TTE information on legacy and novel PFASs for the first time, and additional toxicity studies are needed to evaluate the risk of novel PFASs further.