Non-negligible Toxicity to Fish in the Early Life Stages Triggered by Aqueous Leachate of Takeaway Plastic Containers.

Ordering takeout is a growing social phenomenon and may raise public health concerns. However, the associated health risk of compounds leaching from plastic packaging is unknown due to the lack of chemical and toxicity data. In this study, 20 chemical candidates were tentatively identified in the environmentally relevant leachate from plastic containers through the nontargeted chemical analysis. Three main components with high responses and/or predicted toxicity were further verified and quantified, namely, 3,5-di-tert-butyl-4-hydroxycinnamic acid (BHC), 2,4-di-tert-butylphenol (2,4-DTBP), and 9-octadecenamide (oleamide). The toxicity to zebrafish larvae of BHC, a degradation product of a widely used antioxidant Irganox 1010, was quite similar to that of the whole plastic leachate. In the same manner, RNA-seq-based ingenuity analysis showed that the affected canonical pathways of zebrafish larvae were quite comparable between BHC and the whole plastic leachate, i.e., highly relevant to neurological disease, metabolic disease, and even behavioral disorder. Longer-term exposure (35 days) did not cause any effect on adult zebrafish but led to decreased hatching rate and obvious neurotoxicity in zebrafish offspring. Collectively, this study strongly suggests that plastic containers can leach out a suite of compounds causing non-negligible impacts on the early stages of fish via direct or parental exposure.

Refinement of kinetic model and understanding the role of dichloride radical (Cl2•-) in radical transformation in the UV/NH2Cl process.

The ultraviolet/monochloramine (UV/NH2Cl) process is an emerging advanced oxidation process with promising prospects in water treatment. Previous studies developed kinetic models of UV/NH2Cl for simulating radical concentrations and pollutant degradation. However, the reaction rate constants of Cl2•- with bicarbonate and carbonate (kCl2•-, HCO3- and kCl2•-, CO32-) were overestimated in literature. Consequently, when dosing 1 mM chloride and 1 mM bicarbonate, the current models of UV/NH2Cl severely under-predicted the experimental concentrations of three important radicals (i.e., hydroxyl radical (HO•), chlorine radical (Cl•), and dichloride radical (Cl2•-)) with great deviations (> 90 %). To investigate this issue, the transformation reactions among these three radicals in UV/NH2Cl were systematically studied. For the first time, it was found that in addition to Cl•, Cl2•- was also an important parent radical of HO• in the presence of chloride, and chloride could effectively compensate the inhibitory effect of bicarbonate on HO• generation in the system. Moreover, reactions and rate constants in current models were scrutinized from corresponding literature, and the reaction rate constants of Cl2•- with bicarbonate and carbonate (kCl2•-, HCO3- and kCl2•-, CO32-) were reevaluated to be 1.47 × 105 and 3.78 × 106 M-1s-1, respectively, by laser flash photolysis. With the newly obtained rate constants, the refined model could accurately simulate concentrations of all three radicals under different chloride and bicarbonate dosages with satisfactory deviations (< 30 %). Meanwhile, the refined model performed much better in predicting pollutant degradation and radical contribution compared with the unrefined model (with the previously estimated kCl2•-, HCO3- and kCl2•-, CO32-). The results of this study enhanced the accuracy and applicability of the kinetic model of UV/NH2Cl, and deepened the understanding of radical transformation in the process.

Urine biomarkers for Alzheimer's disease: A new opportunity for wastewater-based epidemiology?

While Alzheimer's disease (AD) diagnosis, management, and care have become priorities for healthcare providers and researcher's worldwide due to rapid population aging, epidemiologic surveillance efforts are currently limited by costly, invasive diagnostic procedures, particularly in low to middle income countries (LMIC). In recent years, wastewater-based epidemiology (WBE) has emerged as a promising tool for public health assessment through detection and quantification of specific biomarkers in wastewater, but applications for non-infectious diseases such as AD remain limited. This early review seeks to summarize AD-related biomarkers and urine and other peripheral biofluids and discuss their potential integration to WBE platforms to guide the first prospective efforts in the field. Promising results have been reported in clinical settings, indicating the potential of amyloid ß, tau, neural thread protein, long non-coding RNAs, oxidative stress markers and other dysregulated metabolites for AD diagnosis, but questions regarding their concentration and stability in wastewater and the correlation between clinical levels and sewage circulation must be addressed in future studies before comprehensive WBE systems can be developed.

High-Throughput Transcriptomics of Water Extracts Detects Reductions in Biological Activity with Water Treatment Processes.

The presence of numerous chemical contaminants from industrial, agricultural, and pharmaceutical sources in water supplies poses a potential risk to human and ecological health. Current chemical analyses suffer from limitations, including chemical coverage and high cost, and broad-coverage in vitro assays such as transcriptomics may further improve water quality monitoring by assessing a large range of possible effects. Here, we used high-throughput transcriptomics to assess the activity induced by field-derived water extracts in MCF7 breast carcinoma cells. Wastewater and surface water extracts induced the largest changes in expression among cell proliferation-related genes and neurological, estrogenic, and antibiotic pathways, whereas drinking and reclaimed water extracts that underwent advanced treatment showed substantially reduced bioactivity on both gene and pathway levels. Importantly, reclaimed water extracts induced fewer changes in gene expression than laboratory blanks, which reinforces previous conclusions based on targeted assays and improves confidence in bioassay-based monitoring of water quality.

Formation of halogenated forms of bisphenol A (BPA) in water: Resolving isomers with ion mobility - mass spectrometry and the role of halogenation position in cellular toxicity.

Halogenated BPA (XBPA) forms resulting from water chlorination can lead to increased toxicity and different biological effects. While previous studies have reported the occurrence of different XBPAs, analytical limitation have hindered the analysis and differentiation of the many potential isomeric forms. Using online solid-phase extraction - liquid chromatography - ion-mobility - high-resolution mass spectrometry (OSPE-LC-IM-HRMS), we demonstrated a rapid analysis method for the analysis of XBPA forms after water chlorination, with a total analysis time of less than 10 min including extraction and concentration and low detection limits (∼5-80 ng/L range). A multi in-vitro bioassay testing approach for the identified products revealed that cytotoxicity and bioenergetics impacts were largely associated with the presence of halogen atoms at positions 2 or 2' and the overall number of halogens incorporated into the BPA molecule. Different XBPA also showed distinct impacts on oxidative stress, peroxisome proliferator-activated receptor gamma - PPARγ, and inflammatory response. While increased DNA damage was observed for chlorinated water samples (4.14 ± 1.21-fold change), the additive effect of the selected 20 XBPA studied could not explain the increased DNA damage observed, indicating that additional species or synergistic effects might be at play.

Evaluation of wastewater-based epidemiology of COVID-19 approaches in Singapore's 'closed-system' scenario: A long-term country-wide assessment.

With the COVID-19 pandemic the use of WBE to track diseases spread has rapidly evolved into a widely applied strategy worldwide. However, many of the current studies lack the necessary systematic approach and supporting quality of epidemiological data to fully evaluate the effectiveness and usefulness of such methods. Use of WBE in a very low disease prevalence setting and for long-term monitoring has yet to be validated and it is critical for its intended use as an early warning system. In this study we seek to evaluate the sensitivity of WBE approaches under low prevalence of disease and ability to provide early warning. Two monitoring scenarios were used: (i) city wide monitoring (population 5,700,000) and (ii) community/localized monitoring (population 24,000 to 240,000). Prediction of active cases by WBE using multiple linear regression shows that a multiplexed qPCR approach with three gene targets has a significant advantage over single-gene monitoring approaches, with R2 = 0.832 (RMSE 0.053) for an analysis using N, ORF1ab and S genes (R2 = 0.677 to 0.793 for single gene strategies). A predicted disease prevalence of 0.001% (1 in 100,000) for a city-wide monitoring was estimated by the multiplexed RT-qPCR approach and was corroborated by epidemiological data evidence in three 'waves'. Localized monitoring setting shows an estimated detectable disease prevalence of ∼0.002% (1 in 56,000) and is supported by the geospatial distribution of active cases and local population dynamics data. Data analysis also shows that this approach has a limitation in sensitivity, or hit rate, of 62.5 % and an associated high miss rate (false negative rate) of 37.5 % when compared to available epidemiological data. Nevertheless, our study shows that, with enough sampling resolution, WBE at a community level can achieve high precision and accuracies for case detection (96 % and 95 %, respectively) with low false omission rate (4.5 %) even at low disease prevalence levels.

Asthma-protective agents in dust from traditional farm environments.

BACKGROUND: Growing up on traditional European or US Amish dairy farms in close contact with cows and hay protects children against asthma, and airway administration of extracts from dust collected from cowsheds of those farms prevents allergic asthma in mice. OBJECTIVES: This study sought to begin identifying farm-derived asthma-protective agents. METHODS: Our work unfolded along 2 unbiased and independent but complementary discovery paths. Dust extracts (DEs) from protective and nonprotective farms (European and Amish cowsheds vs European sheep sheds) were analyzed by comparative nuclear magnetic resonance profiling and differential proteomics. Bioactivity-guided size fractionation focused on protective Amish cowshed DEs. Multiple in vitro and in vivo functional assays were used in both paths. Some of the proteins thus identified were characterized by in-solution and in-gel sodium dodecyl sulfate-polyacrylamide gel electrophoresis enzymatic digestion/peptide mapping followed by liquid chromatography/mass spectrometry. The cargo carried by these proteins was analyzed by untargeted liquid chromatography-high-resolution mass spectrometry. RESULTS: Twelve carrier proteins of animal and plant origin, including the bovine lipocalins Bos d 2 and odorant binding protein, were enriched in DEs from protective European cowsheds. A potent asthma-protective fraction of Amish cowshed DEs (≈0.5% of the total carbon content of unfractionated extracts) contained 7 animal and plant proteins, including Bos d 2 and odorant binding protein loaded with fatty acid metabolites from plants, bacteria, and fungi. CONCLUSIONS: Animals and plants from traditional farms produce proteins that transport hydrophobic microbial and plant metabolites. When delivered to mucosal surfaces, these agents might regulate airway responses.

Analogy or fallacy, unsafe chemical alternatives: Mechanistic insights into energy metabolism dysfunction induced by Bisphenol analogs in HepG2 cells.

Bisphenol analogs (BPs) are widely used as industrial alternatives for Bisphenol A (BPA). Their toxicity assessment in humans has mainly focused on estrogenic activity, while other toxicity effects and mechanisms resulting from BPs exposure remain unclear. In this study, we investigated the effects of three BPs (Bisphenol AF (BPAF), Bisphenol G (BPG) and Bisphenol PH (BPPH)) on metabolic pathways of HepG2 cells. Results from comprehensive cellular bioenergetics analysis and nontarget metabolomics indicated that the most important process affected by BPs exposure was energy metabolism, as evidenced by reduced mitochondrial function and enhanced glycolysis. Compared to the control group, BPG and BPPH exhibited a consistent pattern of metabolic dysregulation, while BPAF differed from both, such as an increased ATP: ADP ratio (1.29-fold, p < 0.05) observed in BPAF and significantly decreased ATP: ADP ratio for BPG (0.28-fold, p < 0.001) and BPPH (0.45-fold, p < 0.001). Bioassay endpoint analysis revealed BPG/BPPH induced alterations in mitochondrial membrane potential and overproductions of reactive oxygen species. Taken together these data suggested that BPG/BPPH induced oxidative stress and mitochondrial damage in cells results in energy metabolism dysregulation. By contrast, BPAF had no effect on mitochondrial health, but induced a proliferation promoting effect on cells, which might contribute to the energy metabolism dysfunction. Interestingly, BPPH induced the greatest mitochondrial damage among the three BPs but did not exhibit Estrogen receptor alpha (ERα) activating effects. This study characterized the distinct metabolic mechanisms underlying energy metabolism dysregulation induced by different BPs in target human cells, providing new insight into the evaluation of the emerging BPA substitutes.

Liquid Crystal Monomer: A Potential PPARγ Antagonist.

Liquid crystal monomers (LCMs) are a large family of artificial ingredients that have been widely used in global liquid crystal display (LCD) industries. As a major constituent in LCDs as well as the end products of e-waste dismantling, LCMs are of growing research interest with regard to their environmental occurrences and biochemical consequences. Many studies have analyzed LCMs in multiple environmental matrices, yet limited research has investigated the toxic effects upon exposure to them. In this study, we combined in silico simulation and in vitro assay validation along with omics integration analysis to achieve a comprehensive toxicity elucidation as well as a systematic mechanism interpretation of LCMs for the first time. Briefly, the high-throughput virtual screen and reporter gene assay revealed that peroxisome proliferator-activated receptor gamma (PPARγ) was significantly antagonized by certain LCMs. Besides, LCMs induced global metabolome and transcriptome dysregulation in HK2 cells. Notably, fatty acid ß-oxidation was conspicuously dysregulated, which might be mediated through multiple pathways (IL-17, TNF, and NF-kB), whereas the activation of AMPK and ligand-dependent PPARγ antagonism may play particularly important parts. This study illustrated LCMs as a potential PPARγ antagonist and explored their toxicological mode of action on the trans-omics level, which provided an insightful overview in future chemical risk assessment.

UV/chlorine and chlorination of effluent organic matter fractions: Tracing nitrogenous DBPs using FT-ICR mass spectrometry.

UV/chlorine process is a promising advanced treatment to eliminate pathogen and remove refractory micropollutants for reclamation of municipal secondary effluent. However, effluent organic matter (EfOM) featuring high organic nitrogen content serves as a potential precursor for nitrogenous disinfection byproducts (N-DBPs) of health concern. The molecular-level alteration of a hydrophobic (HPO) EfOM fraction and a transphilic (TPI) EfOM fraction isolated from the same municipal effluent and the formation of N-DBPs in the UV/chlorine were tracked by ultrahigh-resolution mass spectrometry. Compared with chlorination, UV/chlorine induced a significantly greater modification on the molecular composition of EfOM and resulted in formation of unique formulae and chlorinated molecules with higher degree of oxidation, lower aromaticity, and less carbon number due to the involvement of reactive radical species. For both EfOM fractions, UV/chlorine formed more diverse DBPs with higher intensity and Cl-incorporation than chlorination. The TPI fraction of EfOM characterized by higher O/C and N/C ratios generated more N-DBPs with higher intensity clustered in the high O/C region than the HPO fraction of EfOM by both UV/chlorine and chlorination. Totally, 207 and 117 nitrogen-containing chlorinated formulae were recorded after UV/chlorine treatment of TPI and HPO, respectively. Precursor tracking found a greater number of DBPs were originated from raw EfOM through electrophilic substitution pathway rather than chlorine addition. Toxicity bioassays demonstrated that DBPs can trigger oxidative stress-induced DNA damage, while HPO fraction of EfOM dominated the induction of cytotoxicity. However, no correlation could be established between the diversity/abundance of N-DBPs and the level of DNA damage. A total of 22 DBPs with a significant rank correlation with DNA damage were identified, while C8H6O5NCl was found as the N-DBP with the strongest correlation. The potential toxic chlorine-containing formula with the most abundant intensity was assigned to C5HO3Cl3. This study suggests that the character and transformation of EfOM and associated toxicity is critical to evaluate the UV/chlorine process toward practical application.

Adsorption kinetics of 20 glucocorticoids at environmentally relevant concentrations in wastewater by powdered activated carbons and development of surrogate models.

Glucocorticoids (GCs) are widely used in the treatment of the coronavirus disease of 2019 (COVID-19), and the toxicity of GCs to aquatic organisms has aroused widespread concern. Powdered activated carbon (PAC) has proven effective in removing various trace organic pollutants. In this study, the adsorption behaviors of 20 typical GCs onto PACs were investigated at environmentally relevant concentrations (ng/L) in real wastewater, using four commercially available PACs (HDB, WPH, 20BF, PWA). The results showed that PAC adsorption was feasible for GC removal at ng/L concentrations. After adsorption for 60 min, the GC removal efficiencies obtained by HDB, WPH, 20BF, and PWA were 90-98 %, 89-97 %, 84-96 %, and 71-90 %, respectively. The adsorption processes of 20 GCs on PACs were well fitted by the pseudo-second-order kinetics model (with R 2 >0.98). Among the four PACs, HDB achieved the highest rates because of the electrostatic attraction between HDB (positively charged) and the complex of GCs and natural organic matter (GC-NOM, negatively charged). Among the 20 GCs, compounds with substitutions of halogen atoms or five-membered rings at C-17 achieved higher adsorption rates because of the enhanced formation of hydrogen bonds and a resulting increase in electron density. In addition, surrogate models with total fluorescence (TF) and ultraviolet absorbance at 254 nm (UV254) were developed to monitor the attenuation trend of GCs during adsorption processes. Compared with the UV254 model, the TF model showed better sensitivity to GC monitoring, which could greatly simplify the water quality monitoring process and facilitate online monitoring of GCs in water.

Cell-line and culture model specific responses to organic contaminants in house dust: Cell bioenergetics, oxidative stress, and inflammation endpoints.

Exposure to organic contaminants in house dust is linked to the development or exacerbation of many allergic and immune disorders. In this work, we evaluate the effects of organic contaminants on different cell bioenergetics endpoints using five different cell lines (16HBE14o-, NuLi-1, A549, THP-1 and HepG2), and examine its effects on lung epithelial cells using conventional 2D and 3D (air-liquid interface/ALI) models. Proposed rapid bioenergetic assays relies on a quick, 40 min, exposure protocol that provides equivalent dose-response curves for ATP production, spare respiratory capacity, and cell respiration. Although cell-line differences play an important role in assay performance, established EC50 concentrations for immortalized lung epithelial cells ranged from 0.11 to 0.15 mg/mL (∼2 µg of dust in a 96-well microplate format). Bioenergetic response of distinct cell types (i.e., monocytes and hepatocytes) was significantly different from epithelial cells; with HepG2 showing metabolic activity that might adversely affect results in 24 h exposure experiments. Like in cell bioenergetics, cell barrier function assay in ALI showed a dose dependent response. Although this is a physiologically relevant model, measurements are not as sensitivity as cytokine profiling and reactive oxygen species (ROS) assays. Observed effects are not solely explained by exposure to individual contaminants, this suggests that many causal agents responsible for adverse effects are still unknown. While 16HBE14o- cells show batter barrier formation characteristics, NuLi-1 cells are more sensitivity to oxidative stress induction even at low house dust extract concentrations, (NuLi-1 2.11-fold-change vs. 16HBE14o- 1.36-fold change) at 0.06 µg/mL. Results show that immortalized cell lines can be a suitable alternative to primary cells or other testing models, especially in the development of high-throughput assays. Observed cell line specific responses with different biomarker also highlights the importance of careful in-vitro model selection and potential drawbacks in risk assessment studies.

Genotoxic effects of chlorinated disinfection by-products of 1,3-diphenylguanidine (DPG): Cell-based in-vitro testing and formation potential during water disinfection.

1,3-diphenylguanidine (DPG) is a commonly used rubber and polymer additive, that has been found to be one of the main leachate products of tire wear particles and from HDPE pipes. Its introduction to aquatic environments and potentially water supplies lead to further questions regarding the effects of disinfection by-products potentially formed. Using different bioassay approaches and NGS RNA-sequencing, we show that some of the chlorinated by-products of DPG exert significant toxicity. DPG and its chlorinated by-products also can alter cell bioenergetic processes, affecting cellular basal respiration rates and ATP production, moreover, DPG and its two chlorination products, 1,3-bis-(4-chlorophenyl)guanidine (CC04) and 1-(4-chlorophenyl)-3-(2,4-dichlorophenyl)guanidine (CC11), have an impact on mitochondrial proton leak, which is an indicator of mitochondria damage. Evidence of genotoxic effects in the form of DNA double strand breaks (DSBs) was suggested by RNA-sequencing results and further validated by an increased expression of genes associated with DNA damage response (DDR), specifically the canonical non-homologous end joining (c-NHEJ) pathway, as determined by qPCR analysis of different pathway specific genes (XRCC6, PRKDC, LIG4 and XRCC4). Immunofluorescence analysis of phosphorylated histone H2AX, another DSB biomarker, also confirmed the potential genotoxic effects observed for the chlorinated products. In addition, chlorination of DPG leads to the formation of different chlorinated products (CC04, CC05 and CC15), with analysed compounds representing up to 42% of formed products, monochloramine is not able to effectively react with DPG. These findings indicate that DPG reaction with free chlorine doses commonly applied during drinking water treatment or in water distribution networks (0.2-0.5 mg/L) can lead to the formation of toxic and genotoxic chlorinated products.

In-situ chemical attenuation of pharmaceutically active compounds using CaO2: Influencing factors, mechanistic modeling, and cooperative inactivation of water-borne microbial pathogens.

Water polluted by pharmaceutically active compounds (PhACs) and water-borne pathogens urgently need to develop eco-friendly and advanced water treatment techniques. This paper evaluates the potential of using calcium peroxide (CaO2), a safe and biocompatible oxidant both PhACs (thiamphenicol, florfenicol, carbamazepine, phenobarbital, and primidone) and pathogens (Escherichia coli, Staphylococcus aureus) in water. This paper evaluates the potential of using calcium peroxide (CaO2) as a safe and biocompatible oxidant to remove both PhACs (thiamphenicol, florfenicol, carbamazepine, phenobarbital, and primidone) and pathogens (Escherichia coli, Staphylococcus aureus) in water. The increased CaO2 dosage increased efficiencies of PhACs attenuation and pathogens inactivation, and both exhibited pseudo-first-order degradation kinetics (R2 > 0.90). PhACs attenuation were mainly via oxidization (H2O2, •OH/O•-, and O2•-) and alkaline hydrolysis (OH-) from CaO2. Moreover, concentrations of these reactive species and their contributions to PhACs attenuation were quantified, and mechanistic model was established and validated. Besides, possible transformation pathways of target PhACs except primidone were proposed. As for pathogen indicators, the suitable inactivation dosage of CaO2 was 0.1 g L-1. The oxidability (18-64%) and alkalinity (82-36%) generated from CaO2 played vital roles in pathogen inactivation. In addition, CaO2 at 0.01-0.1 g L-1 can be applied in remediation of SW contaminated by PhACs and pathogenic bacteria, which can degrade target PhACs with efficiencies of 21-100% under 0.01 g L-1 CaO2, and inactivate 100% of test bacteria under 0.1 g L-1 CaO2. In short, capability of CaO2 to remove target PhACs and microbial pathogens reveals its potential to be used as a representative technology for the advanced treatment of waters contaminated by organic compounds and microbial pathogens.

One planet: one health. A call to support the initiative on a global science-policy body on chemicals and waste.

The chemical pollution crisis severely threatens human and environmental health globally. To tackle this challenge the establishment of an overarching international science-policy body has recently been suggested. We strongly support this initiative based on the awareness that humanity has already likely left the safe operating space within planetary boundaries for novel entities including chemical pollution. Immediate action is essential and needs to be informed by sound scientific knowledge and data compiled and critically evaluated by an overarching science-policy interface body. Major challenges for such a body are (i) to foster global knowledge production on exposure, impacts and governance going beyond data-rich regions (e.g., Europe and North America), (ii) to cover the entirety of hazardous chemicals, mixtures and wastes, (iii) to follow a one-health perspective considering the risks posed by chemicals and waste on ecosystem and human health, and (iv) to strive for solution-oriented assessments based on systems thinking. Based on multiple evidence on urgent action on a global scale, we call scientists and practitioners to mobilize their scientific networks and to intensify science-policy interaction with national governments to support the negotiations on the establishment of an intergovernmental body based on scientific knowledge explaining the anticipated benefit for human and environmental health.

Non-targeted metabolomics revealing the effects of bisphenol analogues on human liver cancer cells.

Bisphenol analogues (BPs) are widely used in plastics, food packaging and other commercial products as non safer alternative of BPA. As emerging environmental contaminants, BPs have received considerable attention for their adverse effects on human health. However, their effects on liver metabolisms are only marginally understood. In this study, high-resolution mass spectrometry-based global metabolomics and extracellular flux (XF) analysis were applied to characterize the cellular metabolome alterations and reveal the possible mechanisms of the metabolic disorders associated with BPs-induced toxicity in HepG2 cells. BPE, BPB and BPAP with similar chemical structures were selected to compare their interference with different metabolic pathways. A total of 61 key metabolite profiles were significantly altered after exposure to the three BPs. Overall, BPs altered metabolites which are associated with energy metabolism, oxidative stress, cell proliferation and nucleotides synthesis. The primary dysregulated pathways included energy and nucleotides synthesis related Purine and Glycolysis/Gluconeogenesis metabolism. In addition, attenuated mitochondrial function and enhanced glycolysis were found under BPB and BPAP treatment. While attenuated glycolysis was observed under BPE treatment. These findings may provide potential biomarkers indicating the cytotoxicity of BPs and prompt a deeper understanding of the intramolecular metabolic processes induced by BPs exposure.

Recent advances in mass spectrometry analytical techniques for per- and polyfluoroalkyl substances (PFAS).

The ubiquitous presence of per- and polyfluoroalkyl substances (PFAS) in various environments has led to increasing concern, and these chemicals have been confirmed as global contaminants. Following the chemical regulatory restrictions imposed, PFAS alternatives that are presumed to be less toxic have been manufactured to replace the traditional ones in the market. However, owing to the original release and alternative usage, continuous accumulation of PFAS has been reported in environmental and human samples, with uncertain consequences for ecosystem and human health. It is crucial to promote and improve existing analytical techniques to facilitate the detection of trace amounts of PFAS in diverse environmental matrices. This review summarizes analytical methods that have been applied to and advanced for targeted detection and suspect screening of PFAS, which mainly include (i) sampling and sample preparation methods for various environment matrices and organisms, and quality assurance/quality control during the analysis process, and (ii) quantitative methods for targeted analysis and automated suspect screening strategies for non-targeted PFAS analysis, together with their applications, advantages, shortcomings, and need for new method development.

Which Micropollutants in Water Environments Deserve More Attention Globally?

Increasing chemical pollution of aquatic environments is a growing concern with global relevance. A large number of organic chemicals are termed as "micropollutants" due to their low concentrations, and long-term exposure to micropollutants may pose considerable risks to aquatic organisms and human health. In recent decades, numerous treatment methods and technologies have been proposed to remove micropollutants in water, and typically several micropollutants were chosen as target pollutants to evaluate removal efficiencies. However, it is often unclear whether their toxicity and occurrence levels and frequencies enable them to contribute significantly to the overall chemical pollution in global aquatic environments. This review intends to answer an important lingering question: Which micropollutants or class of micropollutants deserve more attention globally and should be removed with higher priority? Different risk-based prioritization approaches were used to address this question. The risk quotient (RQ) method was found to be a feasible approach to prioritize micropollutants in a large scale due to its relatively simple assessment procedure and extensive use. A total of 83 prioritization case studies using the RQ method in the past decade were compiled, and 473 compounds that were selected by screening 3466 compounds of three broad classes (pharmaceuticals and personal care products (PPCPs), pesticides, and industrial chemicals) were found to have risks (RQ > 0.01). To determine the micropollutants of global importance, we propose an overall risk surrogate, that is, the weighted average risk quotient (WARQ). The WARQ integrates the risk intensity and frequency of micropollutants in global aquatic environments to achieve a more comprehensive priority determination. Through metadata analysis, we recommend a ranked list of 53 micropollutants, including 36 PPCPs (e.g., sulfamethoxazole and ibuprofen), seven pesticides (e.g., heptachlor and diazinon), and 10 industrial chemicals (e.g., perfluorooctanesulfonic acid and 4-nonylphenol) for risk management and remediation efforts. One caveat is that the ranked list of global importance does not consider transformation products of micropollutants (including disinfection byproducts) and new forms of pollutants (including antibiotic resistance genes and microplastics), and this list of global importance may not be directly applicable to a specific region or country. Also, it needs mentioning that there might be no best answer toward this question, and hopefully this review can act as a small step toward a better answer.

Catalytic non-thermal plasma treatment of endocrine disrupting compounds, pharmaceuticals, and personal care products in aqueous solution: A review.

Contaminants of emerging concerns such as endocrine-disrupting compounds (EDCs) and pharmaceuticals/personal-care products (PPCPs) constitute a problem since they are not completely eliminated by traditional water and wastewater treatment methods. Non-thermal plasma (NTP) is considered as one of the most favorable treatment methods for the removal of organic contaminants in water and wastewater. The degradation of selected EDCs and PPCPs of various classes was reviewed, based on the recent literature, to (i) address the effect of the main NTP treatment parameters (water quality and NTP conditions: pH, initial concentration, temperature, background common ion, NOM, scavenger, gas type/flow rate, discharge/reactor type, input power, and energy efficiency/yield) on the degradation of contaminants and their intermediates, (ii) assess the influences of different catalysts and hybrid systems on degradation, (iii) describe EDC and PPCP degradation along with their properties, and (iv) evaluate mineralization, pathway, and degradation mechanism of selected EDCs and PPCPs for different cases studied. Furthermore, areas of potential research in NTP treatment for the degradation of EDCs and PPCPs in aqueous solutions are recommended. It could be reasonably predicted that this review is valid for developing our understanding of the fundamental scientific principles concerning the catalytic NTP of EDCs and PPCPs, providing helpful and practical references for researchers and designers on the effective removal of EDCs/PPCPs and the optimized operation of catalytic NTP systems.

Formation of nitrogenous disinfection byproducts in MP UV-based water treatments of natural organic matters: The role of nitrate.

UV-based water treatment processes have been reported to induce genotoxicity during the treatments of surface water, drinking water and artificial water with natural organic matters (NOMs), causing genotoxicity concerns for the drinking water safety. Nitrogenous disinfection byproducts (N-DBPs) were generally reported to be much more genotoxic than their non-nitrogenous analogues, and might be responsible for the genotoxicity in UV processes. Although nitrate-rich water was getting attention for the possibility of genotoxicity and N-DBPs during UV treatments, the impact mechanism of nitrate on the degradation of NOMs, the formation of N-DBPs and genotoxicity has not been explicated. Here simulation experiments of NOM degradation under medium-pressure (MP) UV and MP UV/H2O2 treatments were conducted to explore the effect of nitrate on the molecular characteristics of NOM, the nitrate-derived N-DBPs and the potential genotoxicity through non-targeted analysis and CALUX® reporter gene assays. The results showed that nitrate can accelerate the degradation of NOMs in the MP UV process but inhibit the degradation of NOMs in the MP UV/H2O2 process. During the degradation of NOMs, the molecular compositions varied by the effect of nitrate on oxygen atoms, molecule analogs, and saturation. A total of 105 and 374 nitrate-derived N-DBPs were identified in the MP UV and MP UV/H2O2 treatment, respectively. Most of these N-DBPs contain one nitrogen atom, and the representative features are nitro-, methoxy- (or hydroxyl-) and ester- groups on benzene. No genotoxicity was observed without nitrate spiking, whereas genotoxicity was induced after both MP UV and MP UV/H2O2 treatments when nitrate was spiked, which is worthy of attention for the drinking water safety management.