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Increasing use of scrubbers on vessels for reduction of SOx emissions has led to environmental concerns due to discharge of partly persistent and toxic substances such as polycyclic aromatic compounds (PAC) into the sea. A comprehensive analysis of the dissolved and particulate phases of the discharge water from open and closed loop operations on four ships was performed. 71 PAC in the discharge waters varied in concentration and were associated with those of the fuels used, as they mainly originate in unburnt fuel. Closed loop discharge water showed higher PAC concentrations, especially of HMW PAC, which partly explains the larger toxic effects reported for this discharge. Alkylnaphthalenes and -phenanthrenes dominated in dissolved and particulate fractions, respectively. 14 NSO-PAC concentrations were relatively low. Alkylated derivatives of 4H-cyclopenta[4,5-def]phenanthrene and/or phenylnaphthalene were for the first time tentatively identified using GC-APLI-MS. The use of low-PAC fuels could significantly reduce PAC ship emissions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Wastewater treatment plants (WWTPs) are an important source of pharmaceuticals in surface water, but information about their transformation products (TPs) is very limited. Here, we investigated occurrence and transformation of pharmaceuticals and TPs in WWTPs and receiving rivers by using suspect and non-target analysis as well as target analysis. Results showed identification of 113 pharmaceuticals and 399 TPs, including mammalian metabolites (n = 100), environmental microbial degradation products (n = 250), photodegradation products (n = 44) and hydrolysis products (n = 5). The predominant parent pharmaceuticals (n = 37) and transformation products (n = 68) were mainly derived from antimicrobials, accounting for 32.7 % and 17.0 %, respectively. The identified compounds were found in the influent (387-428) and effluent (227-400) of WWTPs, as well as upstream (290-451) and downstream (322-416) of receiving rivers, most predominantly from antimicrobials, followed by analgesic and antipyretic drugs. A total of 399 identified TPs were transformed by 110 pathways, of which the oxidation reaction was predominant (27.0 %), followed by photodegradation reaction (10.7 %). Of the 399 TPs, 49 (with lower PNECs) were predicted to be more toxic than their parents. Compounds with potential high risks (hazard quotient >1 and risk index (RI) > 0.1) were found in the WWTP influent (126), effluent (53) and river (61), and the majority were from the antimicrobial and antihypertensive classes. In particular, the potential risks (RI) of TPs from roxithromycin and irbesartan were found higher than those for their corresponding parents. The findings from this study highlight the need to monitor TPs from pharmaceuticals in the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Various industries produce a myriad of synthetic molecules used to satisfy our needs, but all these molecules are likely to reach aquatic environments. The number of organic contaminants found in rivers and lakes continues to rise, and part of this contamination gets transferred into sediments. Analytical methods to detect problematic substances in the environment often use mass spectrometry coupled with chromatography. Here we reviewed a set of 163 articles and compiled the relevant information into a comprehensive database for analysing organic contaminants in continental sediments including suspended particulate matter and surface and bottom sediments in lakes, rivers and estuaries. We found 1204 compounds detected at least once in sediments, and classified them into 11 categories, i.e. hydrocarbons, flame retardants, polychlorinated biphenyls (PCB), plasticizers, per- and poly-fluoroalkyl substances (PFAS), organochlorines (OCP) and other pesticides, pharmaceuticals, hormones, personal care products (PCP), and other contaminants. Concentrations of these compounds varied from a few ng to several mg/kg of dry sediment. Even hydrophilic compounds were detected in high concentrations. Well-known hydrophobic and persistent contaminants tend to be analysed with mass spectrometry coupled to gas chromatography (GC-MS) whereas contaminants of emerging concern (CEC) are usually analysed with liquid chromatography- mass spectrometry (LC-MS). Suspect screening and non-target analysis (NTA), which use high-resolution mass spectrometry, are still scarcely used on sediment but hold promise for gaining deeper knowledge of organic contamination in aquatic environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)

This study utilized liquid chromatography (LC) alongside Fourier-transform ion cyclotron resonance mass spectrometry (FT-ICR MS) to explore the dyes and chemical contaminants in Loji River, Indonesia. We tentatively identified a total of 655 contaminants at various confidence level, subsequently classifying them into 22 distinct categories. Of the 54 dyes we detected, 12 corresponded with entries in our specialized in-house database. These 12 dyes were further confirmed by reference standards, matching both retention time (RT) and MS/MS spectra. LC-FT-ICR MS data showed that dyes from printing batik and textile industries are key contributors to river pollution. Particularly noteworthy were two sample locations that displayed substantial contamination, predominantly from azoic and reactive dyes. Additionally, pharmaceuticals were identified as one of the most frequently occurring contaminants, underscoring the inadequacies in the area's sewage management. To corroborate these findings, we conducted physicochemical, phytotoxicity, and acute toxicity tests, all of which verified the harmful effects of the Loji River's water on both the local flora and human populations. Notably, water samples that tested positive for dye contamination exhibited elevated toxicity levels. To the best of our knowledge, this study is pioneering in its molecular-level investigation of dye contamination in Southeast Asian rivers. Our results accentuate the pressing need for both targeted and non-targeted screening methods to identify contaminants in the surface waters of developing nations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In an attempt to discover and characterize the plethora of xenobiotic substances, this study investigates chemical compounds released into the environment with wastewater effluents. A novel non-targeted screening methodology based on ultra-high resolution Orbitrap mass spectrometry and nanoflow ultra-high performance liquid chromatography together with a newly optimized data-processing pipeline were applied to effluent samples from two state-of-the-art and one small wastewater treatment facility. In total, 785 molecular structures were obtained, of which 38 were identified as single compounds, while 480 structures were identified at a putative level. Most of these substances were therapeutics and drugs, present as parent compounds and metabolites. Using R packages Phyloseq and MetacodeR, originally developed for bioinformatics, significant differences in xenobiotic presence in the wastewater effluents between the three sites were demonstrated., Competing Interests: Declaration of competing interest The authors declare no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier Inc. All rights reserved.)

The comprehensive understanding of the occurrence of benzotriazole UV stabilizers (BZT-UVs) in environmental surface water is imperative due to their widespread application and potential aquatic toxicity. We conducted an analysis of 13 traditional BZT-UVs in surface water samples collected from Taihu Lake (TL, n = 23) and Qiantang River (QR, n = 22) in China. The results revealed that 5‑chloro-2-(3,5-di-tertbutyl-2-hydroxyphenyl)-benzotriazole (UV-327) was consistently the predominant BZT-UV in water samples from TL (mean 16 ng/L; detection frequency 96 %) and QR (14 ng/L; 91 %). Furthermore, we developed a characteristic fragment ion-based strategy to screen and identify unknown BZT-UVs in collected surface water, utilizing a high-resolution mass spectrometer. A total of seven novel BZT-UVs were discovered in water samples, and their chemical structures were proposed. Four of these novel BZT-UVs were further confirmed with standards provided by industrial manufacturers. Semi-quantitative analysis revealed that among discovered novel BZT-UVs, 2-(2‑hydroxy-3‑tert‑butyl‑5-methylphenyl)-benzotriazole was consistently the predominant novel BZT-UV in TL (mean 4.1 ng/L, detection frequency 70 %) and QR (2.8 ng/L, 77 %) water. In TL water, the second predominant novel BZT-UV was 2-(3-allyl-2‑hydroxy-5-methylphenyl)-2H-benzotriazole (mean 3.9 ng/L,

Citalopram (CIT) is one of the most consumed antidepressants and frequently detected in aquatic environments worldwide. Conventional wastewater treatment cannot remove this neuronal active pharmaceutical efficiently. Past studies showed that moving bed biofilm reactors (MBBRs) can degrade CIT but the exact transformation pathways and toxicity reduction remained unclear. In this study, the effects of substrate stimulation on CIT transformation in an MBBR were systematically investigated. The results showed that a co-metabolic stimulation by acetate increased the transformation rate by 54 % and 24 % at high (300 μg/L) and environmental concentration (1.8 μg/L) of CIT, respectively. Conversely, the complex substrates in raw wastewater reduced the reaction rates by 44 %, suggesting a competitive inhibition on the enzymatic sites. The substrate stimulation changed the enantiomeric fraction (EF) of CIT from racemic (EF=0.5) to 0.60 at the high CIT concentrations, while those at lower concentrations resulted in an EF of 0.33, indicating that probably different enantioselective enzymes degraded CIT at high concentrations than at low concentrations, i.e., the presence of 300 µg/L CIT was possibly sufficient to induce the synthesis of different enantioselective enzymes, than those originally present. Through non-target and target analysis, in total 19 transformation products (TPs) including 7 TPs that were hitherto not mentioned in the literature were identified. Among these were quaternary amines, alkenes and conjugate TPs. The major transformation pathways were a) nitrile hydrolysis (up to 43 %), b) amide hydrolysis, and c) N-oxidation. Dosing acetate up-regulated significantly the amide hydrolysis, N-oxidation and conjugation pathways but inhibited the N-demethylation and α-carbon hydroxylation pathways. The in-silico toxicity assessment of CIT and its TPs suggested the overall eco-toxic potential of TPs was reduced by MBBR. Furthermore, the degradation under carbon-limited (famine) conditions favored the formation of the more toxic carboxamide, N-desmethyl and alkene TPs, while carbon-rich conditions, promoted the production of the less toxic carboxylic acid, N-oxide and ester TPs. Therefore, this study demonstrated that a) the co-metabolic stimulation of CIT metabolization by dosing a simple carbon source or b) inhibition of CIT metabolization by complex substrates; c) substrate stimulation made a difference on CIT transformation rates, enantiomeric profiles, pathways and toxic potentials. Overall, a simple-carbon co-metabolic stimulated MBBR was an efficient up-regulation strategy to minimize hazardous CIT and CIT-TPs as much as possible., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Urban surface runoff contains chemicals that can negatively affect water quality. Urban runoff studies have determined the transport dynamics of many legacy pollutants. However, less attention has been paid to determining the first-flush effects (FFE) of emerging micropollutants using suspect and non-target screening (SNTS). Therefore, this study employed suspect and non-target analyses using liquid chromatography-high resolution mass spectrometry to detect emerging pollutants in urban receiving waters during stormwater events. Time-interval sampling was used to determine occurrence trends during stormwater events. Suspect screening tentatively identified 65 substances, then, their occurrence trend was grouped using correlation analysis. Non-target peaks were prioritized through hierarchical cluster analysis, focusing on the first flush-concentrated peaks. This approach revealed 38 substances using in silico identification. Simultaneously, substances identified through homologous series observation were evaluated for their observed trends in individual events using network analysis. The results of SNTS were normalized through internal standards to assess the FFE, and the most of tentatively identified substances showed observed FFE. Our findings suggested that diverse pollutants that could not be covered by target screening alone entered urban water through stormwater runoff during the first flush. This study showcases the applicability of the SNTS in evaluating the FFE of urban pollutants, offering insights for first-flush stormwater monitoring and management., Competing Interests: Declaration of competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

In regulatory environmental monitoring programs, only a very small fraction of the vast number of per- and polyfluoroalkyl substances (PFAS) are investigated by target analysis. Therefore, non-target analysis (NTA) studies are increasingly conducted to detect unknown or unnoticed PFAS. These studies are often based on a few grab samples. Thus, discontinuously emitted PFAS from industrial batch processes might be easily overlooked. To address this deficiency and obtain in-depth information on the occurrence and temporal trend of PFAS in surface water impacted by treated industrial waste water, a comprehensive target and NTA study was implemented for 29 months. Elevated PFAS concentrations with up to 10.8 μg L -1 were detected in the river water by target analysis. In addition to PFAS target analysis, the water samples were analyzed by liquid chromatography-high-resolution tandem mass spectrometry (LC-HRMS/MS). Data processing strategies and various filtering steps were applied to prioritize PFAS. Substances were identified by comparing data to available internal and external PFAS suspect lists, a fragment ion and neutral loss list, and spectral libraries. Several compounds were unequivocally identified based on reference standards. Fifty-five PFAS were (tentatively) identified using NTA. Of those, 43 could be assigned to 13 different homologous series. Partly fluorinated short-chain carboxylic acids (H-PFCA) and sulfonic acids (H-PFSA) were predominantly found in addition to perfluoroalkyl carboxylic acids (PFCA) and the alkyl ether carboxylic acid DONA. To the best of our knowledge, 12 PFAS were reported in surface water for the first time. Signal intensities of individual PFAS and signal ratios varied widely over time, which may indicate batch operations leading to discontinuous emission. Results and insights from this screening approach on PFAS can be used to optimize forthcoming surface water monitoring programs by including newly identified PFAS and selecting appropriate sampling intervals., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

This study investigated the chemical composition of waters in the heavily urbanized and historically polluted Miami River, Florida. The goal was to assess the different water sources and anthropogenic influence in this managed area using nontarget analysis (NTA) combined with high-resolution mass spectrometry (HRMS). Surface water samples were collected from 10 sites during five sampling events in the wet season of 2021 and 2022. The HRMS data was processed using Compound Discoverer™ version 3.3, and the results were analyzed using techniques including Principal Component Analysis and Kendrick Mass Defect plots. Results showed a gradient change in the chemical composition from the Everglades to Biscayne Bay endmembers. The Seybold Canal, an adjacent canal, was consistently identified as a unique source of contaminants, contributing its own specific set of tracers. Increased presence and intensity of organic contaminants along the waterway was observed, indicating significant anthropogenic influence in the area. The NTA and post-processing were evaluated for reproducibility, demonstrating robustness with a 71.2% average reproducibility for compounds detected in 3 out of 5 sampling trips. A detection frequency of 80% (4 out of 5) was the set criterion for detected compounds suggested as tracers. To prioritize samples, hierarchical cluster analysis was employed, and potential tracers for each water source were determined. Tracers included natural products and agricultural herbicides and insecticides for the Everglades, anthropogenic contaminants for the Seybold Canal, and a lack of unique tracers for Biscayne Bay. Additionally, urban-influenced contaminants such as flame retardants, insect repellents, pharmaceuticals, and non-agricultural herbicides were identified along the river. This study highlights the impact of human activities on the Miami River and demonstrates the effectiveness of NTA in differentiating and tracking water sources. The results emphasize the importance of reproducibility in NTA and provide guidance on implementing monitoring strategies by prioritizing samples based on chemical compositions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Chlorine-based disinfectants, such as sodium hypochlorite, are extensively used in our daily lives. In particular, during the recent Covid-19 pandemic and post-pandemic period, excessive amounts of chlorine-based disinfectants were used both indoors and outdoors to interrupt virus transmission. However, the interaction between disinfectants and city dust during the disinfection process has not been sufficiently evaluated. In this study, we conducted a comprehensive investigation into the intrinsic characteristics (e.g. morphology, size, elemental composition, and organic content, etc.) of dust collected from various indoor and outdoor areas. The results showed that the organic carbon content of indoor dust reached 6.14 %, with a corresponding measured dissolved organic carbon value of 4.17 ± 0.23 mg/g (normalized to the dust weight). Concentrations of regulated DBPs, resulting from the interaction between dust and NaClO, ranged from 57.78 ± 2.72 to 102.80 ± 22.63 µg/g for THMs and from 119.18 ± 6.50 to 285.14 ± 36.95 µg/g for HAAs (normalized to the dust weight). More significantly, using non-target analysis through gas chromatography quadrupole time-of-flight mass spectrometry (GC-qTOF-MS), we identified a total of 68, 89, and 87 types of halogenated DBPs from three typical indoor and outdoor sites (R-QH, C-JS, and W-BR, respectively). These unknown DBPs included compounds with higher toxicity compared to regulated DBPs. These findings highlight that city dust is a significant source of DBP generation during chlorine-based disinfection, posing potential harm to both the ecological environment and human health., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Plastic pollution causes detrimental environmental impacts, which are increasingly attributed to chemical additives. However, the behaviour of plastic additives in the marine environment is poorly understood. We used a marine deployment experiment to examine the impact of weathering on the extractables profile, analysed by liquid chromatography-mass spectrometry, of four plastics at two locations over nine months in Aotearoa/New Zealand. The concentration of additives in polyethylene and oxo-degradable polyethylene were strongly influenced by artificial weathering, with deployment location and time less influential. By comparison, polyamide 6 and polyethylene terephthalate were comparatively inert with minimal change in response to artificial weathering or deployment time. Non-target analysis revealed extensive differentiation between non-aged and aged polyethylene after deployment, concordant with the targeted analysis. These observations highlight the need to consider the impact of leaching and weathering on plastic composition when quantifying the potential impact and risk of plastic pollution within receiving environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Non-target analyses were conducted to characterize and compare the molecular profiles (UHPLC-HRMS fingerprint) of water samples from a wastewater treatment plant (WWTP). Inlet and outlet samples were collected from three campaigns spaced 6 months apart in order to highlight common trends. A significant impact of the treatment on the sample fingerprints was shown, with a 65-70% abatement of the number of features detected in the effluent, and more polar, smaller and less intense molecules found overall compared to those in WWTP influent waters. Multivariate analysis (PCA) associated with variations of the features between inlets and outlets showed that features appearing or increasing were correlated with effluents while those disappearing or decreasing were correlated with influents. Finally, effluent features considered as relevant to a potentially adverse effect on aqueous media (i.e. those which appeared or increased or slightly varied from the influent) were highlighted. Three hundred seventy-five features common with the 3 campaigns were thus selected and further characterized. For most of them, elementary composition was found to be C, H, N, O (42%) and C, H, N, O, P (18%). Considering the MS 2 spectra and several reference MS 2 databases, annotations were proposed for 35 of these relevant features. They include synthetic products, pharmaceuticals and metabolites., (© 2023. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Hydraulic fracturing flowback and produced water (HF-FPW) from shale gas extraction processes is a highly complex medium with potential threats to the environment. Current research on ecological risks of FPW in China is limited, and the link between major components of FPW and their toxicological effects on freshwater organisms is largely unknown. By integrating chemical and biological analyses, toxicity identification evaluation (TIE) was used to reveal causality between toxicity and contaminants, potentially disentangling the complex toxicological nature of FPW. Here, FPW from different shale gas wells, treated FPW effluent, and a leachate from HF sludge were collected from southwest China, and TIE was applied to obtain a comprehensive toxicity evaluation in freshwater organisms. Our results showed that FPW from the same geographic zone could cause significantly different toxicity. Salinity, solid phase particulates, and organic contaminants were identified as the main contributors to the toxicity of FPW. In addition to water chemistry, internal alkanes, PAHs, and HF additives (e.g., biocides and surfactants) were quantified in exposed embryonic fish by target and non-target tissue analyses. The treated FPW failed to mitigate the toxicity associated with organic contaminants. Transcriptomic results illustrated that organic compounds induced toxicity pathways in FPW-exposed embryonic zebrafish. Similar zebrafish gene ontologies were affected between treated and untreated FPW, again confirming that sewage treatment did not effectively remove organic chemicals from FPW. Thus, zebrafish transcriptome analyses revealed organic toxicant-induced adverse outcome pathways and served as evidence for TIE confirmation in complex mixtures under data-poor scenarios., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Ltd. All rights reserved.)

Accelerated urbanization and industrialization have led to an alarming increase in the generation of wastewater with complex chemical contents. Industrial wastewaters are often a primary source of water contamination. The chemical characterization of different industrial wastewater types is an essential task to interpret the chemical fingerprints of wastewater to identify pollution sources and develop efficient water treatment strategies. In this study, we conduct a non-target chemical analysis for the source characterization of different industrial wastewater samples collected from a chemical industrial park (CIP) located in southeast China. The chemical screening identified volatile and semi-volatile organic compounds that included dibutyl phthalate at a maximum concentration of 13.4 μg/L and phthalic anhydride at 35.9 μg/L. Persistent, mobile, and toxic (PMT) substances among the detected organic compounds were identified and prioritized as high-concern contaminants given their impact on drinking water resources. Moreover, a source analysis of the wastewater collected from the wastewater outlet station indicated that the dye production industry contributed the largest quantities of toxic contaminates (62.6%), and this result was consistent with the ordinary least squares and heatmap results. Thus, our study utilized a combined approach of a non-target chemical analysis, a pollution source identification method, and a PMT assessment of different industrial wastewater samples collected from the CIP. The results of the chemical fingerprints of different industrial wastewater types as well as the results of the PMT assessment benefit risk-based wastewater management and source reduction strategies., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023. Published by Elsevier Inc.)

Ozonation of natural waters is typically associated with the formation of carbonyl compounds (aldehydes, ketones and ketoacids), a main class of organic disinfection byproducts (DBPs). However, the detection of carbonyl compounds in water and wastewater is challenged by multiple difficulties inherent to their physicochemical properties. A non-target screening method involving the derivatisation of carbonyl compounds with p-toluenesulfonylhydrazine (TSH) followed by their analysis using liquid chromatography coupled to electrospray ionisation high-resolution mass spectrometry (LC-ESI-HRMS) and an advanced non-target screening and data processing workflow was developed. The workflow was applied to investigate the formation of carbonyl compounds during ozonation of different water types including lake water, aqueous solutions containing Suwannee River Fulvic acid (SRFA), and wastewater. A higher sensitivity for most target carbonyl compounds was achieved compared to previous derivatisation methods. Moreover, the method allowed the identification of known and unknown carbonyl compounds. 8 out of 17 target carbonyl compounds were consistently detected above limits of quantification (LOQs) in most ozonated samples. Generally, the concentrations of the 8 detected target compounds decreased in the order: formaldehyde > acetaldehyde > glyoxylic acid > pyruvic acid > glutaraldehyde > 2,3-butanedione > glyoxal > 1-acetyl-1-cyclohexene. The DOC concentration-normalised formation of carbonyl compounds during ozonation was higher in wastewater and SRFA-containing water than in lake water. The specific ozone doses and the type of the dissolved organic matter (DOM) played a predominant role for the extent of formation of carbonyl compounds. Five formation trends were distinguished for different carbonyl compounds. Some compounds were produced continuously upon ozonation even at high ozone doses, while others reached a maximum concentration at a certain ozone dose above which they decreased. Concentrations of target and peak areas of non-target carbonyl compounds during full-scale ozonation at a wastewater treatment plant showed an increase as a function of the specific ozone dose (sum of 8 target compounds ∼ 280 µg/L at 1 mgO 3 /mgC), followed by a significant decrease after biological sand filtration (> 64-94% abatement for the different compounds). This highlights the biodegradability of target and non-target carbonyl compounds and the importance of biological post-treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

The enhanced separation power and identification capabilities make comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC × GC - ToF MS) a valuable instrumental alternative for non-target analysis (NTA). In the present study, GC × GC - ToF MS has been used for the NTA of chlorine- and bromine-containing compounds in composite livers of two scarcely investigated Mediterranean deep-sea fish species, hollowsnout grenadier (Coelorinchus caelorhincus) and roughsnout grenadier (Trachyrhinchus trachyrhinchus). Attention focused on the identification of organohalogenated compounds with structural characteristics similar to those of persistent organic pollutants (POPs). In total, 116 Cl-, Br- and mixed Cl/Br-compounds were either positively or tentatively identified in the analyzed liver samples. Up to 88 of these compounds were legacy POPs, being polychlorinated biphenyls (PCBs) and organochlorinated pesticides (OCPs) the most abundant and frequently detected families. The other 28 identified POP-like compounds were analytes not considered by current regulation and environmental monitoring programs, including, among others, degradation products of specific OCPs, naturally produced organohalogen compounds and several perchlorinated diethyldiphenylmethane-derivatives whose presence in the investigated species is reported here for the first time. The presence of other naturally occurring brominated and mixed halogenated compounds in these fish species is also described for the first time. Our results also showed differences in the accumulation profile of the identified compounds in both species. Thereby, anthropogenic POPs showed higher relative abundances in the livers of roughsnout grenadiers than those in hollowsnout grenadiers, while for naturally occurring compounds the opposite trend or similar levels were found in both species., Competing Interests: Declaration of competing interest The authors declare no conflicts of interest., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

Since glass eels are continuously exposed to contamination throughout their migratory journey in estuaries, to a certain extent the fall in the population of this endangered species might be attributed to this exposure, which is especially acute in estuaries under high urban pressure. In this work, metabolomics was used to address the main objective of this study, to evaluate the effects of two pharmaceuticals previously identified as potential concerning chemicals for fish (diazepam and irbesartan) on glass eels. An exposure experiment to diazepam, irbesartan and their mixture was carried out over 7 days followed by 7 days of depuration phase. After exposure, glass eels were individually sacrificed using a lethal bath of anesthesia, and then an unbiased sample extraction method was used to extract separately the polar metabolome and the lipidome. The polar metabolome was submitted to targeted and non-targeted analysis, whereas for the lipidome only the non-targeted analysis was carried out. A combined strategy using partial least squares discriminant analysis and univariate and multivariate statistical analysis (ANOVA, ASCA, t-test, and fold-change analysis) was used to identify the metabolites altered in the exposed groups with respect to the control group. The results of the polar metabolome analysis revealed that glass eels exposed to the diazepam-irbesartan mixture were the most impacted ones, with altered levels for 11 metabolites, some of them belonging to the energetic metabolism, which was confirmed to be sensitive to these contaminants. Additionally, the dysregulation of the levels of twelve lipids, most of them with energetic and structural functions, was also found after exposure to the mixture, which might be related to oxidative stress, inflammation, or alteration of the energetic metabolism., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

The hypothesis of this study is that the complex organic load of landfill leachate could be reduced by supercritical water oxidation (SCWO) in a single stage, but this operation could lead to the formation of some undesired by-products of phthalate esters (PAEs). In this context, the fate of selected PAEs, butyl benzyl phthalate (BBP), di-2-ethylhexyl phthalate (DEHP) and di-n-octyl phthalate (DNOP), was investigated during the oxidation of leachate under subcritical and supercritical conditions. Experiments were conducted at various temperatures (250-500 °C), pressures (10-35 MPa), residence times (2-18 min) and dimensionless oxidant doses (DOD: 0.2-2.3). The SCWO process decreased the leachate's chemical oxygen demand (COD) from 34,400 mg/L to 1,120 mg/L (97%). Removal efficiencies of DEHP and DNOP with longer chains were higher than BBP. The DEHP, DNOP and BBP compounds were removed in the range of -35 to 100%, -18 to 92%, and 28 to 36%, respectively, by the SCWO process. Many non-target PAEs were qualitatively detected in the raw leachate apart from the selected PAEs. Besides, 97% of total PAEs including both target and non-target PAEs was mineralized at 15 MPa, 300 °C and 5 min. Although PAEs were highly mineralized during SCWO of the leachate, aldehyde, ester, amide and amine-based phthalic substances were frequently detected as by-products. These by-products have transformed into higher molecular weight by-products with binding reactions as a result of complex SCWO process chemistry. It has also been determined that some non-target PAEs such as 1,2-benzenedicarboxylic acid bis(2-methylpropyl)ester and bis(2-ethylhexyl) isophthalate can transform to the DEHP. Therefore, the suggested pathway in this study for PAEs degradation during the SCWO of the leachate includes substitution and binding reactions as well as an oxidation reaction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

The development of analytical methodologies to monitor different antibiotic families in water and the implementation of alternatives for their efficient elimination are a great challenge. The aim of this research was to develop a method based on solid-phase extraction followed by ultra-high performance liquid chromatography coupled to quadrupole time-of-flight mass spectrometry to analyse multi-class antibiotics, including macrolides, cephalosporins, fluoroquinolones, sulfonamides and diaminopyrimidines, in waters. Several parameters affecting the extraction such as the sample pH, type of sorbent and cartridge, elution volume and breakthrough volume were optimized. The method was validated in real samples, and matrix effect was assessed, demonstrating that the use of isotopically labelled surrogate compounds was mandatory to avoid standard addition calibration for each individual samples. Urban and hospital wastewater samples, as well as natural waters, were analysed, confirming the presence of 12 of the 14 target compounds at concentrations up to 3.5 µg L -1 . Non-target analysis based on data-independent workflow was also performed, enabling the identification of 94 pollutants. Preliminary photodegradation experiments were also assessed, revealing the total removal of many target compounds after the first 5-10 min of UVC irradiation. In addition, 20 by-products formed after photolysis could be identified using a non-target approach., (© 2022. The Author(s).)

Industry wastewater is considered one of the worst polluters of our precious water ecologies. However, the types of pollutants present in wastewater from industrial wastewater treatment plants (IWTPs) are still unclear. In this study, a simple and effective chemical fingerprinting method for checking the source-sink relationships among different industrial wastewaters and their effluent-receiving river was established. 107, 228, 155, and 337 chemicals were screened out in wastewater from electronics, steel, textile, and printing and dyeing plants, respectively. Chemical fingerprinting of the detected chemicals was performed, and results showed that aromatic compounds were the most prevalent among the pollutant categories (i.e., 56, 189, and 168 in electronics, iron and steel, and printing and dyeing plants, respectively). The traceability analysis of the chemicals selected in the effluent determined the characteristic pollutants of different industrial enterprises. Sixty-eight compounds were identified as the characteristic pollutants in the different process stages of wastewater of the four IWTPs. Of the 84 effluent-receiving river water signature pollutants, 47.6% (n = 40) were also detected in the effluent from the four IWTPs. Effective screening of organic pollutants in industrial wastewater and determining their sources will help accelerate the improvement of industrial wastewater treatment technology., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Per- and polyfluoroalkyl substances (PFASs) are applied in oil exploitation activity. In this study, non-target and suspect target analyses with high-resolution mass spectrometry were used for identification of novel PFASs in the oilfield environment. A total of thirty-seven PFAS homologues belonging to eight classes were identified as level 4 or above, which partly explained the amount of potential unknown PFAS-precursors that were indicated by total oxidisable precursor assay in our previous study. Hydrogen-substituted and ether-substituted homologues were the main identified PFASs, and seven of them were newly reported homologues. C1-C3 perfluoroalkane sulphonic acids (PFSAs) were also for the first time identified in the oilfield. The sediment-water partitioning coefficients of most identified PFAS homologues positively correlate with their predicted octanol-water partitioning coefficients while those of C1-C3 PFSAs may have elevated sediment partitioning potential as also previously observed for ultra-short chain C2-C3 perfluoroalkyl carboxylic acids. The crude oil and sludge samples were further examined with the target and identified PFAS profiles. An annual flux of 10.4 kg/y via oil production was estimated in Dagang Oilfield with 16.6 % not from the target PFASs. This demonstrates that oil exploitation activities can be a significant underlying source of PFASs to the environment., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The generation of disinfection by-products during water chlorination is a major concern in water treatment, given the potential health risks that these substances may pose. In particular, nitrogen-containing DBPs are believed to have greater toxicological significance than carbon-based DBPs. Hence, high performance liquid chromatography coupled to high-resolution mass spectrometry (HPLC-HRMS) in positive mode was employed to identify new non-volatile nitrogen containing disinfection by-products (DBPs) and to assess their presence in potable water. Nine water samples were taken in the Llobregat river, in the context of a water reuse trial, near the catchment of a drinking water treatment plant (DWTP) in 2019. River samples were disinfected with chlorine under controlled formation potential tests conditions and analysed with a non-target approach. The peak lists of raw and chlorinated samples were compared exhaustively, resulting in an extensive list of 495 DBPs that include bromine and/or chlorine atoms. 172 of these species were found frequently, in three or more chlorinated samples. The empirical formulae of these DBPs were unambiguously annotated on the basis of accurate m/z measurements, isotopic patterns and common heuristic rules. Most of the annotated species (310) contained bromide, which is consistent with the relatively high bromide content of the Llobregat basin (>0.3 mg/l). Drinking water samples were taken at the outlet of the DWTP during the same sampling period. According to their analysis, a large portion of the DBPs detected after the formation potential tests do not reach real-life drinking water, which suggests that the treatment train successfully removes a significant fraction of DBP precursors. However, 131 DBPs could still be detected in the final product water. A larger sampling was carried in the Barcelona water distribution network, during six consecutive weeks, and it revealed the presence of 78 halogenated DBPs in end-consumer water, most of which were nitrogen-containing. MS/MS fragmentation and retention times were employed to tentatively suggest molecular structure for these recalcitrant DBPs., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Landfill sites have been regarded as a significant source of chemicals of emerging concern (CECs) in groundwater. However, our understanding about the compositions of CECs in landfill leachate and adjacent groundwater is still very limited. Here we investigated the CECs in landfill leachates and groundwater of Guangzhou in South China by target, suspect and non-target analysis using high-resolution mass spectrometry (HRMS). A variety of CECs (n = 242), including pharmaceuticals (n = 64), pharmaceutical intermediates (n = 18), personal care products (n = 9), food additives (n = 18), industrial chemicals (n = 82, e.g., flame retardants, plasticizers, antioxidants and catalysts), pesticides (n = 26), transformation products (n = 8) and other organic compounds (n = 17) were (tentatively) identified by non-target and suspect screening. 142 CECs were quantitated with target analysis, and among them 37, 24 and 27 CECs were detected respectively in the raw leachate (272-1780 μg/L), treated leachate (0.25-0.81 μg/L) and groundwater (0.10-53.7 μg/L). The CECs in the raw leachates were efficiently removed with the removal efficiencies greater than 88.7%. Acesulfame, bisphenol F and ketoprofen were the most abundant compounds in both treated leachate and groundwater. The CECs in groundwater was found most likely to be originated from the landfill sites. Our results highlight the importance of non-target screening in identifying CECs, and reveal the contamination risk of groundwater by landfill leachate., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

This study presents a nation-wide assessment of the influence of chemical and pharmaceutical manufacturing (CPM) wastewaters on synthetic organic contaminant (SOC) emissions to Swiss surface waters. Geographic Information System (GIS) based analysis of the presence of CPM in wastewater treatment plant (WWTP) catchments revealed wide distribution of this industrial sector across Switzerland, suggesting that one-third of the 718 Swiss WWTPs may be influenced by CPM wastewaters. To reflect the diversity of this type of wastewaters, we investigated the effluents of 11 WWTPs of diverse sizes and technologies, which treated 0-100% wastewater from a variety of CPM activities. In an extensive sampling campaign, we collected temporally high resolved (i.e., daily) samples for 2-3 months to capture the dynamics of CPM discharges. The > 850 samples were then measured with liquid chromatography high-resolution mass spectrometry (LC-HRMS). Non-target characterization of the LC-HRMS time series datasets revealed that CPM wastewaters left a highly variable and site-specific signature in the effluents of the WWTPs. Particularly, compared to WWTPs with purely domestic input, a larger variety of substances (up to 15 times more compounds) with higher maximum concentrations (1-2 orders of magnitude) and more uncommon substances were found in CPM-influenced effluents. Moreover, in the latter, highly fluctuating discharges often contributed to a substantial fraction of the overall emissions. The largely varying characteristics of CPM discharges between different facilities were primarily related to the type of activities at the industries (i.e., production versus processing of chemicals) as well as to the pre-treatment and storage of CPM wastewaters. Eventually, for one WWTP, LC-HRMS time series were correlated with ecotoxicity time series obtained from bioassays and major toxic components could be identified. Overall, in view of their potential relevance to water quality, a strong focus on SOC discharges from CPM is essential, including the design of situation-specific monitoring, as well as risk assessment and mitigation strategies that consider the variability of industrial emissions., (Copyright © 2022. Published by Elsevier Ltd.)

Most environmental monitoring studies of contaminants of emerging concern (CECs) focus on aquatic species and target specific classes of CECs. Even with wide-scope target screening methods, relevant CECs may be missed. In this study, non-target screening (NTS) was used for tentative identification of potential CECs in muscle tissue of the terrestrial top predator Eurasian lynx (Lynx lynx). Temporal trend analysis was applied as a prioritisation tool for archived samples, using univariate statistical tests (Mann-Kendall and Spearman rank). Pooled lynx muscle tissue collected from 1969 to 2017 was analysed with an eight-point time series using a previously validated screening workflow. Following peak detection, peak alignment, and blank subtraction, 12,941 features were considered for statistical analysis. Prioritisation by time-trend analysis detected 104 and 61 features with statistically significant increasing and decreasing trends, respectively. Following probable molecular formula assignment and elucidation with MetFrag, two compounds with increasing trends, and one with a decreasing trend, were tentatively identified. These results show that, despite low expected concentration levels and high matrix effects in terrestrial species, it is possible to prioritise CECs in archived lynx samples using NTS and univariate statistical approaches., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2022 The Authors. Published by Elsevier B.V. All rights reserved.)

Wide use of various chemicals has resulted in water pollution, which has become a global environmental concern. So far limited information is available on what chemicals in our water. Here we investigated the occurrence and profiles of organic chemicals in the North River, South China by applying non-target screening analysis with high resolution mass spectrometry. A total of 402 organic chemicals belonging to eleven categories were identified in the North River, with notable presence of industrial chemicals, pharmaceuticals and pesticides. Among these detected chemicals, over half of the tentatively identified compounds were rarely reported in the surface water, with a few compounds, e.g., sisomicin, simeton, 2-methyl-4,6-dinitrophenol, xanthurenic acid and indole-3-carboxylic acid that have never been documented in the North River before, while the metabolites like 4-acetamidoantipyrine were also observed. The maximum concentration of the identified chemicals in the North River was above 300 ng/L (Sulfamonomethoxine). Principle component analysis results of the obtained dataset showed significant seasonal distribution, which could be linked to variations in wastewater discharge, river dilution and anthropogenic activities such as pesticide spray. Agricultural activities in the upper reaches led to detection of various pesticides in the river basin, especially in the wet season. The findings from this study demonstrated the widespread presence of chemicals in our waterway, and further retrospective analysis would reveal more information about chemicals of emerging concern., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

Biochar is a low-cost adsorbent with considerable potential for utilization as a water filtration medium; however, organic matter leaching from biochar can lead to the formation of disinfection by-products (DBPs). This study investigated the leaching of dissolved organic carbon (DOC) from eucalyptus-derived biochar and the formation of DBPs generated by chlorination and chloramination. Column experiments with empty bed contact times (EBCTs) of 10 and 30 min were conducted for 200 bed volumes (BVs). The highest DOC concentration (3.5 µg-C/g-biochar) was detected with an EBCT of 30 min. Chloroform (49 µg/L) and dichloroacetonitrile (7 µg/L) because of chlorination were found during the first five BVs, but were reduced thereafter. During the first 10 BVs, unknown chlorinated DBPs generated (CHOCl) by chlorination and chloramination (193 and 152 formulae, respectively) were tentatively identified via an unknown screening analysis. The release of DBP precursors from biochar tentatively identified in this study will impact water filtration applications., (Copyright © 2021 Elsevier B.V. All rights reserved.)

During ozonation in wastewater treatment plants, ozone reacts with emerging pollutants, which are partially removed through the secondary treatment, as long as, with their biotransformation products, triggering the formation of ozonation transformation products (TPs). Although the transformation of parent compounds (PCs) and their metabolites has been reported in the literature, the probable transformation of biotransformation products has not been investigated so far. This study evaluates the fate of citalopram (CTR) and four of its biotransformation products (DESCTR, CTRAM, CTRAC and CTROXO) during ozonation experiments. A Gaussian curve-based trend analysis was performed for the first time for the automated detection of TPs in ozone concentrations ranging from 0.06 to 12 mg/L. In total 46 ozonation TPs were detected; 7 TPs of CTR, 10 of DESCTR, 9 of CTRAM, 12 of CTRAC and 8 of CTROXO and were structurally elucidated based on their high resolution tandem mass spectra interpretation and tandem mass spectra similarity with the respective PC. Results have demonstrated that the examined compounds follow common transformation pathways in reaction with ozone and that common TPs were formed through the ozonation of different structurally-alike compounds. Moreover, the toxicity of the identified TPs was predicted with an in-house risk assessment program., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Advanced treatment is increasingly being applied to improve abatement of micropollutants in wastewater effluent and reduce their load to surface waters. In this study, non-target screening of high-resolution mass spectrometry (HRMS) data, collected at three Swiss wastewater treatment plants (WWTPs), was used to evaluate different advanced wastewater treatment setups, including (1) granular activated carbon (GAC) filtration alone, (2) pre-ozonation followed by GAC filtration, and (3) pre-ozonation followed by powdered activated carbon (PAC) dosed onto a sand filter. Samples were collected at each treatment step of the WWTP and analyzed with reverse-phase liquid chromatography coupled to HRMS. Each WWTP received a portion of industrial wastewater and a prioritization method was applied to select non-target features potentially resulting from industrial activities. Approximately 37,000 non-target features were found in the influents of the WWTPs. A number of non-target features (1207) were prioritized as likely of industrial origin and 54 were identified through database spectral matching. The fates of all detected non-target features were assessed through a novel automated trend assignment method. A trend was assigned to each non-target feature based on the normalized intensity profile for each sampling date. Results showed that 73±4% of influent non-target features and the majority of industrial features (89%) were well-removed (i.e., >80% intensity reduction) during biological treatment in all three WWTPs. Advanced treatment removed, on average, an additional 11% of influent non-target features, with no significant differences observed among the different advanced treatment settings. In contrast, when considering a subset of 66 known micropollutants, advanced treatment was necessary to adequately abate these compounds and higher abatement was observed in fresh GAC (7,000-8,000 bed volumes (BVs)) compared to older GAC (18,000-48,000 BVs) (80% vs 56% of micropollutants were well-removed, respectively). Approximately half of the features detected in the WWTP effluents were features newly formed during the various treatment steps. In ozonation, between 1108-3579 features were classified as potential non-target ozonation transformation products (OTPs). No difference could be observed for their removal in GAC filters at the BVs investigated (70% of OTPs were well-removed on average). Similar amounts (67%) was observed with PAC (7.7-13.6 mg/L) dosed onto a sand filter, demonstrating that a post-treatment with activated carbon is efficient for the removal of OTPs., (Copyright © 2021. Published by Elsevier Ltd.)

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., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Eight samples were obtained to characterize the chemical loads in water recycled for reuse applications. The sources included stormwater, rooftop runoff, wastewater, mixed water, and drinking water as a comparison. The water was reused for irrigation, cleaning, toilet flushing, and cooling purposes. Large-volume injection (650 μL) high-performance liquid chromatography and quadrupole time-of-flight mass spectrometry were employed to separate and detect features by suspect and non-target screening. The instrumental method had the advantage that no sample extractions were required prior to analysis. Two chromatographic methods were developed to separate positive- and negative-ionizing compounds and retention time models were developed for both. Retention time models provide an additional measure of confidence for probable and tentative identifications. The two models had predictive R 2 -which indicates how well the models predicts new observations-of 0.87. After data-reduction, the number of features detected in the samples ranged from 304 to 1513. Feature metrics such as the average response-per-feature provided a simple method to characterize similarities and differences between samples. Additionally, a statistical comparison was performed by principal component analysis. Of the 97 suspect-screening compounds, 20 were positively identified. Benzotriazole/benzothiazole-derivatives and per- and poly-fluoroalkyl substances were the most frequently detectedcompounds during suspect screening. Other compounds detected included pharmaceuticals, drug metabolites, and sucralose. Features were prioritized for non-target analysis based on in-house library matches, magnitude of response, and frequency of occurrence. Fifty-five unique compounds were positively identified via non-target analysis. The identified compounds included 17 pharmaceuticals, 17 pesticides, 13 industrial compounds, four personal-use compounds, and four biological compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Targeting the most relevant organic micropollutants (OMP) in routine analysis appears difficult due to formation of transformation products of unknown concentration or toxicity. Performance assessment of water purification processes is still based upon limited target data. Therefore, we broadened the assessment of the removal efficiencies with combined non-target and effect-directed analysis at four riverbank filtration (RBF) sites in Germany. To assess micropollutant elimination, constancy and formation during different seasons, considering local redox conditions, travel distances and total component number in the river, non-target analysis features were grouped into categories. Furthermore, RBF sites were investigated with four endpoints (baseline toxicity, acetylcholinesterase inhibition, antibiotic effects and estrogenic effects) for thin-layer chromatography - effect-directed analysis for the first time. Results showed elimination or reduction of many features and effects, but also constancy and formation of varying proportions. Fall river samples showed precipitation-caused dilution in both tests. Spring samples showed increased effects only in acetylcholinesterase inhibition and estrogenic effects, probably due to phytoestrogens or algae bloom during vegetation period. Sites were ranked considering the total number of features, group proportions, seasonal variations and intensity and number of effects in abstraction wells. Oxic conditions and low initial component numbers in the river (Ruhr sites) resulted in less effects and fewer formations. Longer travel distances were important for a more efficient reduction of effects and features. Combination of non-target and effect-directed analysis proved to be valuable for a more comprehensive assessment of process performance beyond target analysis as also unknown OMP are observed with both methods., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Publicly available chemical assessments of hydraulic fracturing related waters are generally based on shale gas practices in the U.S. There is a lack of information on hydraulic fracturing related gas development from EU countries and more generally on other types of extractions. This research fills this knowledge gap by presenting chemical and bioassay assessments of hydraulic fracturing related waters from a tight gas development in the Netherlands. Fracturing fluid, flowback water and groundwater from surrounding aquifers before and after the actual fracturing were analysed by means of high resolution liquid chromatography tandem mass spectrometry, the Ames test and three chemical activated luciferase gene expression bioassays aimed at determining genotoxicity, oxidative stress response and polyaromatic hydrocarbon contamination. After sample enrichment a higher number of peaks can be found in both fracturing fluid and flowback samples. No clear differences in chemical composition were shown in the groundwater samples before and after hydraulic fracturing. Preliminary environmental fate data of the tentatively identified chemicals points towards persistence in water. Clear genotoxic and oxidative stress responses were found in the fracturing fluid and flowback samples. A preliminary suspect screening resulted in 25 and 36 matches in positive and negative ionisation respectively with the 338 possible suspect candidates on the list. Extensive measures relating to the handling, transport and treatment of hydraulic fracturing related waters are currently in place within the Dutch context. The results of the present study provide a scientific justification for such measures taken to avoid adverse environmental and human health impacts., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Disinfected drinking water contains hundreds of disinfection by-products (DBPs) that are formed by the reaction of disinfectants with natural and anthropogenic organic matter, bromide, and iodide. Understanding what these DBPs are is important because millions of people worldwide consume drinking water every day, and human epidemiologic studies have reported cancer, miscarriage, and birth defects from consuming such waters. While more than 600 DBPs are reported in the literature, very few studies quantify complete classes of chlorinated, brominated, and iodinated DBPs. Also, very few studies conduct comprehensive non-target analyses of unknown DBPs to characterize the complete DBP exposure (the exposome). We developed a new gas chromatography (GC)-mass spectrometry (MS) method that simultaneously quantifies 39 priority unregulated DBPs from six different chemical classes (haloacetaldehydes, haloketones, haloacetamides, haloacetonitriles, halonitromethanes, and iodinated-trihalomethanes) and analyzes unknown DBPs with mass accuracy <600 ppm under full-scan conditions. Using a new type of time-of-flight (TOF) mass spectrometer, which combines selected ion monitoring (SIM)-level sensitivity with mass accuracy of ±0.05 Da, method detection limits of 3-61 ng/L were achieved. These levels were found to be quite comparable to those of a widely used single quadrupole mass spectrometer (2-90 ng/L) operated in SIM mode. However, analysis using this TOF mass spectrometer offers two additional advantages over traditional quadrupole-MS: (1) full-scan data, which provides additional confidence for target analytes, as well as complete mass spectra for unknown analysis, and (2) two decimal place mass accuracy, which allows additional confidence for target analytes and importantly, molecular formula indication for unknowns. High resolution accurate mass TOF was also used to validate identification of selected compounds. This new method was demonstrated on finished drinking waters from three different drinking water plants, where target quantification and non-target unknown analyses were performed simultaneously during the same run. This enabled the quantification of 39 DBPs, along with the non-target identification of many other drinking water contaminants, including two additional non-target DBPs: N,N-dimethylacetamide and N-nitrosodibutylamine., (Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Monitored contaminants in drinking water represent a small portion of the total compounds present, many of which may be relevant to human health. To understand the totality of human exposure to compounds in drinking water, broader monitoring methods are imperative. In an effort to more fully characterize the drinking water exposome, point-of-use water filtration devices (Brita ® filters) were employed to collect time-integrated drinking water samples in a pilot study of nine North Carolina homes. A suspect screening analysis was performed by matching high resolution mass spectra of unknown features to molecular formulas from EPA's DSSTox database. Candidate compounds with those formulas were retrieved from the EPA's CompTox Chemistry Dashboard, a recently developed data hub for approximately 720,000 compounds. To prioritize compounds into those most relevant for human health, toxicity data from the US federal collaborative Tox21 program and the EPA ToxCast program, as well as exposure estimates from EPA's ExpoCast program, were used in conjunction with sample detection frequency and abundance to calculate a "ToxPi" score for each candidate compound. From ∼15,000 molecular features in the raw data, 91 candidate compounds were ultimately grouped into the highest priority class for follow up study. Fifteen of these compounds were confirmed using analytical standards including the highest priority compound, 1,2-Benzisothiazolin-3-one, which appeared in 7 out of 9 samples. The majority of the other high priority compounds are not targets of routine monitoring, highlighting major gaps in our understanding of drinking water exposures. General product-use categories from EPA's CPCat database revealed that several of the high priority chemicals are used in industrial processes, indicating the drinking water in central North Carolina may be impacted by local industries., (Published by Elsevier Ltd.)

A comprehensive risk management on human exposure to cyanotoxins, whose production is actually unpredictable, is limited by reliable analytical tools for monitoring as many toxic algal metabolites as possible. Two analytical approaches based on a LC-QTOF system for target analysis and suspect screening of cyanotoxins in freshwater were presented. A database with 369 compounds belonging to cyanobacterial metabolites was developed and used for a retrospective data analysis based on high resolution mass spectrometry (HRMS). HRMS fragmentation of the suspect cyanotoxin precursor ions was subsequently performed for correctly identifying the specific variants. Alternatively, an automatic tandem HRMS analysis tailored for cyanotoxins was performed in a single chromatographic run, using the developed database as a preferred precursor ions list. Twenty-five extracts of surface and drinking waters contaminated by cyanobacteria were processed. The identification of seven uncommon microcystins (M(O)R, MC-FR, MSer 7 -YR, D-Asp 3 MSer 7 -LR, MSer 7 -LR, dmAdda-LR and dmAdda-YR) and 6 anabaenopeptins (A, B, F, MM850, MM864, oscyllamide Y) was reported. Several isobaric variants, fully separated by chromatography, were pointed out. The developed methods are proposed to be used by environmental and health agencies for strengthening the surveillance monitoring of cyanotoxins in water., (Copyright © 2017 Elsevier B.V. All rights reserved.)

On-site sewage treatment facilities (OSSFs), which are used to reduce nutrient emissions in rural areas, were screened for anthropogenic compounds with two-dimensional gas chromatography-mass spectrometry (GC×GC-MS). The detected compounds were prioritized based on their persistence, bioaccumulation, ecotoxicity, removal efficiency, and concentrations. This comprehensive prioritization strategy, which was used for the first time on OSSF samples, ranked galaxolide, α-tocopheryl acetate, octocrylene, 2,4,7,9-tetramethyl-5-decyn-4,7-diol, several chlorinated organophosphorus flame retardants and linear alkyl benzenes as the most relevant compounds being emitted from OSSFs. Twenty-six target analytes were then selected for further removal efficiency analysis, including compounds from the priority list along with substances from the same chemical classes, and a few reference compounds. We found significantly better removal of two polar contaminants 2,4,7,9-tetramethyl-5-decyn-4,7-diol (p=0.0003) and tris(2-butoxyethyl) phosphate (p=0.005) in soil beds, a common type of OSSF in Sweden, compared with conventional sewage treatment plants. We also report median removal efficiencies in OSSFs for compounds not studied in this context before, viz. α-tocopheryl acetate (96%), benzophenone (83%), 2-(methylthio)benzothiazole (64%), 2,4,7,9-tetramethyl-5-decyn-4,7-diol (33%), and a range of organophosphorus flame retardants (19% to 98%). The environmental load of the top prioritized compounds in soil bed effluents were in the thousands of nanogram per liter range, viz. 2,4,7,9-tetramethyl-5-decyn-4,7-diol (3000ngL -1 ), galaxolide (1400ngL -1 ), octocrylene (1200ngL -1 ), and α-tocopheryl acetate (660ngL -1 )., (Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.)

Target compound analysis with scanning mass spectrometers such as quadrupole or magnetic sector instruments is used extensively in environmental chemistry because of the selectivity, sensitivity, and robustness. Yet, target compound analysis selectively ignores the majority of compounds present in a sample, especially in complex matrices like fish. In this study, time-of-flight mass spectrometry was used to screen for and identify halogenated compounds in American eels (Anguilla rostrata). Individual and then pooled eel samples were analysed using electron ionization and electron capture negative ionization (ECNI) modes. Eels were differentiated by principal component analysis of chemical profiles and were grouped corresponding to their capture location, all with a single instrument injection per sample. Bromine containing compounds were further investigated by taking advantage of the selectivity of ECNI by utilizing the Br(-) ion m/z 79 and 81. A total of 51 brominated compounds were detected and their identities were attempted by authentic standards, library searching, and/or chemical formula prediction based on accurate mass measurements. Several PBDEs were identified in the samples, and the majority of the non-PBDEs identified were bromophenols, bromoanisoles, and bromobenzenes. These classes of compounds are synthesized for use in flame retardant production either as intermediates or as final products. However, their occurrence in eels was most likely the result of metabolism or break-down products of high production volume flame retardants like polybrominated diphenyl ethers and bromophenoxy compounds., (Crown Copyright © 2014. Published by Elsevier Ltd. All rights reserved.)