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Pharmaceuticals and their human metabolites are contaminants of emerging concern in the aquatic environment. Most monitoring studies focus on a limited set of parent compounds and even fewer metabolites. However, more than 50% of the most consumed pharmaceuticals are excreted in higher amounts as metabolites than as parents, as confirmed by a literature analysis within this study. Hence, we applied a wide-scope suspect screening approach to identify human pharmaceutical metabolites in wastewater influent from three Swiss treatment plants. Based on consumption amounts and human metabolism data, a suspect list comprising 268 parent compounds and over 1500 metabolites was compiled. Online solid phase extraction combined with liquid chromatography coupled to high-resolution tandem mass spectrometry was used to analyze the samples. Data processing, annotation, and structure elucidation were achieved with various tools, including molecular networking as well as SIRIUS/CSI:FingerID and MetFrag for MS2 spectra rationalization. We confirmed 37 metabolites with reference standards and 16 by human liver S9 incubation experiments. More than 25 metabolites were detected for the first time in influent wastewater. Semiquantification with MS2Quant showed that metabolite to parent concentration ratios were generally lower compared to literature expectations, probably due to further metabolite transformation in the sewer system or limitations in the metabolite detection. Nonetheless, metabolites pose a large fraction to the total pharmaceutical contribution in wastewater, highlighting the need for metabolite inclusion in chemical risk assessment.

Cationic surfactants are used in many industrial processes and in consumer products with concurrent release into the aquatic environment, where they may accumulate in aquatic organisms to regulatoryly relevant thresholds. Here, we aimed to better understand the bioconcentration behavior of three selected cationic surfactants, namely N,N -dimethyldecylamine (T10), N -methyldodecylamine (S12), and N,N,N -trimethyltetradecylammonium cation (Q14), in the cells of fish liver (RTL-W1) and gill (RTgill-W1) cell lines. We conducted full mass balances for bioconcentration tests with the cell cultures, in which the medium, the cell surface, the cells themselves, and the plastic compartment were sampled and quantified for each surfactant by HPLC MS/MS. Accumulation in/to cells correlated with the surfactants' alkyl chain lengths and their membrane lipid-water partitioning coefficient, D MLW . Cell-derived bioconcentration factors (BCF) of T10 and S12 were within a factor of 3.5 to in vivo BCF obtained from the literature, while the cell-derived BCF values for Q14 were >100 times higher than the in vivo BCF. From our experiments, rainbow trout cell lines appear as a suitable conservative in vitro screening method for bioconcentration assessment of cationic surfactants and are promising for further testing.

Environmental risk assessment of chemical contaminants requires prioritizing of substances taken up by biota as it is a starting point for potential adverse effects. Although knowledge about the occurrence of known chemical pollutants in aquatic organisms has significantly improved during the last decade, there is still a poor understanding for a broad range of more polar compounds. To tackle this issue, we proposed an approach that identifies bioaccumulative and biomagnifiable polar chemicals using liquid chromatography coupled with electrospray ionization to high resolution tandem mass spectrometry (LC-HRMS/MS) and combine it with trend analysis using hierarchical clustering. As a proof-of-concept, this approach was implemented on various organisms and compartments (sediment, litter leaves, periphytic biofilm, invertebrates and fish) collected from a small urban river. HRMS/MS data measured via data-independent acquisition mode were retrospectively analysed using two analytical strategies: (1) retrospective target and (2) suspect/non-target screening. In the retrospective target analysis, 56 of 361 substances spanning a broad range of contaminant classes were detected (i.e. 26 in fish, 18 in macroinvertebrates, 28 in leaves, 29 in periphyton and 32 in sediments, with only 7 common to all compartments), among which 49 could be quantified using reference standards. The suspect screening approach based on two suspect lists (in-house, Norman SusDat) led to the confirmation of 5 compounds with standards (three xenobiotics at level 1 and two lipids at level 2) and tentative identification of seven industrial or natural chemicals at level 2 and 3 through a mass spectra library match. Overall, this proof-of-concept study provided a more comprehensive picture of the exposure of biota to emerging contaminants (i.e., the internal chemical exposome) and potential bioaccumulation or biomagnification of polar compounds along the trophic chain., 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.)

Wastewater treatment plants (WWTPs) are a major source of micropollutants to surface waters. Currently, their chemical or biological monitoring is realized by using grab or composite samples, which provides only snapshots of the current wastewater composition. Especially in WWTPs with industrial input, the wastewater composition can be highly variable and a continuous assessment would be advantageous, but very labor and cost intensive. A promising concept are automated real-time biological early warning systems (BEWS), where living organisms are constantly exposed to the water and an alarm is triggered if the organism's responses exceed a harmful threshold of acute toxicity. Currently, BEWS are established for drinking water and surface water but are seldom applied to monitor wastewater. This study demonstrates that a battery of BEWS using algae (Chlorella vulgaris in the Algae Toximeter, bbe Moldaenke), water flea (Daphnia magna in the DaphTox II, bbe Moldaenke) and gammarids (Gammarus pulex in the Sensaguard, REMONDIS Aqua) can be adapted for wastewater surveillance. For continuous low-maintenance operation, a back-washable membrane filtration system is indispensable for adequate preparation of treated wastewater. Only minor deviations in the reaction of the organisms towards treated and filtered wastewater compared to surface waters were detected. After spiking treated wastewater with two concentrations of the model compounds diuron, chlorpyrifos methyl, and sertraline, the organisms in the different BEWS showed clear responses depending on the respective compound, concentration and mode of action. Immediate effects on photosynthetic activity of algae were detected for diuron exposure, and strong behavioral changes in water flea and gammarids after exposure to chlorpyrifos methyl or sertraline were observed, which triggered automated alarms. Different types of data analysis were applied to extract more information out of the specific behavioral traits, than only provided by the vendors algorithms. To investigate, whether behavioral movement changes can be linked to impact other endpoints, the effects on feeding activity of G. pulex were evaluated and results indicated significant differences between the exposures. Overall, these findings provide an important basis indicating that BEWS have the potential to act as alarm systems for pollution events in the wastewater sector., 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 Authors. Published by Elsevier Ltd.. All rights reserved.)

Persistent, mobile and toxic (PMT), and very persistent and very mobile (vPvM) substances pose a threat to the water cycle but are often not covered in conventional environmental monitoring programs. Within this realm of substances, one compound class of concern are pesticides and their transformation products as they are deliberately introduced into the environment. To detect very polar anionic substances, including many pesticide transformation products with log D OW values ranging between -7.4 and 2.2, an ion chromatography high-resolution mass spectrometry method was developed in this study. Since inorganic anions, such as chloride and sulfate, interfere with the analysis of organic species, their removal via precipitation with Ba/Ag/H cartridges was assessed. To improve LOQs, vacuum-assisted evaporative concentration (VEC) was evaluated. By using VEC and removing inorganic salt ions, the median LOQ improved from 100 ng/L in evian® water without sample treatment to 10 ng/L after enrichment and 30 ng/L in karst groundwater. Using this method, twelve out of 64 substances covered by the final method were found in karst groundwater in concentrations of up to 5600 ng/L, and seven exceeded 100 ng/L. To the authors' knowledge, the dimethenamid TP M31 and chlorothalonil TP SYN548008 were detected for the first time in groundwater samples. The coupling to a high-resolution mass spectrometer also allows for non-target screening and hence, this method presents a powerful tool to tackle PMT/vPvM substances., Competing Interests: Declaration of competing interest The authors declare no competing financial interest., (Copyright © 2023 The Author(s). Published by Elsevier B.V. All rights reserved.)

Bioaccumulation of organic contaminants from contaminated food sources might pose an underestimated risk toward shredding invertebrates. This assumption is substantiated by monitoring studies observing discrepancies of predicted tissue concentrations determined from laboratory-based experiments compared with measured concentrations of systemic pesticides in gammarids. To elucidate the role of dietary uptake in bioaccumulation, gammarids were exposed to leaf material from trees treated with a systemic fungicide mixture (azoxystrobin, cyprodinil, fluopyram, and tebuconazole), simulating leaves entering surface waters in autumn. Leaf concentrations, spatial distribution, and leaching behavior of fungicides were characterized using liquid chromatography coupled with high-resolution tandem mass spectrometry (LC-HRMS/MS) and matrix-assisted laser desorption ionization-mass spectrometric imaging. The contribution of leached fungicides and fungicides taken up from feeding was assessed by assembling caged (no access) and uncaged (access to leaves) gammarids. The fungicide dynamics in the test system were analyzed using LC-HRMS/MS and toxicokinetic modeling. In addition, a summer scenario was simulated where water was the initial source of contamination and leaves contaminated by sorption. The uptake, translocation, and biotransformation of systemic fungicides by trees were compound-dependent. Internal fungicide concentrations of gammarids with access to leaves were much higher than in caged gammarids of the autumn scenario, but the difference was minimal in the summer scenario. In food choice and dissectioning experiments gammarids did not avoid contaminated leaves and efficiently assimilated contaminants from leaves, indicating the relevance of this exposure pathway in the field. The present study demonstrates the potential impact of dietary uptake on in situ bioaccumulation for shredders in autumn, outside the main application period. The toxicokinetic parameters obtained facilitate modeling of environmental exposure scenarios. The uncovered significance of dietary uptake for detritivores warrants further consideration from scientific as well as regulatory perspectives. Environ Toxicol Chem 2023;42:1993-2006. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC., (© 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.)

Permanent rainbow trout (Oncorhynchus mykiss) cell lines represent potential in vitro alternatives to experiments with fish. We here developed a method to assess the bioaccumulation potential of anionic organic compounds in fish, using the rainbow trout liver-derived RTL-W1 cell line. Based on the availability of high quality in vivo bioconcentration (BCF) and biomagnification (BMF) data and the substances' charge state at physiological pH, four anionic compounds were selected: pentachlorophenol (PCP), diclofenac (DCF), tecloftalam (TT) and benzotriazol-tert-butyl-hydroxyl-phenyl propanoic acid (BHPP). The fish cell line acute toxicity assay (OECD TG249) was used to derive effective concentrations 50 % and non-toxic exposure concentrations to determine exposure concentrations for bioaccumulation experiments. Bioaccumulation experiments were performed over 48 h with a total of six time points, at which cell, medium and plastic fractions were sampled and measured using high resolution tandem mass spectrometry after online solid phase extraction. Observed cell internal concentrations were over-predicted by K OW -derived predictions while pH-dependent octanol-water partitioning (D OW ) and membrane lipid-water partitioning (D MLW ) gave better predictions of cell internal concentrations. Measured medium and cell internal concentrations at steady state were used to calculate RTL-W1-based BCF, which were compared to D OW - or D MLW -based model approaches and in vivo data. With the exception of PCP, the cell-derived BCF best compared to D OW -based model predictions, which were higher than predictions based on D MLW . All methods predicted the in vivo BCF for diclofenac well. For PCP, the cell-derived BCF was lowest although all BCF predictions underestimated the in vivo BCF by ≥ 1 order of magnitude. The RTL-W1 cells, and all other prediction methods, largely overestimated in vivo BMF, which were available for PCP, TT and BHPP. We conclude that the RTL-W1 cell line can supplement BCF predictions for anionic compounds. For BMF estimations, however, in vitro-in vivo extrapolations need adaptation or a multiple cell line approach., 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 acceleration of global climate change draws increasing attention towards interactive effects of temperature and organic contaminants. Many studies reported a higher sensitivity of aquatic invertebrates towards contaminant exposure with increasing or fluctuating temperatures. The hypothesis of this study was that the higher sensitivity of invertebrates is associated with the changes of toxicokinetic processes that determine internal concentrations of contaminants and consequently toxic effects. Therefore, the influence of temperature on toxicokinetic processes and the underlying mechanisms were studied in two key amphipod species (Gammarus pulex and Hyalella azteca). Bioconcentration experiments were carried out at four different temperatures with a mixture of 12 exposure relevant polar organic contaminants. Tissue and medium samples were taken in regular intervals and analysed by online solid-phase extraction liquid chromatography high-resolution tandem mass spectrometry. Subsequently, toxicokinetic rates were modelled and analysed in dependence of the exposure temperature using the Arrhenius equation. An exponential relationship between toxicokinetic rates versus temperature was observed and could be well depicted by applying the Arrhenius equation. Due to a similar Arrhenius temperature of uptake and elimination rates, the bioconcentration factors of the contaminants were generally constant across the temperature range. Furthermore, the Arrhenius temperature of the toxicokinetic rates and respiration was mostly similar. However, in some cases (citalopram, cyprodinil), the bioconcentration factor appeared to be temperature dependent, which could potentially be explained by the influence of temperature on active uptake mechanisms or biotransformation. The observed temperature effects on toxicokinetics may be particularly relevant in non-equilibrated systems, such as exposure peaks in summer as exemplified by the exposure modelling of a field measured pesticide peak where the internal concentrations increased by up to fourfold along the temperature gradient. The results provide novel insights into the mechanisms of chemical uptake, biotransformation and elimination in different climate scenarios and can improve environmental risk assessment., (© 2022 The Authors. Global Change Biology published by John Wiley & Sons Ltd.)

Bioaccumulation and trophic transfer of persistent legacy contaminants have been intensively characterized, but little is known on the contaminants of emerging concern (CECs) in freshwater food webs. Herein, we comprehensively screened CECs with a focus on polar substances and further evaluated their trophic transfer behavior in selected items from the food web of Lake Templin, Germany. Weselected one plankton, two mussel, and nine fish samples covering three trophic levels. With an effective multi-residue sample preparation method and high-resolution mass spectrometry-based target, suspect, and non-target screening, we characterized 477 targets and further screened unknown features in complex biota matrices. Of the 477 targets, 145 were detected and quantified in at least one species (0.02-3640 ng/g, dry weight). Additionally, the suspect and non-target analysis with experimental mass spectra libraries and in silico techniques (MetFrag and SIRIUS4/CSI:FingerID) enabled further identification of 27 unknown compounds with 19 confirmed by reference standards. Overall, the detected compounds belong to a diverse group of chemicals, including 71 pharmaceuticals, 27 metabolites, 26 pesticides, 16 per- and polyfluoroalkyl substances (PFASs), 4 plasticizers, 3 flame retardants, 11 other industrial chemicals and 14 others. Moreover, we determined the trophic magnification factor (TMF) of 34 polar CECs with >80% detection frequency, among which 6 PFASs including perfluorooctane sulfonic acid (PFOS), perfluorodecanoic acid (PFDA), perfluorohexane sulfonic acid (PFHxS), perfluorotridecanoic acid (PFTrA), perfluorotetradecanoic acid (PFTeA), and perfluoroundecanoic acid (PFUnA), exhibited biomagnification potential (TMF =1.8 - 4.2, p < 0.05), whereas 5 pharmaceuticals (phenazone, progesterone, venlafaxine, levamisole, and lidocaine) and 1 personal care product metabolite (galaxolidone) showed biodilution potential (TMF = 0.4 - 0.6, p < 0.05)., (Copyright © 2022. Published by Elsevier Ltd.)

Toxic plant secondary metabolites (PSMs), so-called phytotoxins, occur widely in plant species. Many of these phytotoxins have similar mobility, persistence, and toxicity properties in the environment as anthropogenic micropollutants, which increasingly contaminate surface waters. Although recent case studies have shown the aquatic relevance of phytotoxins, the overall exposure remains unknown. Therefore, we performed a detailed occurrence analysis covering 134 phytotoxins from 27 PSM classes. Water samples from seven small Swiss streams with catchment areas from 1.7 to 23 km 2 and varying land uses were gathered over several months to investigate seasonal impacts. They were complemented with samples from different biogeographical regions to cover variations in vegetation. A broad SPE-LC-HRMS/MS method was applied with limits of detection below 5 ng/L for over 80% of the 134 included phytotoxins. In total, we confirmed 39 phytotoxins belonging to 13 PSM classes, which corresponds to almost 30% of all included phytotoxins. Several alkaloids were regularly detected in the low ng/L-range, with average detection frequencies of 21%. This is consistent with the previously estimated persistence and mobility properties that indicated a high contamination potential. Coumarins were previously predicted to be unstable, however, detection frequencies were around 89%, and maximal concentrations up to 90 ng/L were measured for fraxetin produced by various trees. Overall, rainy weather conditions at full vegetation led to the highest total phytotoxin concentrations, which might potentially be most critical for aquatic organisms., 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 © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Natural estrogens are present in high concentrations in livestock slurries, which are often applied to agricultural fields in large quantities. As such, the export of slurry-derived natural estrogens from tile-drained fields is a potential source for estrogenic pollution in surface waters. Yet despite the abundance of tile-drained fields in Central Europe, export of natural estrogens from agricultural fields receiving livestock slurries is rarely studied in this region. In an effort to fill this knowledge gap, here we applied natural estrogens to Swiss experimental fields in the form of cattle slurry, pig slurry or dissolved in water, and quantified them in flow-proportionally collected drainage water over 18 months. After pig and cattle slurry applications, concentration maxima in drainage water of 73, 8, 37, and 60 ng L -1 for 17α-estradiol (E2α), 17β-estradiol (E2β), estrone (E1), and estriol (E3), respectively, were observed shortly after rain events. The exported fractions of individual natural estrogens to tile drains were on average 0.26% (ranging from 0.08 to 0.41%) after cattle, and 0.18% (0.03-0.40%) after pig slurry applications. Such numbers were higher than expected from the leaching potential based on substance properties, and comparable to those of more mobile micropollutants previously studied on the same fields. Natural estrogens were mainly exported to tile drains through preferential flow. Exported fractions were lower when applied in aqueous solution than when applied in slurry, pointing to particle-facilitated transport to tile drains when applied in slurry. In Switzerland, the estimated 6.3, 0.6, 7.4, and 7.7 g of E2α, E2β, E1, and E3, respectively, exported through the tile-drained agricultural area per year contribute little to the total natural estrogen load received by surface waters. However, after slurry applications in highly drained catchments, natural estrogen emissions to tile drains can cause short term (i.e. less than 1 week) estrogenic exposure in nearby streams., Competing Interests: Declaration of competing interest The authors declare no competing financial interest or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by 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.)

The exposure of ecologically critical invertebrate species to biologically active pharmaceuticals poses a serious risk to the aquatic ecosystem. Yet, the fate and toxic effects of pharmaceuticals on these nontarget aquatic invertebrates and the underlying mechanisms are poorly studied. Herein, we investigated the toxicokinetic (TK) processes (i.e., uptake, biotransformation, and elimination) of the pharmaceutical diclofenac and its biotransformation in the freshwater invertebrate Hyalella azteca . We further employed mass spectrometry-based metabolomics to assess the toxic effects of diclofenac on the metabolic functions of H . azteca exposed to environmentally relevant concentrations (10 and 100 μg/L). The TK results showed a quick uptake of diclofenac by H . azteca (maximum internal concentration of 1.9 μmol/kg) and rapid formation of the conjugate diclofenac taurine (maximum internal concentration of 80.6 μmol/kg), indicating over 40 times higher accumulation of diclofenac taurine than that of diclofenac in H . azteca . Depuration kinetics demonstrated that the elimination of diclofenac taurine was 64 times slower than diclofenac in H . azteca . Metabolomics results suggested that diclofenac inhibited prostaglandin synthesis and affected the carnitine shuttle pathway at environmentally relevant concentrations. These findings shed light on the significance of the TK process of diclofenac, especially the formation of diclofenac taurine, as well as the sublethal effects of diclofenac on the bulk metabolome of H . azteca . Combining the TK processes and metabolomics provides complementary insights and thus a better mechanistic understanding of the effects of diclofenac in aquatic invertebrates.

Groundwater is a major drinking water resource but its quality with regard to organic micropollutants (MPs) is insufficiently assessed. Therefore, we aimed to investigate Swiss groundwater more comprehensively using liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS). First, samples from 60 sites were classified as having high or low urban or agricultural influence based on 498 target compounds associated with either urban or agricultural sources. Second, all LC-HRMS signals were related to their potential origin (urban, urban and agricultural, agricultural, or not classifiable) based on their occurrence and intensity in the classified samples. A considerable fraction of estimated concentrations associated with urban and/or agricultural sources could not be explained by the 139 detected targets. The most intense nontarget signals were automatically annotated with structure proposals using MetFrag and SIRIUS4/CSI:FingerID with a list of >988,000 compounds. Additionally, suspect screening was performed for 1162 compounds with predicted high groundwater mobility from primarily urban sources. Finally, 12 nontargets and 11 suspects were identified unequivocally (Level 1), while 17 further compounds were tentatively identified (Level 2a/3). amongst these were 13 pollutants thus far not reported in groundwater, such as: the industrial chemicals 2,5-dichlorobenzenesulfonic acid (19 detections, up to 100 ng L -1 ), phenylphosponic acid (10 detections, up to 50 ng L -1 ), triisopropanolamine borate (2 detections, up to 40 ng L -1 ), O-des[2-aminoethyl]-O-carboxymethyl dehydroamlodipine, a transformation product (TP) of the blood pressure regulator amlodipine (17 detections), and the TP SYN542490 of the herbicide metolachlor (Level 3, 33 detections, estimated concentrations up to 100-500 ng L -1 ). One monitoring site was far more contaminated than other sites based on estimated total concentrations of potential MPs, which was supported by the elucidation of site-specific nontarget signals such as the carcinogen chlorendic acid, and various naphthalenedisulfonic acids. Many compounds remained unknown, but overall, source related prioritisation proved an effective approach to support identification of compounds in groundwater., 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 © 2021 The Author(s). Published by Elsevier Ltd.. All rights reserved.)

Synthetic water-soluble polymeric materials are widely employed in e.g. cleaning detergents, personal care products, paints or textiles. Accordingly, these compounds reach sewage treatment plants and may enter receiving waters and the aquatic environment. Characteristically, these molecules show a polydisperse molecular weight distribution, comprising multiple repeating units, i.e. a homologous series (HS). Their analysis in environmentally relevant samples has received some attention over the last two decades, however, the majority of previous studies focused on surfactants and a molecular weight range <1000 Da. To capture a wider range on the mass versus polarity plane and extend towards less polar contaminants, a workflow was established using three different ionization strategies, namely conventional electrospray ionization, atmospheric pressure photoionization and atmospheric pressure chemical ionization. The data evaluation consisted of suspect screening of ca. 1200 suspect entries and a non-target screening of HS with pre-defined accurate mass differences using ca. 400 molecular formulas of repeating units of HS as input and repeating retention time shifts as HS indicator. To study the fate of these water-soluble polymeric substances in the wastewater treatment process, the different stages, i.e. after primary and secondary clarifier, and after ozonation followed by sand filtration, were sampled at a Swiss wastewater treatment plant. Remaining with two different ionization interfaces, ESI and APPI, in both polarities, a non-targeted screening approach led to a total number of 146 HS (each with a minimum number of 4 members), with a molecular mass of up to 1200 detected in the final effluent. Of the 146 HS, ca 15% could be associated with suspect hits and approximately 25% with transformation products of suspects. Tentative characterization or probable chemical structure could be assigned to almost half of the findings. In positive ionization mode various sugar derivatives with differing side chains, for negative mode structures with sulfonic acids, could be characterized. The number of detected HS decreased significantly over the three treatment stages. For HS detectable also in the biological and oxidative treatment stages, a change in HS distribution towards to lower mass range was often observed., 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. Published by Elsevier Ltd.)

Pesticide contamination of agricultural streams has widely been analysed in regions of high intensity agriculture such as in Western Europe or North America. The situation of streams subject to low intensity agriculture relying on human and animal labour, as in parts of Romania, remains unknown. To close this gap, we determined concentrations of 244 pesticides and metabolites at 19 low-order streams, covering sites from low to high intensity agriculture in a region of Romania. Pesticides were sampled with two passive sampling methods (styrene-divinylbenzene (SDB) disks and polydimethylsiloxane (PDMS) sheets) during three rainfall events and at base flow. Using the toxic unit approach, we assessed the toxicity towards algae and invertebrates. Up to 50 pesticides were detected simultaneously, resulting in sum concentrations between 0.02 and 37 µg L -1 . Both, the sum concentration as well as the toxicities were in a similar range as in high intensity agricultural streams of Western Europe. Different proxies of agricultural intensity did not relate to in-stream pesticide toxicity, contradicting the assumption of previous studies. The toxicity towards invertebrates was positively related to large scale variables such as the catchment size and the agricultural land use in the upstream catchment and small scale variables including riparian plant height, whereas the toxicity to algae showed no relationship to any of the variables. Our results suggest that streams in low intensity agriculture, despite a minor reported use of agrochemicals, exhibit similar levels of pesticide pollution as in regions of high intensity agriculture., 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.)

Natural estrogens such as 17α-estradiol (E2α), 17β-estradiol (E2β), estrone (E1), and estriol (E3), released to surface waters from both urban and agricultural sources, are endocrine disrupting for fish. Here, we assess the prevalence of livestock farming derived natural estrogens in tributaries and ponds in the agriculturally dominated catchment of Lake Baldegg, Switzerland. Passive samplers were deployed in the main tributary and daily time-proportional water samples were collected in five tributaries for 30 days at the beginning of the vegetation period. Furthermore, we took grab samples of 12 ponds in the catchment. Aqueous samples were liquid-liquid extracted, derivatized, and analysed with LC-MS/MS and stream water samples additionally with ERα-CALUX, a bioassay for assessing total estrogenic activity. Natural estrogens were regularly detected, with mean concentrations ranging from below the limit of detection to 0.55 ng L -1 for E2β and E1, respectively, and passive sampling and bioassay results largely confirmed these findings. Monte Carlo simulated mean natural estrogen concentrations underestimated measured ones by a factor of three to 11. An agricultural area's hydrological contribution and connectivity to surface waters seemed to be more important for the development of estrogen concentrations in streams than livestock densities in a catchment or the actual loads of slurry applied. Pond water occasionally contained natural estrogens in concentrations up to 8.6 ng L -1 for E2α. The environmental quality standards of the European Union (0.4 ng L -1 for E2β and 3.6 ng L -1 for E1) were never exceeded for longer than a day in tributaries, but E1 reached critical concentrations for aquatic organisms in ponds.

Chlorothalonil, a fungicide applied for decades worldwide, has recently been banned in the European Union (EU) and Switzerland due to its carcinogenicity and the presence of potentially toxic transformation products (TPs) in groundwater. The spread and concentration range of chlorothalonil TPs in different drinking water resources was examined (73 groundwater and four surface water samples mainly from Switzerland). The chlorothalonil sulfonic acid TPs (R471811, R419492, R417888) occurred more frequently and at higher concentrations (detected in 65-100% of the samples, ≤2200 ngL -1 ) than the phenolic TPs (SYN507900, SYN548580, R611968; detected in 10-30% of the samples, ≤130 ngL -1 ). The TP R471811 was found in all samples and even in 52% of the samples above 100 ngL -1 , the drinking water standard in Switzerland and other European countries. Therefore, the abatement of chlorothalonil TPs was investigated in laboratory and pilot-scale experiments and along the treatment train of various water works, comprising aquifer recharge, UV disinfection, ozonation, advanced oxidation processes (AOPs), activated carbon treatment, and reverse osmosis. The phenolic TPs can be abated during ozonation (second order rate constant k O3 ∼10 4  M -1 s -1 ) and by reaction with hydroxyl radicals (OH) in AOPs (k OH ∼10 9  M -1 s -1 ). In contrast, the sulfonic acid TPs, which occurred in higher concentrations in drinking water resources, react only very slowly with ozone (k O3 <0.04 M -1 s -1 ) and OH (k OH  <5.0 × 10 7  M -1 s -1 ) and therefore persist in ozonation and OH-based AOPs. Activated carbon retained the very polar TP R471811 only up to a specific throughput of 25 m 3 kg -1 (20% breakthrough), similarly to the X-ray contrast agent diatrizoic acid. Reverse osmosis was capable of removing all chlorothalonil TPs by ≥98%., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Preventing and remedying fresh waters from chemical pollution is a fundamental societal and scientific challenge. With other nonchemical stressors potentially co-occurring, assessing the ecological consequences of reducing chemical loads in the environment is arduous. In this case study, we comparatively assessed the community structure, functions, and tolerance of stream biofilms to micropollutant mixtures extracted from deployed passive samplers at wastewater treatment plant effluents. These biofilms were growing up- and downstream of one upgraded and two nonupgraded wastewater treatment plants before being sampled for analyses. Our results showed a substantial decrease in micropollutant concentrations by 85%, as the result of upgrading the wastewater treatment plant at one of the sampling sites with activated carbon filtration. This decrease was positively correlated with a loss of community tolerance to micropollutants and the recovery of the community structure downstream of the effluent. On the other hand, downstream biofilms at the nonupgraded sites displayed higher tolerance to the extracts than the upstream biofilms. The observed higher tolerance was positively linked to micropollutant levels both in stream water and in biofilm samples, and to shifts in the community structure. Although more investigations of upgraded sites are needed, our findings point toward the suitability of using community tolerance for the retrospective assessment of the risks posed by micropollutants, to assess community recovery, and to relate effects to causes in complex environmental conditions.

Sertraline is one of the most commonly prescribed antidepressants in the last few years. Therefore, it is not surprising that it is regularly detected in wastewaters, surface waters, sediments, biosolids and biota. Effluents from wastewater treatment plants are the main contributors to its presence in the environment. The presented study aims to elucidate the processes involved in its removal, concentrating mainly on sorption and biodegradation during wastewater treatment. We performed our laboratory scale experiments in two sets of experiments: 1) batch biodegradation and sorption experiments and 2) flow-through laboratory scale pilot wastewater treatment bioreactors. The batch experiments revealed that sorption to activated sludge was the leading removal process, eliminating up to 90% of sertraline present in the batches. Biodegradation was however the secondary removal process, influenced by the presence of alternative easily biodegradable carbon sources. We postulated chemical structures of ten detected biotransformation products. Among these, we propose the previously recognized metabolite norsertraline, sertraline ketone and hydroxy-sertraline. All the remaining biotransformation products are herein reported for the first time. The removal efficiency of approximately 94% was determined after the treatment in the flow-through bioreactors. To support our findings, we sampled influents and effluents from two wastewater treatment plants and untreated wastewater from a psychiatric hospital. Removal efficiencies of 81% and 77% were determined, and along with the parent compound sertraline, the presence of eight transformation products was confirmed in the actual wastewaters., 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.)

Many organic contaminants entering the aquatic environment feature stereogenic structural elements that give rise to enantiomerism. While abiotic processes usually act identical on enantiomers, biotic processes, such as biodegradation often result in enantiomeric fractionation (EFr), i.e., the change of the relative abundance of enantiomers. Therefore, EFr offers the opportunity to differentiate biodegradation in complex environmental systems from abiotic processes. In this study, an achiral-chiral two-dimensional liquid chromatographic method for the enantioseparation of selected pharmaceuticals was developed. This method was then applied to determine the enantiomeric compositions of eight chiral pharmaceuticals in 20 water-sediment test flumes and test EFr as an indicator of biodegradation. While all eight substances were attenuated by at least 60%, five (atenolol, metoprolol, celiprolol, propranolol, and flecainide) displayed EFr. No EFr was observed for citalopram, fluoxetine, and venlafaxine despite almost complete attenuation (80 to 100%). Celiprolol, a barely studied β-blocker, revealed the most distinct EFr among all investigated substances; however, EFr varied considerably with biodiversity. Celiprolol-H2 was identified as a biological transformation product possibly formed by reduction of the celiprolol keto group through a highly regio- and enantioselective carbonyl reductase. While celiprolol-H2 was observed across all flumes, as expected, its formation was faster in flumes with high bacterial diversity where also EFr was highest. Overall, EFr and transformation product formation together served as good indicators of biological processes; however, the strong dependence of EFr on biodiversity limits its usefulness in complex environmental systems.

Environmental risk assessment associated with aquatic and terrestrial contamination is mostly based on predicted or measured environmental concentrations of a limited list of chemicals in a restricted number of environmental compartments. High resolution mass spectrometry (HRMS) can provide a more comprehensive picture of exposure to harmful chemicals, particularly through the retrospective analysis of digitally stored HRMS data. Using this methodology, our study characterized the contamination of various environmental compartments including 154 surface water, 46 urban effluent, 67 sediment, 15 soil, 34 groundwater, 24 biofilm, 41 gammarid and 49 fish samples at 95 sites widely distributed over the Swiss Plateau. As a proof-of-concept, we focused our investigation on antifungal azoles, a class of chemicals of emerging concern due to their endocrine disrupting effects on aquatic organisms and humans. Our results demonstrated the occurrence of antifungal azoles and some of their (bio)transformation products in all the analyzed compartments (0.1-100 ng/L or ng/g d.w.). Comparison of actual and predicted concentrations showed the partial suitability of level 1 fugacity modelling in predicting the exposure to azoles. Risk quotient calculations additionally revealed risk of exposure especially if some of the investigated rivers and streams are used for drinking water production. The case study clearly shows that the retrospective analysis of HRMS/MS data can improve the current knowledge on exposure and the related risks to chemicals of emerging concern and can be effectively employed in the future for such purposes., 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 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Hyporheic zones are the water-saturated flow-through subsurfaces of rivers which are characterized by the simultaneous occurrence of multiple physical, biological, and chemical processes. Two factors playing a role in the hyporheic attenuation of organic contaminants are sediment bedforms (a major driver of hyporheic exchange) and the composition of the sediment microbial community. How these factors act on the diverse range of organic contaminants encountered downstream from wastewater treatment plants is not well understood. To address this knowledge gap, we investigated dissipation half-lives (DT50s) of 31 substances (mainly pharmaceuticals) under different combinations of bacterial diversity and bedform-induced hyporheic flow using 20 recirculating flumes in a central composite face factorial design. By combining small-volume pore water sampling, targeted analysis, and suspect screening, along with quantitative real-time PCR and time-resolved amplicon Illumina MiSeq sequencing, we determined a comprehensive set of DT50s, associated bacterial communities, and microbial transformation products. The resulting DT50s of parent compounds ranged from 0.5 (fluoxetine) to 306 days (carbamazepine), with 20 substances responding significantly to bacterial diversity and four to both diversity and hyporheic flow. Bacterial taxa that were associated with biodegradation included Acidobacteria (groups 6, 17, and 22), Actinobacteria ( Nocardioides and Illumatobacter ), Bacteroidetes ( Terrimonas and Flavobacterium ) and diverse Proteobacteria (Pseudomonadaceae, Sphingomonadaceae, and Xanthomonadaceae). Notable were the formation of valsartan acid from irbesartan and valsartan, the persistence of N -desmethylvenlafaxine across all treatments, and the identification of biuret as a novel transformation product of metformin. Twelve additional target transformation products were identified, which were persistent in either pore or surface water of at least one treatment, indicating their environmental relevance.

Biotransformation plays a crucial role in regulating the bioaccumulation potential and toxicity of organic compounds in organisms but is, in general, poorly understood for emerging contaminants. Here, we have used diclofenac as a model compound to study the impact of biotransformation on the bioaccumulation potential and toxicity in two keystone aquatic invertebrates: Gammarus pulex and Hyalella azteca . In both species, diclofenac was transformed into several oxidation products and conjugates, including two novel products, that is, diclofenac taurine conjugate (DCF-M403) and unexpected diclofenac methyl ester (DCF-M310.03). The ratios of biotransformation products to parent compound were 12-17 for DCF-M403 and 0.01-0.7 for DCF-M310.03 after 24 h exposure. Bioconcentration factors (BCFs) of diclofenac were 0.5 and 3.2 L kg ww -1 in H. azteca and G. pulex , respectively, whereas BCFs of DCF-M310.03 was 164.5 and 104.7 L kg ww -1 , respectively, representing a 25- to 110-fold increase. Acute toxicity of DCF-M310.03 was also higher than the parent compound in both species, which correlated well with the increased bioconcentration potential. The LC 50 of diclofenac in H. azteca was 216 mg L -1 , while that of metabolite DCF-M310.03 was reduced to only 0.53 mg L -1 , representing a 430-fold increase in acute toxicity compared to diclofenac. DCF-M403 is less toxic than its parent compound toward H. azteca , which may be linked to its slightly lower hydrophobicity. Furthermore, the transformation of diclofenac to its methyl ester derivative was explored in crude invertebrate extracts spiked with an S -adenosylmethionine cofactor, revealing possible catalysis by an S -adenosylmethionine-dependent carboxylic acid methyltransferase. Methylation of diclofenac was further detected in fish hepatocytes and human urine, indicating a broader relevance. Therefore, potentially methylated metabolites of polar contaminants should be considered for a comprehensive risk assessment in the future.

Oceans are the ultimate sink for many of the over 100 million man-made substances. Until now, monitoring was limited to a reduced number of targeted persistent organic pollutants, reaching open waters mainly via atmospheric deposition. However, the composition and fate of the thousands of pollutants reaching the marine environment though wastewater discharges from coastal sources remain largely unexplored. By combining a newly developed nontarget screening (NTS) workflow and high-resolution mass spectrometry (HRMS), we have identified over 500 sewage-derived contaminants occurring in the ocean. Samples from the NE Atlantic contained this anthropogenic imprint at distances over 50 km from the coastline and >500 m depth, beyond the continental margin. The range of identified compounds spans from pharmaceuticals and personal care products to food additives and industrial chemicals, including several that have never been reported in the environment, as they escaped conventional targeted analytical methods. Predicting the effects of the continuous input of this chemical "cocktail" on marine ecosystems is a formidable challenge, since 40% of the detected compounds lack information regarding their use and ecotoxicity.

Although the exposure assessment of wastewater-derived micropollutants via chemical, bioanalytical, and modeling methods in environmental compartments is becoming more frequent, the whole-body burden (i.e., internal concentrations) in nontarget organisms is rarely assessed. An understanding of the internal concentration fluctuation is especially important when exploring the mechanistic linkage between exposure and effects. In this study, we coupled a simple river model with a first-order toxicokinetic (TK) model to predict the concentrations of wastewater-derived micropollutants in freshwater invertebrates ( Gammarus spp.). We applied Monte Carlo simulations and conducted laboratory experiments to account for the uncertain input data and the lack of uptake/depuration rate constants required for the TK model. The internal concentrations in field gammarids were predicted well, and the estimates varied only by a factor of 0.1-1.9. Fast equilibrium may also be assumed such that bioconcentration factors (BCFs) are used together with the daily river dilution patterns to predict internal concentrations. While this assumption is suitable for compounds observed in our experiment to reach the steady state within 48 h in gammarids, the model overpredicted the concentrations of substances that reach this condition after longer periods. Nevertheless, this approach provides conservative estimates and simplifies the coupling of models as BCFs are slightly more accessible than the rate constants. However, if one is interested in a more detailed exposure information (e.g., peak concentration and the whole-body burden recovery after a spill), then the nonsteady-state formulation should be employed.

Enhancing the understanding of the fate of wastewater-derived organic micropollutants in rivers is crucial to improve risk assessment, regulatory decision making and river management. Hyporheic exchange and sediment bacterial diversity are two factors gaining increasing importance as drivers for micropollutant degradation, but are complex to study in field experiments and usually ignored in laboratory tests aimed to estimate environmental half-lives. Flume mesocosms are useful to investigate micropollutant degradation processes, bridging the gap between the field and batch experiments. However, few studies have used flumes in this context. We present a novel experimental setup using 20 recirculating flumes and a response surface model to study the influence of hyporheic exchange and sediment bacterial diversity on half-lives of the anti-epileptic drug carbamazepine (CBZ) and the artificial sweetener acesulfame (ACS). The effect of bedform-induced hyporheic exchange was tested by three treatment levels differing in number of bedforms (0, 3 and 6). Three levels of sediment bacterial diversity were obtained by diluting sediment from the River Erpe in Berlin, Germany, with sand (1 : 10, 1 : 1000 and 1 : 100 000). Our results show that ACS half-lives were significantly influenced by sediment dilution and number of bedforms. Half-lives of CBZ were higher than ACS, and were significantly affected only by the sediment dilution variable, and thus by bacterial diversity. Our results show that (1) the flume-setup is a useful tool to study the fate of micropollutants in rivers, and that (2) higher hyporheic exchange and bacterial diversity in the sediment can increase the degradation of micropollutants in rivers.

Passive sampling is a well-established tool for monitoring time-weighted average concentrations of polar and semi-polar organic contaminants in streams at flow velocities between 0.1 and 0.4 m s -1 . However, its application under low-flow conditions (10 -5 to 0.01 m s -1 ) - as encountered in hyporheic zones - has been scarcely reported. In this study, 3 novel passive sampler configurations were developed for the monitoring of (semi-)polar organic pollutants and related transformation products across the water-sediment interface and thus across varying hydrodynamic conditions. Their design was inspired by Chemcatcher and diffusive gradients in thin films for organics. To determine the most optimal sampler design, an uptake experiment was completed involving the 3 novel passive sampler configurations and a reference Chemcatcher in polar configuration. The experiments consisted of a circular flume that simulated the main channel of a stream and an aquarium with stagnant water that represented the underlying hyporheic zone. The systems were exposed to 192 organic pollutants at environmental concentrations, and the samplers were then collected, extracted and analyzed using liquid chromatography high-resolution mass spectrometry after 2, 6 and 14 days. The configuration that was most insensitive to different hydrodynamic conditions consisted of a reversed-phase sulfonated styrenedivinylbenzene disk as the receiving phase that was covered by an agarose diffusion gel and topped with a polyethersulfone membrane filter. To further evaluate its environmental application, samplers were installed downstream of a sewage treatment plant located at an urban stream in Berlin, Germany (Erpe). The samplers were mounted on custom-made holders which were subsequently embedded in the stream bed to position samplers above (0.30 m) and within the sediment (-0.15/-0.30/-0.45 m) for 11 days. Target and suspect screening workflows were then applied to identify common concentration patterns and link parent attenuation to transformation product formation. A total of 104 concentration profiles were determined, suggesting the efficiency of the proposed sampling strategy in the water-sediment interface. Valsartan acid was the only known transformation product indicative of hyporheic zone-driven attenuation as its concentration in porewater by far exceeded its concentration in surface water. Similar patterns were observed for a larger list of suspected transformation products, of which a sotalol transformation product was tentatively identified. Overall, the established sampling methodology can be effectively used to quantify organic contaminants during low-flow conditions and is suitable for the characterization of attenuation patterns of organic pollutants in hyporheic zones., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Groundwater is a major drinking water resource, but its quality is threatened by a broad variety of anthropogenic micropollutants (MPs), originating from agriculture, industry, or households, and undergoing various transformation processes during subsurface passage. To determine a worst-case impact of pesticide application in agriculture on groundwater quality, a target and suspect screening for more than 300 pesticides and more than 1100 pesticide transformation products (TPs) was performed in 31 Swiss groundwater samples which predominantly originated from areas with intensive agriculture. To assess additional urban contamination sources, more than 250 common urban MPs were quantified. Most of the screened pesticide TPs were experimentally observed by the pesticide producers within the European pesticide registration. To cover very polar pesticide TPs, vacuum-assisted evaporative concentration was used for enrichment, followed by liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS). Based on intensity, isotope pattern, retention time, and in silico fragmentation, the suspect hits were prioritised and verified. We identified 22 suspects unequivocally and five tentatively; 13 TPs are reported here for the first time to be detected in groundwater. In 13 out of 31 groundwater samples, the total concentration of the 20 identified and quantified suspects (1 pesticide and 19 pesticide TPs) exceeded the total concentration of the 519 targets (236 pesticides and TPs; 283 urban MPs) for which we screened. Pesticide TPs had higher concentrations than the parent pesticides, illustrating their importance for groundwater quality. The newly identified very polar chlorothalonil TP R471811 was the only compound detected in all samples with concentrations ranging from 3 to 2700 ng/L. Agricultural MP concentration and detection frequency correlated with agricultural land use in the catchment, except for aquifers, where protective top layers reduced MP transport from the surface. In contrast to agricultural MPs, urban MPs displayed almost no correlation with land use. The dominating entry pathway of urban MPs was river bank filtration., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The aim of the present study was to develop (i) a technique for identifying metabolites of organic contaminants by using an in vitro system of trout S9 and liquid chromatography-high-resolution mass spectrometry-based identification method and (ii) to apply this technique to identify the interactive potential of carbamazepine on the formation rate of other metabolites. The pharmaceuticals carbamazepine and propranolol and the pesticides azoxystrobin, diazinon, and fipronil were selected as test contaminants. As a result, a total of ten metabolites were identified for the five parent substances, six of which were confirmed using reference standards. Metabolic reactions included hydroxylation, epoxidation, S-oxidation, and dealkylation. The metabolic transformation rate ranged from 0.2 to 3.5 pmol/mg protein/min/μmol substrate. In the binary exposure experiment with increasing carbamazepine concentration, the formation rates of diazinon and fipronil metabolites (MDI2 and MFP2, respectively) increased, while formation of metabolites of propranolol and azoxystrobin (MPR1, MPR2, MPR3, and MAZ1) slowed down. Meanwhile, S9 pre-exposed to carbamazepine produced diazoxon, a toxic metabolite of diazinon, and pyrimidinol, a less toxic metabolite, more rapidly. These results suggest that carbamazepine, a perennial environmental pollutant, might modulate the toxicity of other substances such as diazinon but further in vivo studies are needed., (Copyright © 2019 Elsevier Inc. All rights reserved.)

With the growth in production and use of chemicals and the fact that many end up in the aquatic environment, there is an increasing need for advanced water treatment technologies that can remove chemicals of emerging concern (CECs) from water. The current lack of a homogenous approach for testing advanced water treatment technologies hampers the interpretation and evaluation of CEC removal efficiency data, and hinders informed decision making by stakeholders with regard to which treatment technology could satisfy their specific needs. Here a data evaluation framework is proposed to improve the use of current knowledge in the field of advanced water treatment technologies for drinking water and wastewater, consisting of a set of 9 relevance criteria and 51 reliability criteria. The two criteria sets underpin a thorough, unbiased and standardised method to select studies to evaluate and compare CEC removal efficiency of advanced water treatment technologies in a scientifically sound way. The relevance criteria set was applied to 244 papers on removal efficiency, of which only 20% fulfilled the criteria. The reliability criteria were applied to the remaining papers. In general these criteria were fulfilled with regards to information on the target compound, the water matrix and the treatment process conditions. However, there was a lack of information on data interpretation and statistics. In conclusion, a minority of the evaluated papers are suited for comparison across techniques, compounds and water matrixes. There is a clear need for more uniform reporting of water treatment studies for CEC removal. In the future this will benefit the selection of appropriate technologies., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Aqueous film-forming foams (AFFFs) are proprietary mixtures containing hydrocarbon surfactants and per- and polyfluoroalkyl substances (PFASs) that are used to extinguish hydrocarbon-based fuel fires. There is limited information on hydrocarbon surfactants in AFFFs and AFFF-contaminated groundwater even though hydrocarbon surfactants are more abundant (5-10% w/w) than PFASs (0.9-1.5% w/w) in AFFFs. Eight commercial AFFFs manufactured between 1988 and 2012 and 10 AFFF-contaminated groundwaters collected from near source zones of fire-fighter training areas were analyzed for suspect hydrocarbon surfactants by liquid chromatography quadrupole time-of-flight mass spectrometry. A suspect list and a homologous series detection computational tool, enviMass, were combined to screen for hydrocarbon surfactants. Nine classes of hydrocarbon surfactants were detected in AFFFs including octylphenol polyethoxylates, linear alcohol ethoxylates, ethoxylated cocoamines, alkyl ether sulfates, alkyl amido dipropionates, linear alkyl benzenesulfonates, alkyl sulfates, and polyethylene glycols. Of those, six were also found in groundwater along with diethanolamines and alkyl amido betaines, which were not found in the eight archived AFFFs. This indicates that although aerobically biodegradable, hydrocarbon surfactants likely persist in groundwater due to anaerobic aquifer conditions. To the best of our knowledge, this is the first screening for hydrocarbon surfactants in AFFFs and in AFFF-contaminated groundwater.

The historic emissions of polar micropollutants in a natural drinking water source were investigated by nontarget screening with high-resolution mass spectrometry and open cheminformatics tools. The study area consisted of a riverbank filtration transect fed by the river Lek, a branch of the lower Rhine, and exhibiting up to 60-year travel time. More than 18,000 profiles were detected. Hierarchical clustering revealed that 43% of the 15 most populated clusters were characterized by intensity trends with maxima in the 1990s, reflecting intensified human activities, wastewater treatment plant upgrades and regulation in the Rhine riparian countries. Tentative structure annotation was performed using automated in silico fragmentation. Candidate structures retrieved from ChemSpider were scored based on the fit of the in silico fragments to the experimental tandem mass spectra, similarity to openly accessible accurate mass spectra, associated metadata, and presence in a suspect list. Sixty-seven unique structures (72 over both ionization modes) were tentatively identified, 25 of which were confirmed and included contaminants so far unknown to occur in bank filtrate or in natural waters at all, such as tetramethylsulfamide. This study demonstrates that many classes of hydrophilic organics enter riverbank filtration systems, persisting and migrating for decades if biogeochemical conditions are stable.

Neonicotinoids are widely used insecticides that have frequently been found in freshwater with concentrations ranging from ng to μg/L. It is known that these compounds impact non-target invertebrates, such as bees and gammaridae, in terms of toxicity and behavior, but impacts and species differences on vertebrates such as fish are little explored. The aim of this study was to investigate and compare the effects of one widely used neonicotinoid, imidacloprid, on development and behavior of two fish model species: Zebrafish (Danio rerio) and Japanese medaka (Oryzias latipes). Fish were exposed for 5 (zebrafish) and 14 (medaka) days from 0.2 to 2000 μg/L imidacloprid by aqueous exposure. Survival, development, behavior and histological features were monitored and organism-internal concentrations and biotransformation products measured. Imidacloprid caused sublethal effects in both species but the effects were much stronger in medaka with deformities, lesions and reduced growth being the most prominent impacts. Due to the overall longer time of development, time-integrated exposure of medaka was about 2-fold higher compared to zebrafish, potentially accounting for parts of the sensitivity differences. Our results underline the importance of taking species sensitivity differences into account especially when considering that medaka responded at imidacloprid concentrations that have been measured in the environment., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Aquatic organisms are consistently exposed to a mixture of micropollutants that can bioaccumulate, undergo biotransformation, and may exert mixture effects. However, little is known on the underlying mechanisms and species-specificity. Herein we investigated bioaccumulation, biotransformation and synergistic effects of azole (i.e., prochloraz) and strobilurin (i.e., azoxystrobin) fungicides in the two aquatic invertebrate species, Hyalella azteca and Gammarus pulex. Bioaccumulation of azoxystrobin was similar, whereas bioaccumulation of prochloraz was slightly different in the two species but was still significantly below the REACH criteria for bioaccumulative substances. Similar biotransformation patterns were observed in both species, and only a few unique biotransformation reactions were detected in H. azteca such as malonyl-glucose and taurine conjugation. Toxicokinetic modeling additionally indicated that biotransformation is a more important elimination pathway in H. azteca. In mixtures, no-observed-adverse-effect levels of prochloraz decreased the LC 50 s of azoxystrobin in both species which correlated well with increased internal azoxystrobin concentrations. This synergistic effect is partly due to the inhibition of cytochrome P450 monooxygenases by prochloraz which subsequently triggered the reduced biotransformation of azoxystrobin (lower by five folds in H. azteca). The largely similar responses in both species suggest that the easier-to-cultivate H. azteca is a promising representative of invertebrates for toxicity testing.

Ozonation and subsequent post-treatments are increasingly implemented in wastewater treatment plants (WWTPs) for enhanced micropollutant abatement. While this technology is effective, micropollutant oxidation leads to the formation of ozonation transformation products (OTPs). Target and suspect screening provide information about known parent compounds and known OTPs, but for a more comprehensive picture, non-target screening is needed. Here, sampling was conducted at a full-scale WWTP to investigate OTP formation at four ozone doses (2, 3, 4, and 5 mg/L, ranging from 0.3 to 1.0 gO 3 /gDOC) and subsequent changes during five post-treatment steps (i.e., sand filter, fixed bed bioreactor, moving bed bioreactor, and two granular activated carbon (GAC) filters, relatively fresh and pre-loaded). Samples were measured with online solid-phase extraction coupled to liquid chromatography high-resolution tandem mass spectrometry (LC-HRMS/MS) using electrospray ionization (ESI) in positive and negative modes. Existing non-target screening workflows were adapted to (1) examine the formation of potential OTPs at four ozone doses and (2) compare the removal of OTPs among five post-treatments. In (1), data processing included principal component analysis (PCA) and chemical knowledge on possible oxidation reactions to prioritize non-target features likely to be OTPs. Between 394 and 1328 unique potential OTPs were detected in positive ESI for the four ozone doses tested; between 12 and 324 unique potential OTPs were detected in negative ESI. At a specific ozone dose of 0.5 gO 3 /gDOC, 27 parent compounds were identified and were related to 69 non-target features selected as potential OTPs. Two OTPs were confirmed with reference standards (venlafaxine N-oxide and chlorothiazide); 34 other potential OTPs were in agreement with literature data and/or reaction mechanisms. In (2), hierarchical cluster analysis (HCA) was applied on profiles detected in positive ESI mode across the WWTP and revealed 11 relevant trends. OTP removal was compared among the five post-treatments and 54-83% of the non-target features that appeared after ozonation were removed, with the two GAC filters performing the best. Overall, these data analysis strategies for non-target screening provide a useful tool to understand the behavior of unknown features during ozonation and post-treatment and to prioritize certain non-targets for further identification., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Internal concentrations link external exposure to the potential effect, as they reflect what the organisms actually take up and experience physiologically. In this study, we investigated whether frequently detected risk-driving substances in water were found in the exposed organisms and if they are classified the same based on the whole body internal concentrations. Field gammarids were collected upstream and downstream of ten wastewater treatment plants in mixed land use catchments. The sampling was conducted in autumn and winter, during low flow conditions when diffuse agricultural input was reduced. The field study was complemented with laboratory and flume experiments to determine the bioaccumulation potentials of selected substances. For 32 substances, apparent bioaccumulation factors in gammarids were determined for the first time. With a sensitive multiresidue method based on online-solid phase extraction followed by liquid chromatography coupled to high resolution mass spectrometry, we detected 63 (semi-) polar organic substances in the field gammarids, showing higher concentrations downstream than upstream. Interestingly, neonicotinoids, which are particularly toxic toward invertebrates, were frequently detected and were further determined as major contributors to the toxic pressure based on the toxic unit approach integrating internal concentration and toxic potency. The total toxic pressure based on internal concentrations was substantially higher compared to when external concentrations were used. Thus, internal concentrations may add more value to the current environmental risk assessment that is typically based solely on external exposure.

Wastewater treatment plant (WWTP) effluents are major sources of endocrine-disrupting chemicals (EDCs) and other chemicals of toxicological concern for the aquatic environment. In the present study, we used an integrated strategy combining passive sampling (Chemcatcher®), developmental toxicity, and mechanism-based in vitro and in vivo bioassays to monitor the impacts of a WWTP on a river. In vitro screening revealed the WWTP effluent as a source of estrogen, glucocorticoid, and aryl hydrocarbon (AhR) receptor-mediated activities impacting the downstream river site where significant activities were also measured, albeit to a lesser extent than in the effluent. Effect-directed analysis of the effluent successfully identified the presence of potent estrogens (estrone, 17α-ethinylestradiol, and 17β-estradiol) and glucocorticoids (clobetasol propionate and fluticasone propionate) as the major contributors to the observed in vitro activities, even though other unidentified active chemicals were likely present. The impact of the WWTP was also assessed using zebrafish embryo assays, highlighting its ability to induce estrogenic response through up-regulation of the aromatase promoter-dependent reporter gene in the transgenic (cyp19a1b-green fluorescent protein [GFP]) zebrafish assay and to generate teratogenic effects at nonlethal concentrations in the zebrafish embryo toxicity test. The present study argues for the use of such an integrated approach, combining passive sampling, bioassays, and effect-directed analysis, to comprehensively identify endocrine active compounds and associated hazards of WTTP effluents. Environ Toxicol Chem 2018;37:2079-2088. © 2018 SETAC., (© 2018 SETAC.)

The production of toxic plant secondary metabolites (phytotoxins) for defense is a widespread phenomenon in the plant kingdom and is even present in agricultural crops. These phytotoxins may have similar characteristics to anthropogenic micropollutants in terms of persistence and toxicity. However, they are only rarely included in environmental risk assessments, partly because a systematic overview of phytotoxins is missing. Here, we present a newly developed, freely available database, Toxic Plants-PhytoToxins (TPPT), containing 1586 phytotoxins of potential ecotoxicological relevance in Central Europe linked to 844 plant species. Our database summarizes phytotoxin patterns in plant species and provides detailed biological and chemical information as well as in silico estimated properties. Using the database, we evaluated phytotoxins regarding occurrence, approximated from the frequencies of Swiss plant species; environmental behavior based on aquatic persistence and mobility; and toxicity. The assessment showed that over 34% of all phytotoxins are potential aquatic micropollutants and should be included in environmental investigations.

Occurrence and fate of glyphosate, a widely used herbicide, and its main metabolite AMPA was investigated in Lake Greifensee, Switzerland. Monthly vertical concentration profiles in the lake showed an increase of glyphosate concentrations in the epilimnion from 15 ng/L in March to 145 ng/L in July, followed by a sharp decline to <5 ng/L in August. A similar pattern was observed for AMPA. Concentrations of glyphosate and AMPA in the two main tributaries generally were much higher than in the lake. Simulations using a numerical lake model indicated that a substantial amount of glyphosate and AMPA dissipated in the epilimnion, mainly in July and August, with half-lives of only ≈2-4 days which is ≫100 times faster than in the preceding months. Fast dissipation coincided with high water temperatures and phytoplankton densities, and low phosphate concentrations. This indicates that glyphosate might have been used as an alternative phosphorus source by bacterio- and phytoplankton. Metagenomic analysis of lake water revealed the presence of organisms known to be capable of degrading glyphosate and AMPA.

In vitro bioassays are increasingly used for water quality monitoring. Surface water samples often need to be enriched to observe an effect and solid-phase extraction (SPE) is commonly applied for this purpose. The applied methods are typically optimised for the recovery of target chemicals and not for effect recovery for bioassays. A review of the few studies that have evaluated SPE recovery for bioassays showed a lack of experimentally determined recoveries. Therefore, we systematically measured effect recovery of a mixture of 579 organic chemicals covering a wide range of physicochemical properties that were spiked into a pristine water sample and extracted using large volume solid-phase extraction (LVSPE). Assays indicative of activation of xenobiotic metabolism, hormone receptor-mediated effects and adaptive stress responses were applied, with non-specific effects determined through cytotoxicity measurements. Overall, effect recovery was found to be similar to chemical recovery for the majority of bioassays and LVSPE blanks had no effect. Multi-layer SPE exhibited greater recovery of spiked chemicals compared to LVSPE, but the blanks triggered cytotoxicity at high enrichment. Chemical recovery data together with single chemical effect data were used to retrospectively estimate with reverse recovery modelling that there was typically less than 30% effect loss expected due to reduced SPE recovery in published surface water monitoring studies. The combination of targeted experiments and mixture modelling clearly shows the utility of SPE as a sample preparation method for surface water samples, but also emphasizes the need for adequate controls when extraction methods are adapted from chemical analysis workflows.

Urban regions of the world are expanding rapidly, placing additional stress on water resources. Urban water bodies serve many purposes, from washing and sources of drinking water to transport and conduits for storm drainage and effluent discharge. These water bodies receive chemical emissions arising from either single or multiple point sources, diffuse sources which can be continuous, intermittent, or seasonal. Thus, aquatic organisms in these water bodies are exposed to temporally and compositionally variable mixtures. We have delineated source-specific signatures of these mixtures for diffuse urban runoff and urban point source exposure scenarios to support risk assessment and management of these mixtures. The first step in a tiered approach to assessing chemical exposure has been developed based on the event mean concentration concept, with chemical concentrations in runoff defined by volumes of water leaving each surface and the chemical exposure mixture profiles for different urban scenarios. Although generalizations can be made about the chemical composition of urban sources and event mean exposure predictions for initial prioritization, such modeling needs to be complemented with biological monitoring data. It is highly unlikely that the current paradigm of routine regulatory chemical monitoring alone will provide a realistic appraisal of urban aquatic chemical mixture exposures. Future consideration is also needed of the role of nonchemical stressors in such highly modified urban water bodies. Environ Toxicol Chem 2018;37:703-714. © 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC., (© 2017 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals, Inc. on behalf of SETAC.)

The significant increase in traces of human activity in the environment worldwide provides evidence of the beginning of a new geological era, informally named the Anthropocene. The rate and variability of these human modifications at the local and global scale remain largely unknown, but new analytical methods such as high-resolution mass spectrometry (HRMS) can help to characterize chemical contamination. We therefore applied HRMS to investigate the contamination history of two lakes in Central Europe over the preceding 100 years. A hierarchical clustering analysis (HCA) of the collected time series data revealed more than 13 000 profiles of anthropogenic origin in both lakes, defining the beginning of large-scale human impacts during the 1950s. Our results show that the analysis of temporal patterns of nontarget contaminants is an effective method for characterizing the contamination pattern in the Anthropocene and an important step in prioritizing the identification of organic contaminants not yet successfully targeted by environmental regulation and pollution reduction initiatives. As proof of the concept, the success of the method was demonstrated with the identification of the pesticide imazalil, which probably originated from imported fruits. This new approach applicable to palaeoarchives can effectively be used to document the time and rate of change in contamination over time and provide additional information on the onset of the Anthropocene.

The vast, diverse universe of organic pollutants is a formidable challenge for environmental sciences, engineering, and regulation. Nontarget screening (NTS) based on high resolution mass spectrometry (HRMS) has enormous potential to help characterize this universe, but is it ready to go for real world applications? In this Feature article we argue that development of mass spectrometers with increasingly high resolution and novel couplings to both liquid and gas chromatography, combined with the integration of high performance computing, have significantly widened our analytical window and have enabled increasingly sophisticated data processing strategies, indicating a bright future for NTS. NTS has great potential for treatment assessment and pollutant prioritization within regulatory applications, as highlighted here by the case of real-time pollutant monitoring on the River Rhine. We discuss challenges for the future, including the transition from research toward solution-centered and robust, harmonized applications.

The efficiency of ozone-based processes under various conditions was studied for the treatment of a surface water (Lake Zürich water, Switzerland) spiked with 19 micropollutants (pharmaceuticals, pesticides, industrial chemical, X-ray contrast medium, sweetener) each at 1 μg L -1 . Two pilot-scale ozonation reactors (4-5 m 3  h -1 ), a 4-chamber reactor and a tubular reactor, were investigated by either conventional ozonation and/or the advanced oxidation process (AOP) O 3 /H 2 O 2 . The effects of selected operational parameters, such as ozone dose (0.5-3 mg L -1 ) and H 2 O 2 dose (O 3 :H 2 O 2  = 1:3-3:1 (mass ratio)), and selected water quality parameters, such as pH (6.5-8.5) and initial bromide concentration (15-200 μg L -1 ), on micropollutant abatement and bromate formation were investigated. Under the studied conditions, compounds with high second-order rate constants k O3 >10 4  M -1  s -1 for their reaction with ozone were well abated (>90%) even for the lowest ozone dose of 0.5 mg L -1 . Conversely, the abatement efficiency of sucralose, which only reacts with hydroxyl radicals (OH), varied between 19 and 90%. Generally, the abatement efficiency increased with higher ozone doses and higher pH and lower bromide concentrations. H 2 O 2 addition accelerated the ozone conversion to OH, which enables a faster abatement of ozone-resistant micropollutants. Interestingly, the abatement of micropollutants decreased with higher bromide concentrations during conventional ozonation due to competitive ozone-consuming reactions, except for lamotrigine, due to the suspected reaction of HOBr/OBr - with the primary amine moieties. In addition to the abatement of micropollutants, the evolution of the two main transformation products (TPs) of hydrochlorothiazide (HCTZ) and tramadol (TRA), chlorothiazide (CTZ) and tramadol N-oxide (TRA-NOX), respectively, was assessed by chemical analysis and kinetic modeling. Both selected TPs were quickly formed initially to reach a maximum concentration followed by a decrease of their concentrations for longer contact times. For the studied conditions, the TP's concentrations at the outlet of the reactors ranged from 0 to 61% of the initial parent compound concentration, CTZ being a more persistent TP against further oxidation than TRA-NOX. Finally, it was demonstrated in both reactors that the formation of bromate (BrO 3 - ), a potentially carcinogenic oxidation by-product, could be controlled by H 2 O 2 addition with a general improvement on micropollutant abatement. Post-treatment by granular activated carbon (GAC) filtration enabled the reduction of micropollutants and TPs concentrations but no changes in bromate were observed. The combined algae assay showed that water quality was significantly improved after oxidation and GAC post-treatment, driven by the abatement of the spiked pesticides (diuron and atrazine)., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Phytoplankton constitute an important component of surface water ecosystems; however little is known about their contribution to biotransformation of organic micropollutants. To elucidate biotransformation processes, batch experiments with two cyanobacterial species (Microcystis aeruginosa and Synechococcus sp.) and one green algal species (Chlamydomonas reinhardtii) were conducted. Twenty-four micropollutants were studied, including 15 fungicides and 9 pharmaceuticals. Online solid phase extraction (SPE) coupled with liquid chromatography (LC)-high resolution tandem mass spectrometry (HRMS/MS) was used together with suspect and nontarget screening to identify transformation products (TPs). 14 TPs were identified for 9 micropollutants, formed by cytochrome P450-mediated oxidation, conjugation and methylation reactions. The observed transformation pathways included reactions likely mediated by promiscuous enzymes, such as glutamate conjugation to mefenamic acid and pterin conjugation of sulfamethoxazole. For 15 compounds, including all azole fungicides tested, no TPs were identified. Environmentally relevant concentrations of chemical stressors had no influence on the transformation types and rates.

The overarching aim of this field study was to examine causal links between in-situ exposure to complex mixtures of micropollutants from wastewater treatment plants and effects on freshwater microbial communities in the receiving streams. To reach this goal, we assessed the toxicity of serial dilutions of micropollutant mixtures, extracted from deployed passive samplers at the discharge sites of four Swiss wastewater treatment plants, to in situ periphyton from upstream and downstream of the effluents. On the one hand, comparison of the sensitivities of upstream and downstream periphyton to the micropollutant mixtures indicated that algal and bacterial communities composing the periphyton displayed higher tolerance towards these micropollutants downstream than upstream. On the other hand, molecular analyses of the algal and bacterial structure showed a clear separation between upstream and downstream periphyton across the sites. This finding provides an additional line of evidence that micropollutants from the wastewater discharges were directly responsible for the change in the community structure at the sampling sites by eliminating the micropollutant-sensitive species and favouring the tolerant ones. What is more, the fold increase of algal and bacterial tolerance from upstream to downstream locations was variable among sampling sites and was strongly correlated to the intensity of contamination by micropollutants at the respective sites. Overall, our study highlights the sensitivity of the proposed approach to disentangle effects of micropollutant mixtures from other environmental factors occurring in the field and, thus, establishing a causal link between exposure and the observed ecological effects on freshwater microbial communities., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Micropollutants enter surface waters through various pathways, of which wastewater treatment plants (WWTPs) are a major source. The large diversity of micropollutants and their many modes of toxic action pose a challenge for assessing environmental risks. In this study, we investigated the potential impact of WWTPs on receiving ecosystems by describing concentration patterns of micropollutants, predicting acute risks for aquatic organisms and validating these results with macroinvertebrate biomonitoring data. Grab samples were taken upstream, downstream and at the effluent of 24 Swiss WWTPs during low flow conditions across independent catchments with different land uses. Using liquid chromatography high resolution tandem mass spectrometry, a comprehensive target screening of almost 400 organic substances, focusing mainly on pesticides and pharmaceuticals, was conducted at two time points, and complemented with the analysis of a priority mixture of 57 substances over eight time points. Acute toxic pressure was predicted using the risk assessment approach of the multi-substance potentially affected fraction, first applying concentration addition for substances with the same toxic mode of action and subsequently response addition for the calculation of the risk of the total mixture. This toxic pressure was compared to macroinvertebrate sensitivity to pesticides (SPEAR index) upstream and downstream of the WWTPs. The concentrations were, as expected, especially for pharmaceuticals and other household chemicals higher downstream than upstream, with the detection frequency of plant protection products upstream correlating with the fraction of arable land in the catchments. While the concentration sums downstream were clearly dominated by pharmaceuticals or other household chemicals, the acute toxic pressure was mainly driven by pesticides, often caused by the episodic occurrence of these compounds even during low flow conditions. In general, five single substances explained much of the total risk, with diclofenac, diazinon and clothianidin as the main drivers. Despite the low predicted acute risk of 0%-2.1% for affected species, a significant positive correlation with macroinvertebrate sensitivity to pesticides was observed. However, more effect data for pharmaceuticals and a better quantification of episodic pesticide pollution events are needed for a more comprehensive risk assessment., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The efficiency of wastewater ozonation for the abatement of three nitrogen-containing pharmaceuticals, two antihistamine drugs, cetirizine (CTR) and fexofenadine (FXF), and the diuretic drug, hydrochlorothiazide (HCTZ), was investigated. Species-specific second-order rate constants for the reactions of the molecular, protonated (CTR, FXF) or deprotonated (HCTZ) forms of these compounds with ozone were determined. All three compounds are very reactive with ozone (apparent second order rate constants at pH 7: kO3,pH7 = 1.7·10(5) M(-1)s(-1), 8.5·10(4) M(-1)s(-1) and 9.0·10(3) M(-1)s(-1) for CTR, HCTZ and FXF, respectively). Transformation product (TP) structures were elucidated using liquid chromatography coupled with high-resolution tandem mass spectrometry, including isotope-labeled standards. For cetirizine and hydrochlorothiazide 8 TPs each and for fexofenadine 7 TPs were identified. The main TPs of cetirizine and fexofenadine are their respective N-oxides, whereas chlorothiazide forms to almost 100% from hydrochlorothiazide. In the bacteria bioluminescence assay the toxicity was slightly increased only during the ozonation of cetirizine at very high cetirizine concentrations. The main TPs detected in bench-scale experiments were also detected in full-scale ozonation of a municipal wastewater, for >90% elimination of the parent compounds., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Online solid-phase extraction was combined with nano-liquid chromatography coupled to high-resolution mass spectrometry (HRMS) for the analysis of micropollutants in environmental samples from small volumes. The method was validated in surface water, Microcystis aeruginosa cell lysate, and spent Microcystis growth medium. For 41 analytes, quantification limits of 0.1-28 ng/L (surface water) and 0.1-32 ng/L (growth medium) were obtained from only 88 μL of sample. In cell lysate, quantification limits ranged from 0.1-143 ng/L or 0.33-476 ng/g dry weight from a sample of 88 μL, or 26 μg dry weight, respectively. The method matches the sensitivity of established online and offline solid-phase extraction-liquid chromatography-mass spectrometry methods but requires only a fraction of the sample used by those techniques, and is among the first applications of nano-LC-MS for environmental analysis. The method was applied to the determination of bioconcentration in Microcystis aeruginosa in a laboratory experiment, and the benefit of coupling to HRMS was demonstrated in a transformation product screening.