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Excess rainfall events could lead to overflows and combined sewer overflows, which could threaten local mussel populations. This study sought to compare the long- term effects of combined sewer overflows and treated municipal effluents in caged Elliptio complanata mussels. Mussels were caged at 2 overflow sites, one downstream site of a major municipal effluent dispersion plume and a reference upstream site for 3 months during the summer. At the end of the exposure period, mussels were collected, analyzed for municipal contaminants (including pharmaceuticals), and effects biomarkers based on endocrine disruption (vitellogenin expression), xenobiotic detoxification (glutathione S-transferase and metallothioneins), oxidative stress/inflammation (cyclooxygenase and lipid peroxidation) and DNA damage. The data revealed that surface waters contained less pharmaceutical products than the downstream site but atrazine and its metabolite were at higher levels in overflow sites. Mussels contained elevated amounts of total heterotrophic bacteria, caffeine, acebutolol and venlafaxine at the downstream site relative to the upstream site where caffeine was higher at one of the overflow site. The levels of vitellogenin gene expression were significantly increased in both sexes of mussels caged at the downstream site only. Multivariate analysis revealed that the biomarker responses were completely separated between upstream, overflow and downstream sites. The site discrimination was based on vitellogenin, metallothioneins, DNA damage in gonad and digestive gland, gonad lipids/proteins reserves, lipid peroxidation, gonado-somatic index and condition factor. Adverse outcome pathways analysis using the power law approach revealed that most changes in the biomarkers identified by discriminant function analysis were significantly scaled to gonad energy reserves, tissue/ mussel size and loss of weight following air emersion stress. In conclusion, the toxic effects of mussels caged at overflow sites generally displayed lower responses than mussels caged downstream a treated municipal effluent suggesting that these overflows pose a lower risk than the continuous exposure to treated municipal effluent. [ABSTRACT FROM AUTHOR]

A rapid on-line solid-phase extraction liquid chromatography high-resolution mass spectrometry (on-line SPE-LC-HRMS) method was developed to analyze 11 ultra-short and short-chain PFAS in surface water. Analytical optimization involved screening 7 chromatographic columns and 5 on-line SPE columns, as well as evaluating SPE loading conditions, filters, sample acidification, chromatographic mobile phases, and SPE loading mobile phases. The optimized method was then applied to 44 river water samples collected in Eastern Canada, including sites near airports with fire-training areas. Among the 11 targeted PFAS, the most frequently detected were trifluoroacetic acid (TFA, 4.6-220 ng/L), perfluorobutanoic acid (PFBA, 0.85-33 ng/L), perfluoropentanoic acid (PFPeA, 1.2-2100 ng/L), trifluoromethane sulfonic acid (TMS, 0.01-4.3 ng/L), and perfluorobutane sulfonic acid (PFBS, 0.07-450 ng/L). Levels of C3-C5 perfluoroalkyl carboxylic acids (PFCAs), C2-C4 perfluoroalkyl sulfonates (PFSAs) and n:3 polyfluoroalkyl acids (n = 2,3; n:3 acids) were significantly higher in water bodies near fire-training area sites compared with rivers in urban areas. In contrast, TFA, TMS, and 1:3 acid were not significantly elevated, likely reflecting atmospheric deposition or other diffuse sources for these compounds. Nontarget and suspect screening analysis revealed an abundance of other ultra-short and short-chain PFAS in AFFF-impacted water bodies. Perfluoroalkyl sulfonamides (FASA, C2, C3, and C5), perfluoroalkyl sulfonamide propanoic acids (FASA-PrA, C1-C2) and n:3 acids (n = 1, 4, and 5) were detected for the first time in environmental surface waters., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

A reconnaissance survey was undertaken to evaluate the occurrence and risks of 27 pharmaceuticals and metabolites in the St. Lawrence watershed. Surface water samples were collected over a five-year period (2017-2021) along a 700-km reach of the St. Lawrence River as well as 55 tributary rivers (overall N = 406 samples). Additionally, depth water samples and sediments were collected near a major wastewater effluent. Caffeine, diclofenac, and venlafaxine were the most recurrent substances (detection rates >80 %), and extremely high levels were found near a municipal effluent (e.g., ibuprofen (860 ng/L), hydroxyibuprofen (1800 ng/L) and caffeine (7200 ng/L)). Geographical mapping and statistical analyses indicated that the St. Lawrence River water mass after the Montreal City effluent was significantly more contaminated than the other water masses, and that contamination could extend up to 70 km further downstream. This phenomenon was repeatedly observed over the five years of sampling, confirming that this is not a random trend. A slight increase in contamination was also observed near Quebec City, but concentrations rapidly declined in the estuarine transition zone. Tributaries with the highest pharmaceutical levels (ΣPharmas ∼400-900 ng/L) included the Mascouche, Saint-Régis, and Bertrand rivers, all located in the densely populated Greater Montreal area. When flowrate was factored in, the top five tributaries in terms of mass load (ΣPharmas ∼200-2000 kg/year) were the Des Prairies, Saint-François, Richelieu, Ottawa, and Yamaska rivers. All samples met the Canadian Water Quality Guideline for carbamazepine. Despite the large dilution effect of the St. Lawrence River, a risk quotient approach based on freshwater PNEC values suggested that four compounds (caffeine, carbamazepine, diclofenac, and ibuprofen) could present intermediate to high risks for aquatic organisms in terms of chronic exposure., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Methods targeting anionic per- and polyfluoroalkyl substances (PFAS) in aquatic biota are well established, but commonly overlook many PFAS classes present in aqueous film-forming foams (AFFFs). Here, we developed an analytical method for the expanded analysis of negative and positive ion mode PFAS in fish tissues. Eight variations of extraction solvents and clean-up protocols were first tested to recover 70 AFFF-derived PFAS from the fish matrix. Anionic, zwitterionic, and cationic PFAS displayed the best responses with methanol-based ultrasonication methods. The response of long-chain PFAS was improved for extracts submitted to graphite filtration alone compared with those involving solid-phase extraction. The validation included an assessment of linearity, absolute recovery, matrix effects, accuracy, intraday/interday precision, and trueness. The method was applied to a set of freshwater fish samples collected in 2020 in the immediate vicinity (creek, n = 15) and downstream (river, n = 15) of an active fire-training area at an international civilian airport in Ontario, Canada. While zwitterionic fluorotelomer betaines were major components of the subsurface AFFF source zone, they were rarely detected in fish, suggesting limited bioaccumulation potential. PFOS largely dominated the PFAS profile, with record-high concentrations in brook sticklebacks (Culaea inconstans) from the creek (16000-110,000 ng/g wet weight whole-body). These levels exceeded the Canadian Federal Environmental Quality Guidelines (FEQG) for PFOS pertaining to the Federal Fish Tissue Guideline (FFTG) for fish protection and Federal Wildlife Diet Guidelines (FWiDG) for the protection of mammalian and avian consumers of aquatic biota. Perfluorohexane sulfonamide and 6:2 fluorotelomer sulfonate were among the precursors detected at the highest levels (maximum of ∼340 ng/g and ∼1100 ng/g, respectively), likely reflecting extensive degradation and/or biotransformation of C6 precursors originally present in AFFF formulations., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Some contemporary aqueous film-forming foams (AFFFs) contain n :3 and n :1:2 fluorotelomer betaines (FTBs), which are often detected at sites impacted by AFFFs. As new chemical replacements, little is known about their environmental fate. For the first time, we investigated the biotransformation potential of 5:3 and 5:1:2 FTBs and a commercial AFFF that mainly contains n :3 and n :1:2 FTBs ( n = 5, 7, 9, 11, and 13). Although some polyfluoroalkyl compounds are precursors to perfluoroalkyl acids, 5:3 and 5:1:2 FTBs exhibited high persistence, with no significant changes even after 120 days of incubation. While the degradation of 5:3 FTB into suspected products such as fluorotelomer acids or perfluoroalkyl carboxylic acids (PFCAs) could not be conclusively confirmed, we did identify a potential biotransformation product, 5:3 fluorotelomer methylamine. Similarly, 5:1:2 FTB did not break down or produce short-chain hydrogen-substituted polyfluoroalkyl acids ( n :2 H-FTCA), hydrogen-substituted PFCA (2H-PFCA), or any other products. Incubating the AFFF in four soils with differing properties and microbial communities resulted in 0.023-0.25 mol % PFCAs by day 120. Most of the products are believed to be derived from n :2 fluorotelomers, minor components of the AFFF. Therefore, the findings of the study cannot be fully explained by the current understanding of structure-biodegradability relationships.

Limited monitoring data are available regarding the occurrence of emerging per- and polyfluoroalkyl substances (PFAS) in drinking water. Here, we validated an analytical procedure for 42 PFAS with individual detection limits of 0.001-0.082 ng/L. We also evaluated how different sample pH conditions, dechlorinating agents, and storage holding times might affect method performance. PFAS were analyzed in tap water samples collected at a large spatial scale in Quebec, Canada, covering 376 municipalities within 17 administrative regions. Target and nontarget screening revealed the presence of 31 and 23 compounds, respectively, representing 24 homolog classes. Overall, 99.3% of the tap water samples were positive for at least one PFAS, and the ƩPFAS ranged from below detection limits to 108 ng/L (95th percentile: 13 ng/L). On average, ƩPFAS was 12 times higher in tap water produced from surface water than groundwater; however, 6 of the top 10 contaminated locations were groundwater-based. Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) had high detection rates (88% and 80%, respectively). PFOS (median: 0.15 ng/L; max: 13 ng/L) and PFOA (median: 0.27 ng/L; max: 8.1 ng/L) remained much lower than current Health Canada guidelines but higher than USEPA's interim updated health advisories. Short-chain (C3-C6) perfluoroalkyl sulfonamides were also recurrent, especially the C4 homolog (FBSA: detection rate of 50%). The 6:2 fluorotelomer sulfonyl propanoamido dimethyl ethyl sulfonate (6:2 FTSO2PrAd-DiMeEtS) was locally detected at ∼15 ng/L and recurred in 8% of our samples. Multiple PFAS that are most likely to originate from aqueous film-forming foams were also reported for the first time in tap water, including X:3 and X:1:2 fluorotelomer betaines, hydroxylated X:2 fluorotelomer sulfonates, N-trimethylammoniopropyl perfluoroalkane sulfonamides (TAmPr-FHxSA and TAmPr-FOSA), and N-sulfopropyl dimethylammoniopropyl perfluoroalkane sulfonamidopropyl sulfonates (N-SPAmP-FPeSAPS and N-SPAmP-FHxSAPS)., Competing Interests: Declaration of Competing Interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:, (Copyright © 2023 Elsevier Ltd. All rights reserved.)

The widespread distribution of contaminants of emerging concern (CECs) is a major concern due to their potential effects on human health and the environment. The insufficient sewage treatment plant infrastructures is a global problem most accentuated in less developed countries and results in the discharge of CECs to water bodies. Pacu (Piaractus mesopotamicus) is a ray-finned freshwater fish species native to the Paraná basin. It is also the most produced aquaculture fish species in Argentina since 2012. Though uninvestigated to date, the occurrence of CECs in pacu may be of high relevance due to production volumes and relevance to human exposure through fish consumption. In this study, we applied a high-resolution mass spectrometry screening method to qualitatively analyze over 100 CECs in pacu. Four extraction/cleanup methods were tested on pooled pacu fillet, including solid-phase extraction and QuEChERS. The method that produced the highest number of detections was selected for further analysis of pacu purchased in supermarkets and fish markets in Argentina between 2017 and 2020. Residues of pesticides, antibiotics, pharmaceuticals, personal care products, plasticizers, sweeteners, drug metabolites, stimulants, and illegal drugs were detected in the samples. A total of 38 CECs were detected, ranging between 24 and 35 CECs per individual sample. 100% of the samples had positive detections of caffeine, 1,7-dimethylxanthine, xanthine, benzoylecgonine, methylparaben, ethylparaben, bis(2-ethylhexyl) phthalate (DEHP), metolachlor, carbendazim, salicylic acid, 2,4-D, saccharin, cyclamate, and dodecanedioic acid. Mappings generated with correspondence analysis were used to explore similarities/dissimilarities among the detected compounds. To our knowledge this is the first report of saccharin, cyclamate, 2,4 - D, carbendazim, metolachlor, ethylparaben, propylparben, bisphenol A, DEHP, and benzotriazole in fish from Argentina, and the first report on the presence of lisinopril, metropolol acid and dodecanedioic acid in fish worldwide., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Quantification of drugs residues in wastewaters of different sources could help better understand contamination pathways, eventually leading to effluent regulation. However, limited data are available for hospital-derived wastewaters. Here, an analytical method based on automated on-line solid-phase extraction liquid chromatography tandem mass spectrometry (on-line SPE - UPLC-MS/MS) was developed for the quantification of multi-class pharmaceuticals in wastewaters. Filtrate phase and suspended solids (SPM) were both considered to evaluate the distribution of targeted analytes. Experimental design optimization involved testing different chromatographic columns, on-line SPE columns, and loading conditions for the filtrate phase, and different organic solvents and cleanup strategies for suspended solids. The selected methods were validated with suitable limits of detection, recovery, accuracy, and precision. A total of 30 hospital effluents and 6 wastewater treatment plants were sampled to evaluate concentrations in real field-collected samples. Certain pharmaceuticals were quantified at high levels such as caffeine at 670,000 ng/L in hospital wastewaters and hydroxyibuprofen at 49,000 ng/L in WWTP influents. SPM samples also had high contaminant concentrations such as ibuprofen at 31,000 ng/g in hospital effluents, fluoxetine at 529 ng/g in WWTP influents or clarithromycin at 295 ng/g in WWTP effluents. Distribution coefficients (K d ) and particle-associated fractions (Φ) indicate that pharmaceuticals tend to have better affinity to suspended solids in hospital wastewater than in municipal wastewaters. The results also bring arguments for at source treatment of these specific effluents before their introduction into urban wastewater systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Cyanobacterial blooms present challenges for water treatment, especially in regions like the Canadian prairies where poor water quality intensifies water treatment issues. Buoyant cyanobacteria that resist sedimentation present a challenge as water treatment operators attempt to balance pre-treatment and toxic disinfection by-products. Here, we used microscopy to identify and describe the succession of cyanobacterial species in Buffalo Pound Lake, a key drinking water supply. We used indicator species analysis to identify temporal grouping structures throughout two sampling seasons from May to October 2018 and 2019. Our findings highlight two key cyanobacterial bloom phases - a mid-summer diazotrophic bloom of Dolichospermum spp. and an autumn Planktothrix agardhii bloom. Dolichospermum crassa and Woronichinia compacta served as indicators of the mid-summer and autumn bloom phases, respectively. Different cyanobacterial metabolites were associated with the distinct bloom phases in both years: toxic microcystins were associated with the mid-summer Dolichospermum bloom and some newly monitored cyanopeptides (anabaenopeptin A and B) with the autumn Planktothrix bloom. Despite forming a significant proportion of the autumn phytoplankton biomass (>60%), the Planktothrix bloom had previously not been detected by sensor or laboratory-derived chlorophyll- a . Our results demonstrate the power of targeted taxonomic identification of key species as a tool for managers of bloom-prone systems. Moreover, we describe an autumn Planktothrix agardhii bloom that has the potential to disrupt water treatment due to its evasion of detection. Our findings highlight the importance of identifying this autumn bloom given the expectation that warmer temperatures and a longer ice-free season will become the norm.

Zwitterionic, cationic, and anionic per- and polyfluoroalkyl substances (PFAS) are increasingly reported in terrestrial and aquatic environments, but their inputs to agricultural lands are not fully understood. Here, we characterized PFAS in 47 organic waste products (OWP) applied in agricultural fields of France, including historical and recent materials. Overall, 160 PFAS from 42 classes were detected from target screening and homologue-based nontarget screening. Target PFAS were low in agriculture-derived wastes such as pig slurry, poultry manure, or dairy cattle manure (median ∑ 46 PFAS: 0.66 μg/kg dry matter). Higher PFAS levels were reported in urban and industrial wastes, paper mill sludge, sewage sludge, or residual household waste composts (median ∑ 46 PFAS: 220 μg/kg). Historical municipal biosolids and composts (1976-1998) were dominated by perfluorooctanesulfonate (PFOS), N -ethyl perfluorooctanesulfonamido acetic acid (EtFOSAA), and cationic and zwitterionic electrochemical fluorination precursors to PFOS. Contemporaneous urban OWP (2009-2017) were rather dominated by zwitterionic fluorotelomers, which represented on average 55% of ∑ 160 PFAS (max: 97%). The fluorotelomer sulfonamidopropyl betaines (X:2 FTSA-PrB, median: 110 μg/kg, max: 1300 μg/kg) were the emerging class with the highest occurrence and prevalence in contemporary urban OWP. They were also detected as early as 1985. The study informs for the first time that urban sludges and composts can be a significant repository of zwitterionic and cationic PFAS.

EPA method 539.1 recently introduced an expanded list of priority endocrine-disrupting compounds (EDCs), some of which were also included in the Unregulated Contaminant Monitoring Rule 3 (UCMR3). Though standardized methods are available for drinking water, analysis of steroid hormones and bisphenol A (BPA) at the ultra-trace level remains challenging. This study set out to evaluate the suitability of automated off-line solid-phase extraction (SPE) liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) for the determination of EPA-priority EDCs in environmental water matrixes (tap water, surface water, and wastewater influents and effluents). The target molecules included 14 steroid hormones (altrenogest, androstenedione, equilenin, equilin, α-estradiol, β-estradiol, estriol, estrone, ethinylestradiol, levonorgestrel, medroxyprogesterone, norethindrone, progesterone, testosterone) and BPA. Factors that may influence the analytical performance were assessed. This involved, for instance, testing combinations of SPE materials from different brands and protocol variations. Several materials presented absolute extraction efficiencies in acceptable ranges. Initial sample pH, nature of reconstitution medium, and mobile phase salt concentration were among the potential factors affecting analyte signal. Storage conditions (different preservative agents) possibly exerted the strongest influence, in agreement with the literature. Limits of detection were in the range of 0.03-0.5 ng/L in drinking water, 0.1-0.5 ng/L in surface water, and 0.16-1 ng/L in wastewater. Method validation also involved testing linearity, accuracy, and precision in reagent water and matrix-matched extracted calibrants. The method was applied to field-collected water samples in Eastern Canada. Summed EDC concentrations remained low in tap water (

The proliferation of harmful cyanobacterial algal blooms is of concern due to the associated release of toxins affecting ecosystems and human health. The paralytic shellfish poison saxitoxin (STX) is a small polar alkaloid that can occur in inland and marine aquatic environments. Here, we optimized a fast and sensitive analytical method for the determination of STX, neosaxitoxin (NeoSTX), and their decarbamoyl analogues in surface waters. The method involves a simple filtration, addition of isotope-labelled internal standard (ILIS), and analysis by on-line solid-phase extraction coupled to hydrophilic interaction liquid chromatography high-resolution mass spectrometry (on-line SPE-HILIC-HRMS). Except glass fiber filters, other tested materials (e.g., nylon, nitrocellulose) provided suitable filtration performance. Time-dependent adsorptive losses occurred during the LC-MS batch sequence if glass autosampler vials were used, while no such effect was observed for polypropylene autosampler vials. Matrix effects were evaluated for 4 different quantification scenarios, including external vs. internal curves and neat reagent water vs. matrix-matched curves. Matrix-matched calibration with ILIS correction (NeoSTX- 15 N 7 ) provided the best performance overall. The analytical method was validated in freshwater lake water and estuarine brackish water (30‰ salinity), with suitable determination coefficients (R 2  > 0.9975), matrix spike accuracy (90-107%), and intraday/interday precision (RSD of 0.61-16%). Method limits of detection (LOD in lake water: 0.72-3.9 ng/L) are also improved over most of the recent literature. The method was applied to a set of 302 surface water samples collected in Canada, France, and the United Kingdom, and positive detections were reported for STX (max: 98 ng/L), decarbamoyl-STX (max: 15 ng/L), and NeoSTX (max: 87 ng/L)., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Emerging PFAS were recently reported at sites impacted by aqueous film-forming foams (AFFFs) and near major manufacturing centers; however, few studies have evaluated whether these can occur far from release sites. Here, newly identified PFAS were investigated in wild sporting fish from boreal freshwater ecosystems (background sites, 2013-2014 summer seasons), compared to fish impacted by a major AFFF release (summer 2013 and autumn 2014). Different freshwater wild sporting fish species (Esox lucius, Esox masquinongy, Micropterus dolomieu, Sander vitreus, Perca flavescens, and Semotilus corporalis, n = 74) were collected from 13 ecosystems (lakes, reservoirs, and rivers) across Eastern Canada. Of 29 quantitative PFAS, 15 compounds were detected in fish from background sites, including perfluorocarboxylates (C 6,8 - 14 ), perfluoroalkane sulfonates (C 6,8,10 ), perfluorooctane sulfonamide (FOSA), 6:2 fluorotelomer sulfonate (6:2 FTSA), 7:3 fluorotelomer carboxylic acid (7:3 FTCA), and a zwitterionic PFAS-perfluorooctane sulfonamidoalkyl betaine (PFOSB). To our knowledge, this is the first report of PFOSB in biota. It is also one of the first reports of anionic fluorotelomers (6:2 FTSA, 7:3 FTCA, 9:3 FTCA) in wildlife from background sites. Long-chain fluorotelomer sulfonamidoalkyl betaines (e.g., 8:2 and 10:2 FTAB), fluorotelomer betaines (e.g., 9:3 and 9:1:2 FTB), and fluorotelomer sulfone propanoic acids (e.g., 8:2 FT(SO 2 )-PA, 10:2 FT(SO 2 )-PA)) were solely prevalent (up to 97% of summed suspect PFAS) in Smallmouth Bass (M. dolomieu) from the AFFF-impacted site. Perfluorobutane sulfonamide (FBSA), perfluorohexane sulfonamide (FHxSA), 6:2 FTSA and 7:3 FTCA were detected in at least one Smallmouth Bass sample both at the AFFF-impacted and background sites. According to the estimated chronic daily intake and current tolerable daily intake suggested by national agencies, the observed PFOS levels would not pose a health risk to anglers who might consume these wild-caught fish., 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 Elsevier B.V. All rights reserved.)

The neurotoxic alkaloid β-N-methyl-amino-l-alanine (BMAA) and related isomers, including N-(2-aminoethyl glycine) (AEG), β-amino-N-methyl alanine (BAMA), and 2,4-diaminobutyric acid (DAB), have been reported previously in cyanobacterial samples. However, there are conflicting reports regarding their occurrence in surface waters. In this study, we evaluated the impact of amending lake water samples with trichloroacetic acid (0.1 M TCA) on the detection of BMAA isomers, compared with pre-existing protocols. A sensitive instrumental method was enlisted for the survey, with limits of detection in the range of 5−10 ng L−1. Higher detection rates and significantly greater levels (paired Wilcoxon’s signed-rank tests, p < 0.001) of BMAA isomers were observed in TCA-amended samples (method B) compared to samples without TCA (method A). The overall range of B/A ratios was 0.67−8.25 for AEG (up to +725%) and 0.69−15.5 for DAB (up to +1450%), with absolute concentration increases in TCA-amended samples of up to +15,000 ng L−1 for AEG and +650 ng L−1 for DAB. We also documented the trends in the occurrence of BMAA isomers for a large breadth of field-collected lakes from Brazil, Canada, France, Mexico, and the United Kingdom. Data gathered during this overarching campaign (overall, n = 390 within 45 lake sampling sites) indicated frequent detections of AEG and DAB isomers, with detection rates of 30% and 43% and maximum levels of 19,000 ng L−1 and 1100 ng L−1, respectively. In contrast, BAMA was found in less than 8% of the water samples, and BMAA was not found in any sample. These results support the analyses of free-living cyanobacteria, wherein BMAA was often reported at concentrations of 2−4 orders of magnitude lower than AEG and DAB. Seasonal measurements conducted at two bloom-impacted lakes indicated limited correlations of BMAA isomers with total microcystins or chlorophyll-a, which deserves further investigation.

In urban areas served by separate sewerage systems, illicit connections to the storm drain system from residences or commercial establishments are frequent whether these misconnections were made accidentally or deliberately. As a result, untreated and contaminated wastewater enters into storm sewers leading to pollution of receiving waters and non-compliance with water quality standards. Typical procedures for detecting illicit connections to the storm sewer system are time consuming and expensive, especially in a highly urbanised area. In this study, we investigated the use of human wastewater micropollutants WWMPs (caffeine, theophylline, and carbamazepine) and advanced DNA molecular markers (human specific Bacteroides HF183 and mitochondrial DNA) as anthropogenic tracers in order to assist identifying potential cross connections. Water samples from storm outfalls and storm sewer pipes in three urban subcatchments were collected in dry weather from 2013 to 2018. All samples contained various concentrations of these markers especially HF183, caffeine and theophylline, suggesting that the storm pipe system studied is widely contaminated by sanitary sewers. None of the traditional indicators or markers tested is sufficient alone to determine the origin of fecal pollution. In a highly urbanised area, the combination of at least three specific human markers was needed in order to locate the residential section with likely misconnections. The human specific Bacteroides HF183, and theophylline appeared to be the most effective markers (along with E. coli) of crossconnections, whereas carbamazepine can provide an indication of contamination through sanitary sewer exfiltration. A composite sewer cross-connection index was developed, and eight misconnected houses were identified and corrected. The index approach enables the reduction of false positives that could lead to expensive interventions to identify cross-connected households. The results show the multiparameter source tracking toolbox as an effective method to identify sewer cross connections for sustainable storm water management., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021. Published by Elsevier B.V.)

Global warming and eutrophication may lead to increased incidence of harmful algal blooms and related production of cyanotoxins that can be toxic to aquatic plants. Previous studies have evaluated the phytotoxic effects of cyanotoxins on aquatic plants. However, most studies have evaluated only a limited number of plant species and cyanotoxins; there is also considerable variability between studies, which obscures general patterns and hinders understanding of the phytotoxic effects of cyanotoxins. Here, we conducted a comprehensive meta-analysis by compiling 41 published papers to estimate the phytotoxic effects of anatoxin-a, cylindrospermopsin, and microcystins in 34 species of aquatic plants, with the aim of 1) investigating the phytotoxicity of different cyanotoxins to aquatic plants; 2) determining the aquatic plant species most sensitive to the phytotoxic effects of cyanotoxins; and 3) evaluating the bioaccumulation potential of cyanotoxins in aquatic plants. Most aquatic plants were negatively affected by cyanotoxin exposure and their response was dose-dependent; however, morphological indicators and photosynthesis of certain aquatic plants were marginally stimulated under low concentrations of anatoxin-a and cylindrospermopsin. Anatoxin-a showed the greatest bioaccumulation capacity in aquatic plants compared to cylindrospermopsin and microcystin variants. Bioaccumulation factors of cyanotoxins in aquatic plants generally decreased with increasing water exposure concentrations. Our study supports the One Health goal to manage the risk of public exposure to toxic substances, and indicates that cyanotoxins warrant further investigations in aquatic plants. Environmental managers and public health authorities need to be alert to the long-term exposure and chronic toxicity of cyanotoxins, and the potential trophic transfer of cyanotoxins from aquatic plants to higher-order organisms., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2021 Elsevier B.V. All rights reserved.)

The occurrence of 93 classes of per- and polyfluoroalkyl substances (PFASs) was investigated at aqueous film-forming foam (AFFF)-impacted sites of four Canadian airports. Surface/subsurface soil and groundwater samples were characterized using high-resolution mass spectrometry (HRMS) and an improved total oxidizable precursor (TOP) assay. PFAS profiles, loads, and spatial trends were highly site-specific, influenced by the AFFF use history, variations in sorption, transport, and in situ transformation potential of PFASs. All sites have been impacted by more than one AFFF chemistry, with the active firefighter training area exhibiting a greater PFAS variety and total PFAS burden than decommissioned sites. Zwitterionic and cationic compounds composed a large percentage (34.5-85.5%) of the total PFAS mass in most surface soil samples in the source zone but a relatively low percentage (<20%) in groundwater samples. Background soils surrounding the source zone contained predominantly unidentified precursors attributed to atmospheric deposition, while in AFFF-impacted soils, precursors originating from AFFFs can be largely captured by HRMS using available suspect lists. Horizontal transfer of PFASs in surface soils was limited, but vertical migration down the soil column occurred even in locations of low permeability. This study provides a critical data set to support developing new priority analyte lists and integrating TOP assay for comprehensive PFAS monitoring at AFFF-impacted sites.

Harmful algal blooms of cyanobacteria (CyanoHABs) can lead to the release of potent toxins that can seriously affect ecosystem integrity. Some freshwater watersheds are particularly at risk considering the threats to already imperiled wildlife. The consumption of tainted drinking water and contaminated food also raises concerns for human health. In the present study, a pilot survey was conducted in the riverine ecosystem of the Pike River Ecological Reserve (QC, Canada) near Missisquoi Bay, Lake Champlain. We examined the occurrence of multiclass cyanotoxins including 12 microcystins, anatoxins, cylindrospermopsin (CYN), anabaenopeptins (AP-A, AP-B), and cyanopeptolin-A in surface waters and wild-caught fish during the summer 2018. Out of the 18 targeted cyanotoxins, 14 were detected in bloom-impacted surface water samples; toxins peaked during early-mid September with the highest concentrations for MC-LR (3.8 μg L -1 ) and MC-RR (2.9 μg L -1 ). Among the 71 field-collected fish from 10 species, 30% had positive detections to at least one cyanotoxin. In positive samples, concentration ranges in fish muscle were as follows for summed microcystins (∑MCs: 0.16-9.2 μg kg -1 ), CYN (46-75 μg kg -1 ), AP-A (1.1-5.4 μg kg -1 ), and AP-B (0.12-5.0 μg kg -1 ). To the best of our knowledge, this is one the first reports of anabaenopeptins occurrence in wildlife. The maximum ∑MCs in fish was 1.15-fold higher than the World Health Organization (WHO) daily intake recommendation for adults and nearly equated the derived value for young children. The concentration of CYN was also about 3-fold higher than the limit derived from the human health guideline values., (Copyright © 2021 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Zwitterionic per- and polyfluoroalkyl substances (PFASs) used in aqueous film-forming foams (AFFFs) could face diverse environmental fates once released at military bases, airports, fire-training areas, and accidental release sites. Here, we studied for the first time the transformation potential of four electrochemical fluorination (ECF)-based PFAS zwitterions (two carboxyl betaines and two tertiary amines) in aerobic soils. The two perfluoroalkyl sulfonamide derivatives were precursors to perfluorooctanesulfonate (PFOS), while the amide derivatives were precursors to perfluorooctane carboxylate (PFOA). These zwitterions and four other previously reported zwitterions or cations were compared for their transformation pathways and kinetics. Structural differences, especially the nitrogen head groups, largely influenced the persistence of these compounds in aerobic soils. The perfluoroalkyl sulfonamide-based compounds showed higher microbial stability than the corresponding perfluoroalkyl amide-based ones. Their stability in aerobic soils is ranked based on the magnitude of DT 50 (time for 50% of substance to disappear): quaternary ammonium ≈ carboxyl betaine ≫ tertiary amine > amine oxide. The PFASs containing quaternary ammonium or betaine groups showed high stability in soils, with the longest DT 50 likely to be years or decades, while those with tertiary amine or amine oxide groups showed DT 50 of weeks or months. These eight ECF-based precursors provide insights into the degradation pathways and persistence in surface soils of other perfluoroalkyl cations and zwitterions present in AFFFs.

Reproducible analytical procedures and rigorous quality control are imperative for an accurate monitoring of cyanobacterial toxins in environmental water samples. In this study, the short-term and long-term storage stability of diverse cyanotoxins (anatoxins, cylindrospermopsin, anabaenopeptins, and 12 microcystins) was evaluated in water samples, under different scenarios. Transport controls were performed at three monitoring sites in spiked ultrapure water and lake water to investigate short-term stability issues. Medium-term storage stability was evaluated for up to 14-28 days in ultrapure water, chlorine-treated drinking water (amended with reductant), and surface water (filtered and unfiltered) stored at different temperatures (20 °C, 4 °C, and -20 °C). Substantial decreases of cylindrospermopsin and anabaenopeptins were observed in tap water (20 °C) and unfiltered surface water (20 °C or 4 °C). Regardless of matrix type, cyanotoxin recoveries generally remained within an 80-120% range when the water samples were kept frozen. After a prolonged storage duration of 365 days at -20 °C, most cyanotoxins experienced decreases in the range of 10-20%. The notable exception was for the tryptophan-containing MC-LW and MC-WR, with more substantial variations (30% to 50% decrease) and conversion to N-formylkynurenine analogs. Reanalysis of field-collected surface waters after long-term storage at -20 °C also indicated significantly decreasing trends of cyanotoxins (between 6% and 23% decrease). In view of the above, short sample hold times should be favored as recommended in EPA methods., (Copyright © 2020. Published by Elsevier B.V.)

With the consumption of chemotherapy agents, residues of anticancer drugs may be increasingly found in hospital and municipal wastewaters. Quantification of these highly polar micropollutants remains challenging due to poor chromatographic retention on typical reversed phases. This study investigated different solid-phase extraction (SPE) materials for automated on-line preconcentration of complex matrices (hospital and municipal wastewaters) and various chromatographic column options. A hyper crosslinked hydroxylated polystyrene-divinylbenzene copolymer SPE sorbent coupled on-line with hydrophilic interaction liquid chromatography tandem mass spectrometry (HILIC-MS/MS) yielded suitable limits of detection (LOD: 1-2 ng L -1 ) for 5-fluorouracil (5-FU) and 2',2'-difluorodeoxyuridine (dFdU). Optimization of chromatographic conditions led to a single LC-MS/MS method for the analysis of other cytostatic drugs including cytarabine (CYT), gemcitabine (GEM), methotrexate (MTX), ifosfamide (IFO), cyclophosphamide (CYC) and capecitabine (CAP). The filter membrane for sample pre-treatment, HPLC mobile phase additives, and on-line SPE loading parameters were also investigated. The methods were validated in wastewater matrix with suitable determination coefficients (R 2 range: 0.9982-0.9999), LODs (0.5-5 ng L -1 ), accuracy (78-111%), intraday precision (2.6-12%), and interday precision (2.1-13%). The occurrence of cytostatic drugs was examined in field-collected water samples from hospital effluents and municipal wastewater treatment plants (WWTP) in Canada. CAP (3.7-64 ng L -1 ), dFdU (6.1-300 ng L -1 ), and MTX (1.8-68 ng L -1 ) were frequently detected across both matrix types, while IFO was detected in hospital wastewater (23-140 ng L -1 ) but not in municipal WWTPs., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Cyanotoxins are associated with harmful cyanobacterial blooms, but also exist in biological soil crusts and soils irrigated with cyanobacteria-contaminated water. To achieve an accurate analysis of cyanotoxins in soil, effective extraction, purification and determination methods are imperative. The most challenging aspect is extracting cyanotoxins from soil, due to their tendency to bind strongly to the soil matrix. We used a methanol-ammonium acetate solution to efficiently extract 17 cyanotoxins (microcystins, cylindrospermopsin, anatoxins, anabaenopeptins and cyanopeptolin) from soil. The extract was purified by on-line solid-phase extraction coupled with ultra-high-performance liquid chromatography tandem mass spectrometry. The optimized procedure involved two ultrasonication cycles of 15 min with 4 mL of methanol + 200 mM ammonium acetate, which recovered 60% to >90% of the added cyanotoxins from five soils with diverse organic matter, pH and texture. The method improved extraction by up to 10 times compared to a methanol/water solution. Linearity, accuracy and precision were validated on matrix-mixed soil with surrogate microcystin and cylindrospermopsin internal standards. Limits of detection were 0.001-0.3 ng g -1 , depending on the cyanotoxins. The method was used to analyze cyanotoxins in 25 field-collected soils from Quebec, Canada. Out of the 25 soil samples, 11 soils had at least one cyanotoxin, and up to 8 different cyanotoxins were detected in one soil. The sum of all microcystins congeners was from 0.02 to 31 ng microcystins g -1 soil. We also detected anabaenopeptin, the first reported occurrence of this cyanotoxin in soil., 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 B.V. All rights reserved.)

Sand as a filter media is often challenged by the presence of organics in the form of natural organic matter, metal ions, and various micropollutants in the source water. It is mainly due to the presence of limited active adsorption sites and low surface area that governs an ineffective adsorption potential of the sand material. Herein, graphitized sand was synthesized to tackle the above limitations using two sugar solution sources: a) brewery effluent (as a low-cost solution) (GS1) and; b) sucrose solution (GS2). GS1 showed 68%, 60%, and 99% higher maximum adsorption constant (q max ) for divalent metal ions: iron, copper, and manganese, respectively as compared to raw sand (RS). Coating of MnO 2 over the graphitized sand (GSMs: GS1M and GS2M) further helped in Microcystin-LR (MC-LR) removal (3%-9%) when inoculated with MC-LR-degraders, but was not as effective in removing metals, organic carbon and nitrogen when compared to just graphitized sand (GS1 or GS2). Inoculating GS and GSMs (for both sugar sources) not only helped in higher MC-LR removal (10%-15% more) but also enhanced the removal of other water contaminants including metals, organic nitrogen, and carbon. GS1 showed 20% and 50% more MC-LR removal than the sand material when tested at a low and high initial concentration of MC-LR (5 µg/L and 50 µg/L). The highest breakthrough period was obtained for GS1 filter using 1 mg/L Rhodamine-B dye, which was 12 times (48 min) more than the raw sand filter and almost 2.5 times (second best, 21 min) than GS1M. After three cycles of regeneration and reuse of GS1 filter, a decrease of just 14% in saturation adsorption capacity indicated its high reusability aspects., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Critical knowledge gaps remain regarding the fate and effects of zwitterionic, cationic, and anionic perfluoroalkyl and polyfluoroalkyl substances (PFASs), including assessment of their bioaccumulation potential. Here, biota soil accumulation factors (BSAFs) were assessed in earthworms ( Eisenia fetida ) exposed to soil microcosms amended with zwitterionic fluorotelomers and anionic perfluoroalkyl acids. The 6:2 fluorotelomer sulfonamidoalkyl betaine (6:2 FTAB) bioaccumulated in earthworms [BSAF ∼ 2.5-5.4 (g dw,worm /g dw,soil ) -1 ] but to a lesser extent than perfluorooctane sulfonate (PFOS: BSAF ∼ 21-29). The BSAF of perfluorocarboxylates increased from ∼2.0 for C 4 -C 6 analogues to ∼92 for perfluorotridecanoate (C 13 ). In earthworms exposed to Ansulite and Arctic Foam aqueous film-forming foams (AFFFs), the BSAF was related to perfluorinated chain length for n :3 fluorotelomer betaines (FtBs), n :1:2 FtB, and n :2 FTAB. Earthworms were also collected in situ from a fire-equipment testing site at a major Canadian airport. Summed PFAS concentrations were between 65 000 and 830 000 ng g -1 wet weight, possibly the highest burden recorded in terrestrial biota. Fluorotelomer sulfonates (6:2 FTS, 8:2 FTS, and 10:2 FTS) and FtB were particularly prevalent. Field worms also displayed elevated concentrations of n :3 acids ( n = 3-11), but not those from laboratory microcosms exposed to fluorotelomer-based AFFFs. The findings provide an important confirmation to recent data suggesting that fluorotelomer compounds may accumulate in invertebrate species with limited metabolization.

The neurotoxin β-N-methylamino-L-alanine (BMAA), suspected to trigger neurodegenerative diseases, can be produced during cyanobacterial bloom events and subsequently affect ecosystems and water sources. Some of its isomers including β-amino-N-methylalanine (BAMA), N-(2-aminoethyl) glycine (AEG), and 2,4-diaminobutyric acid (DAB) may show different toxicities than BMAA. Here, we set out to provide a fast and sensitive method for the monitoring of AEG, BAMA, DAB and BMAA in surface waters. A procedure based on aqueous derivatization with 9-fluorenylmethyl chloroformate (FMOC-Cl) was investigated for this purpose. Under optimized conditions, a small aqueous sample aliquot (5 mL) was spiked with BMAA-d3 internal standard, subjected to FMOC-Cl derivatization, centrifuged, and analyzed. The high-throughput instrumental method (10 min per sample) involved on-line pre-concentration and desalting coupled to ultra-high-performance liquid chromatography high-resolution mass spectrometry (UHPLC-HRMS). Chromatographic gradient and mobile phases were adjusted to obtain suitable separation of the 4 isomers. The method limits of detection were in the range of 2-5 ng L-1. In-matrix validation parameters including linearity range, accuracy, precision, and matrix effects were assessed. The method was applied to surface water samples (n = 82) collected at a large spatial scale in lakes and rivers in Canada. DAB was found in >70% of samples at variable concentrations (<3-1,900 ng L-1), the highest concentrations corresponding to lake samples in cyanobacterial bloom periods. BMAA was only reported (110 ng L-1) at one HAB-impacted location. This is one of the first studies to report on the profiles of AEG, BAMA, DAB, and BMAA in background and impacted surface waters., Competing Interests: The authors have declared that no competing interests exist.

The occurrence and spatial distribution of selected pesticides were investigated along a 200-km reach of the St. Lawrence River (SLR) and tributaries in Quebec, Canada. Surface water samples (n = 68) were collected in the summer 2017 and analyzed for glyphosate, atrazine (ATZ), 8 systemic insecticides (acetamiprid, clothianidin, dinotefuran, fipronil, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam) and some metabolites. Overall, 99% of the surface water samples were positive to at least one of the targeted pesticides. The most recurrent compounds were glyphosate (detection frequency: 84%), ATZ (82%), thiamethoxam (59%), desethylatrazine (DEA: 47%), and clothianidin (46%). Glyphosate displayed variable levels (4-3,000 ng L -1 ), with higher concentrations in south tributaries (e.g., Nicolet and Yamaska). In positive samples, the sum of ATZ and DEA varied between 5 and 860 ng L -1 , and the sum of 6 priority neonicotinoids between 1.5 and 115 ng L -1 . From Repentigny to the Sorel Islands, the spatial distribution of pesticides within the St. Lawrence River was governed by the different upstream sources (i.e., Great Lakes vs. Ottawa River) due to the limited mixing of the different water masses. Cross-sectional patterns revealed higher concentrations of glyphosate and neonicotinoids in the north portions of transects, while the middle and south portions showed higher levels of atrazine. In Lake St. Pierre and further downstream, cross-sections revealed higher levels of the targeted pesticides near the southern portions of the SLR. This may be due to the higher contributions from south shore tributaries impacted by major agricultural areas, compared to north shore tributaries with forest land and less cropland use. Surface water samples were compliant with guidelines for the protection of aquatic life (chronic effects) for glyphosate and atrazine. However, 31% of the samples were found to surpass the guideline value of 8.3 ng L -1 for the sum of six priority neonicotinoids., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

The herbicide atrazine remains in use in Canada, the United States, and several other countries, while being banned since 2003 in the European Union. A comprehensive quality survey of atrazine (ATZ) and one of its metabolites, desethylatrazine (DEA), was conducted in 2015-2018 in drinking water available to consumers in Quebec, Canada. Temporal variations of ATZ and DEA were monitored in tap water from the Montreal area for 18 consecutive months (Temporal survey 2015-2016). Within this time window, the sum of ATZ and DEA in tap water samples (n = 450) varied from 40 to 250 ng L -1 (median: 98 ng L -1 ). ATZ was systematically detected (100%), with a concentration range of 30-195 ng L -1 (median: 49 ng L -1 ) while DEA was in the range of 10-187 ng L -1 (median: 36 ng L -1 ). Maximum ATZ concentrations remained about 25× lower than the Canadian drinking water quality guideline (5000 ng L -1 ), but 48% of the samples were above that of the European Union (100 ng L -1 ) regarding the sum of ATZ and DEA. Trends of ATZ and DEA in drinking water were also examined across southwestern Quebec (Spatial survey 2017-2018). The sum of the two triazines in this second set of samples varied from below the method detection limit (for 33 out of the 52 surveyed municipalities) to 104 ng L -1 . Apart from Montreal, locations in the southern shore of the St. Lawrence showed generally higher levels of atrazine and DEA. The highest concentrations clustered in the Montérégie region, along the St. Lawrence River (e.g., Brossard, Longueuil, Saint-Constant) and/or downstream from agricultural areas. The ATZ concentrations are suggested to have decreased compared to previous surveys, which is consistent with the decrease in the sales of active ingredients in Ontario (upstream sources) and Quebec., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The list of endocrine disrupting compounds (EDCs) defined under U.S. EPA Method 539 was recently expanded to include additional hormones and bisphenol A (BPA). Here, we validated a fast and robust alternative method compliant with Method 539.1 requirements in diverse water matrixes (i.e., ultra-pure water, tap water, surface water, and wastewater influent and effluent). Automated large volume injection solid phase extraction (SPE) coupled on-line to ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was investigated for this purpose. The surveyed molecules included 13 EPA-priority hormones (testosterone, progesterone, medroxyprogesterone, levonorgestrel, norethindrone, androstenedione, estrone, β-estradiol, α-estradiol, equilin, equilenin, ethinylestradiol, estriol) and BPA. Combinations of ionization source and mobile phases were optimized for improved sensitivity. Suitable chromatographic performances were obtained and the implementation of an on-line SPE washing step consecutive to sample loading was investigated. On-line SPE extraction efficiencies in acceptable ranges (64-79%) and detection limits in the order of nanogram per liter or sub-nanogram per liter were obtained. The linearity range extended over 2-3 orders of magnitude, with determination coefficients (R 2 ) typically > 0.9980. Robust precision and trueness complying with acceptance criteria (70-130%) were obtained for the scope of analytes/matrix combinations. Limited internal standard variations were also observed across samples (±18%), well within the ±50% acceptance criterion. The method was successfully applied to field-collected samples in Canada and summed EDC concentrations were reported in the range of 0.80-2.8 ng L -1 , 6.8-19 ng L -1 , 260-790 ng L -1 , and 37-360 ng L -1 in tap water, surface water, effluent and influent wastewater samples, respectively., (Copyright © 2019 Elsevier B.V. All rights reserved.)

This database presents the optimization of ultra-high-performance liquid chromatography electrospray ionization tandem mass spectrometry (UHPLC-MS/MS) for the analysis of EPA-priority endocrine disruptor compounds (13 hormones and bisphenol A). Various method parameters were tested and compared for improved sensitivity. Data related to the selection of the ionization source (heated-ESI vs. APCI) are presented, including optimization results of source parameters. Compound-dependent responses when varying the UHPLC mobile phase salt concentration of ammonium fluoride (NH 4 F) are supplied. Details on the chromatographic gradient program and chromatographic data demonstrating the separation of α-estradiol and β-estradiol are provided. In addition, we supply the details on mass spectrometry parameters under the optimized conditions, relative responses of quantification and confirmation MS/MS transitions (QT/CT), and number of points present in UHPLC-MS/MS spectra. The sample preparation and instrumental analysis procedures under the retained conditions are also described. The herein dataset supports the research " Analysis of Environmental Protection Agency priority endocrine disruptor hormones and bisphenol A in tap, surface and wastewater by online concentration liquid chromatography tandem mass spectrometry " Goeury et al., 2019.

The occurrence of micropollutants in water resources is raising substantial concerns, worldwide. These pollutants may have adverse impacts on the aquatic ecosystem and human health. Even though activated carbon is commonly used as an adsorbent to remove micropollutants from water, its low removal of hydrophilic components, energy-intensive regeneration procedure and slow adsorption can impair its applicability. Polymeric resins have been suggested as an effective alternative adsorbent due to their high porosity and accessible adsorption sites, significant adsorption concentration and stable chemical properties. In this work, we evaluated the performance of five commercially available polymeric resins (including two ion exchange resins) for the removal of nine selected micropollutants in water. More specifically, we investigated the effect of polymeric resin type and concentration, contact time and water matrix on the removal efficiency of five pharmaceuticals, two pesticides and two endocrine disruptors of high current concern (diclofenac, sulfamethoxazole, fluoxetine, caffeine, carbamazepine, 17-β estradiol, norethindrone, atrazine and desesthylatrazine). Results presented herein indicated that two hydrophobic polymeric resins can effectively adsorb over 80% of the targeted micropollutants within 30 min when the resin concentration was higher than 2.5 mL L -1 . The adsorption data were well described with the Freundlich isotherm and the pseudo-second order kinetic model very well described the kinetic process of the selected micropollutants onto the polymeric resins. Moreover, we observed that increasing the synthetic water temperature from 4 to 22 °C led to a marginally higher micropollutant uptake and the presence of natural organic matter had no noted impact on the efficiency of the resins in removing the tested micropollutants when the resin dosage was 5.4 mL L -1 . On the basis of these promising results, we conclude that polymeric resins are a promising alternative to activated carbon for micropollutants sorption in drinking water treatment., (Copyright © 2019 Elsevier B.V. All rights reserved.)

The comprehensive analysis of aqueous film forming foam (AFFF) formulations has led in recent years to the discovery of novel classes of perfluoroalkyl and polyfluoroalkyl substances (PFASs). Whether the pre-existing analytical methods for historically monitored PFASs, including perfluorooctane sulfonate (PFOS), could be transferable to a large breadth of newly identified PFASs remains, however, an open question. Data from various lines of evidence indicate that current extraction procedures previously validated with anionic and neutral PFASs may seriously underperform for many cationic and zwitterionic PFASs. The extraction efficiency and instrumental response could be strongly matrix-dependent, which may preclude a robust analysis. The present study sought to investigate a suitable sample preparation procedure for the analysis of anionic, cationic, and zwitterionic PFASs in soil samples. In total, 86 PFASs, representing 24 chemical classes previously discovered in AFFF formulations or at AFFF-impacted sites, were evaluated. The merits and limitations of various extraction media were examined using an AFFF-impacted field-weathered loam soil, as well as a background loam soil amended with AFFFs in-house. Methanol with hydrochloric acid provided excellent recoveries for most cationic and zwitterionic PFASs, including fluorotelomer sulfonamidoalkyl betaines (e.g., 6:2 FTAB) and fluorotelomer betaines (e.g., 9:1:2 FTB), yet performed less satisfactorily for certain anionic PFASs, and may also cause conversion of some PFASs. Sequential extractions using methanol with ammonium acetate exhibited limited matrix effects and suitable recoveries of PFASs from soils of diverse textural classes and organic matter content. The newly-developed extraction method presented the best option for future in-depth characterization of PFASs at AFFF-impacted sites., (Copyright © 2018 Elsevier B.V. All rights reserved.)

This study evaluated the adsorption capacity and rate constants for 9 micropollutants (MP) on fresh and aged magnetic powdered activated carbon (MPAC) as a magnetically separable alternative to conventional PAC for drinking water treatment. MPAC with mass fractions of 10%, 38% and 54% maghemite nanoparticles were compared to bare PAC and pure maghemite in batch adsorption experiments. Pure maghemite alone did not adsorb significant amounts of MP and when normalized to PAC content, no significant differences of MP adsorption between MPAC and PAC were observed. Freundlich constants K F (normalized to PAC content) ranged between 2.3-37 μg/mg (L/μg) 1/n for all MP and adsorbents. Pseudo-second order rate constants for MP decreased with increasing maghemite content ranging between 0.2-2.7 mg/μg/min for bare PAC and 0.02-2.19 mg/μg/min for MPAC. Residual adsorption capacities of 90-days old colonized adsorbents were 10 times lower than for fresh adsorbent. At typical concentrations of 3.5 g colonized adsorbent/L found inside reactors, kinetics were still fast and removals of all MP except sulfamethoxazole exceeded 90% within 5 min., (Copyright © 2018 Elsevier B.V. All rights reserved.)

In the last decade or so, concerns have arisen with respect to the widespread occurrence of perfluoroalkyl acids (PFAAs) in the environment, food, drinking water, and humans. In this study, the occurrence and levels of a large range of perfluoroalkyl and polyfluoroalkyl substances (PFASs) were investigated in drinking water (bottled and tap water samples) from various locations around the world. Automated off-line solid phase extraction followed by ultra-high-performance liquid chromatography coupled to high-resolution mass spectrometry was used to analyze PFASs of various chain lengths and functional groups. In total, 29 target and 104 suspect-target PFASs were screened in drinking water samples (n=97) from Canada and other countries (Burkina Faso, Chile, Ivory Coast, France, Japan, Mexico, Norway, and the USA) in 2015-2016. Out of the 29 PFASs quantitatively analyzed, perfluorocarboxylates (PFCAs: C 4/14 ), perfluoroalkane sulfonates (PFSAs: C 4 , C 6 , C 8 ), and perfluoroalkyl acid precursors (e.g., 5:3 fluorotelomer carboxylate (5:3 FTCA)) were recurrently detected in drinking water samples (concentration range: -1 ). Tap water samples from Canada showed noteworthy differences depending on their source; for instance, ∑ 29 PFASwas significantly greater in those produced from the Great Lakes/St. Lawrence River ecosystem than those produced from other types of sources (14 versus 5.3ngL -1 , respectively). A suspect-target screening approach indicated that other perfluoroalkane sulfonamides (FBSA, FHxSA), perfluoroethyl cyclohexane sulfonate (PFECHS), ultrashort chain (C 2 -C 3 ) PFSAs (PFEtS, PFPrS), and two additional PFSAs (PFPeS (C 5 ) and PFHpS (C 7 )) were repeatedly present in tap water samples (concentration ranges: -1 ). To the authors' best knowledge, this constitutes the first observation of a cyclic perfluoroalkane sulfonate (PFECHS) and C 4 -C 6 perfluoroalkane sulfonamides (FBSA, FHxSA) in drinking water. According to the newly updated US EPA health advisory for PFOS and PFOA (70ngL -1 ), the drinking water samples collected in the present monitoring would not pose a health risk to consumers as regards PFAA levels., (Copyright © 2017 Elsevier B.V. All rights reserved.)

A fast and high-throughput method is proposed for the determination of total microcystins (ΣMC) in environmental surface waters. After a 1-h Lemieux-von Rudloff oxidation step to yield the 2-methyl-3-methoxy-4-phenylbutyric acid (MMPB) moiety, samples were quenched, filtered, and directly analyzed. This was achieved via solid phase extraction (SPE) coupled on-line to ultra-high performance liquid chromatography electrospray ionization triple stage quadrupole mass spectrometry. The choice of on-line SPE settings was conducted using experimental designs. Given the matrix complexity of oxidation extracts, the on-line desalting step was found to be a critical parameter to ensure suitable method robustness. The on-line sample loading volume was 5mL, and the wash volume applied for on-line desalting was 3mL. Instrumental analysis was performed in just 8min. The method limit of quantification was 0.5ngL -1 ΣMC (i.e. 2000 times lower than the current World Health Organization - WHO drinking water guideline). Excellent determination coefficients were observed for matrix-free and matrix-based calibration curves alike, and the linearity range tested spanned∼4 orders of magnitude. Accuracy and intermediate precision did not depend on the spike level and proved satisfactory (in the range of 93-110% and 3-6%, respectively). A thorough assessment of instrumental matrix effects was conducted by comparing standard additions curves in several lake and river oxidation extracts with the matrix-free reference. Regardless of the internal standard used (4-PB or D3-MMPB), instrumental matrix effects were efficiently compensated. The matrix effect that may occur at the earlier sample preparation stage was evaluated separately. While the oxidation step was generally not complete (yield ∼65%), the conversion rates of MCs into MMPB remained within a consistent range of values regardless of matrix type. No significant back-pressure was observed upon consecutive injections of oxidation-based samples, while the instrumental sensitivity remained unaffected. The herein described method could therefore be eligible for future large-scale monitoring surveys. The method was applied to a selection of surface water samples (n=30) collected across the province of Québec, Canada, and the results were compared to those achieved by an individual variant analysis of 8 MC congeners and a commercial ELISA kit., (Copyright © 2017 Elsevier B.V. All rights reserved.)

The derailment of an unmanned train carrying crude oil and subsequent fire in the town of Lac-Mégantic, Quebec, led to the use of 33 000 L of aqueous film forming foam (AFFF) concentrate. While it is known that per- and polyfluoroalkyl substances (PFASs) contained in AFFFs pose a potential environmental and health risk, critical knowledge gaps remain as regards to their environmental fate after release. The accident in Lac-Mégantic provided valuable information regarding the identity and concentration of PFASs present in the soil after the AFFF deployment, as well as their possible transformation over time. The current study analyzed four sets of samples from Lac-Mégantic: soil collected days after the accident from a heavily impacted area, soil sampled two years later from the treatment biopiles, soil collected two years after the accident from downtown Lac-Mégantic, and nonimpacted soil from a nearby area. A total of 33 PFASs were quantified in the soils. The highest observed concentrations correspond to those of 6:2 fluorotelomer sulfonamidoalkyl betaine, 6:2 and 8:2 fluorotelomer sulfonates, and short chain perfluorocarboxylic acids. The soils collected in Lac-Mégantic two years after the accident show a total PFAS concentration that is ∼50 times lower than soils collected in 2013, while the proportion of perfluoroalkyl acids in those samples shows an increase. Qualitative analysis revealed the presence in soil of 55 additional PFASs that had been previously identified in AFFF formulations. The present study highlights the need to perform detailed analysis of AFFF impacted sites, instead of focusing solely on perfluoroalkyl acids.

The effects of fluoxetine, one of the most prescribed selective serotonin-reuptake inhibitors (SSRIs) during pregnancy, and its active metabolite norfluoxetine were studied on placental aromatase (CYP19) and feto-placental steroidogenesis. Fluoxetine did not alter estrogen secretion in co-culture of fetal-like adrenocortical (H295R) and trophoblast-like (BeWo) cells used as a model of the feto-placental unit, although it induced CYP19 activity, apparently mediated by the serotonin (5-HT) 2A receptor/PKC signaling pathway. Norfluoxetine decreased estrogen secretion in the feto-placental co-culture and competitively inhibited catalytic CYP19 activity in BeWo cells. Decreased serotonin transporter (SERT) activity in the co-culture was comparable to 17β-estradiol treatment of BeWo cells. This work shows that the complex interaction of fluoxetine and norfluoxetine with placental estrogen production, involves 5-HT-dependent and -independent mechanisms. Considering the crucial role of estrogens during pregnancy, our results raise concern about the impact of SSRI treatment on placental function and fetal health., (Copyright © 2016 Elsevier Ireland Ltd. All rights reserved.)

Trace emerging contaminants (ECs) occur in both waste and surface waters that are rich in particulates that have been found to sorb several organic contaminants. An analytical method based on off-line solid-phase extraction (SPE) followed by liquid chromatography-mass spectrometry (LC-MS) analysis was developed for the detection and quantification of 31 ECs from surface water, wastewater, suspended particulate matter (SPM) as well as sediments. Lyophilized sediments and air-dried SPM were subjected to ultrasonic extraction. Water samples and extracts were then concentrated and cleaned-up by off-line SPE. Quantification was realized using a Q Exactive mass spectrometer in both full scan (FS) and MS 2 modes. These two modes were optimized and compared to determine which one was the most suitable for each matrix studied. Yeast estrogen screen assay (YES-assay) adapted from the direct measurement of estrogenic activity without sample extraction was tested on filtered wastewater samples. An endocrine disrupting effect was detected in all effluent samples analyzed with estradiol equivalent concentrations ranging from 4.4 to 720 ng eq E2 L -1 for the WWTP-1 and 6.5-42 ng eq E2 L -1 for the WWTP-2. The analytical methods were also applied on six samples of surface water, the corresponding SPM, the sediments and thirty-nine effluent samples from two wastewater treatment plants (WWTPs) sampled over a period of five months (February to June 2014)., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

The aerobic biotransformation over 180 days of two cationic quaternary ammonium compounds (QACs) with perfluoroalkyl chains was determined in soil microcosms, and biotransformation pathways were proposed. This is the first time that polyfluoroalkyl cationic surfactants used in aqueous film-forming foam (AFFF) formulations were studied for their environmental fate. The biotransformation of perfluorooctaneamido quaternary ammonium salt (PFOAAmS) was characterized by a DT50 value (time necessary to consume half of the initial mass) of 142 days and significant generation of perfluoroalkyl carboxylic acid (PFOA) at a yield of 30 mol % by day 180. The biotransformation of perfluorooctane sulfonamide quaternary ammonium salt (PFOSAmS) was very slow with unobservable change of the spiked mass; yet the generation of perfluorooctanesulfonate (PFOS) at a yield of 0.3 mol % confirmed the biotransformation of PFOSAmS. Three novel biotransformation intermediates were identified for PFOAAmS and three products including perfluorooctane sulfonamide (FOSA) for PFOSAmS through high-resolution mass spectrometry (MS) analysis and t-MS(2) fragmentation. The significantly slower PFOSAmS biotransformation is hypothesized to be due to its stronger sorption to soil owing to a longer perfluoroalkyl chain and a bulkier sulfonyl group, when compared to PFOAAmS. This study has demonstrated that despite overall high stability of QACs and their biocide nature, the ones with perfluoroalkyl chains can be substantially biotransformed into perfluoroalkyl acids in aerobic soil.

Adsorption of mixtures of cyanotoxins onto sediment as a dominant mechanism in the elimination of cyanotoxins from the aqueous phase has not been extensively investigated. The aim of this study was to investigate adsorption and desorption behavior of six microcystins including microcystin (MC)-LR, RR, YR, LY, LW and LF and cylindrospermopsin (CYN) on natural sediment. Freundlich and Langmuir isotherms could be fitted for MC-LR, RR, YR and CYN. Sorption kinetics showed immediate rapid adsorption for all cyanotoxins: CYN, MCLW and MCLF were adsorbed 72.6%, 56.7% and 55.3% respectively within 2 h. Results of desorption experiments demonstrated that less than 9% of cyanotoxins desorbed from sediment within 96 h. Adsorption of cyanotoxins onto three fractionated sediments particles, clay-silt (<75 μm), find sand (75-315 μm) and coarse sand (315-2000 μm) demonstrated that adsorption capacity of coarse sand fraction for all the tested cyanotoxins was less than 4% of the clay-silt fraction. Results of this study revealed that there is a potential for cyanotoxins to accumulate in the sediments of lakes, as well as in drinking water treatment plants. Monitoring programs must consider cyanotoxins in the particulate phase to avoid largely underestimating toxin concentrations following their release from blooms., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

An alternative analysis technique for the quantitation of 15 poly- and perfluoroalkyl substances (PFASs) in water matrices is reported. Analysis time between each sample was reduced to less than 20s, all target molecules being analyzed in a single run with the use of laser diode thermal desorption atmospheric pressure chemical ionization (LDTD/APCI) coupled with high resolution accurate mass (HRMS) orbitrap mass spectrometry. LDTD optimal settings were investigated using either one-factor-at-a-time or experimental design methodologies, while orbitrap parameters were optimized simultaneously by means of a Box-Behnken design. Following selection of an adequate sample concentration and purification procedure based on solid-phase extraction and graphite clean-up, the method was validated in an influent wastewater matrix. Environmentally significant limits of detection were reported (0.3-4ngL(-1) in wastewater and 0.03-0.2ngL(-1) in surface water) and out of the 15 target analytes, 11 showed excellent accuracies (±20% of the target values) and recovery rates (75-125%). The method was successfully applied to a selection of environmental samples, including wastewater samples in 7 locations across Canada, as well as surface and tap water samples from the Montreal region, providing insights into the degree of PFAS contamination in this area., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A molecularly imprinted polymer (MIP) was synthesized by non-covalent imprinting polymerization using irinotecan as template. Methacrylic acid and 4-vinylpyridine were selected as functional monomers. An optimized procedure coupled to LC-PDA analysis was developed for the selective solid-phase extraction of irinotecan from various organic media. A specific capacity of 0.65 µmol•g-1 for the MIP was determined. The high specificity of this MIP was demonstrated by studying the retention behaviour of two related compounds, camptothecin and SN-38. This support was applied for the extraction of irinotecan from human serum samples.

It is remarkable that the famous écorchés of Honoré Fragonard have survived the centuries to reach us today. Studies carried out by several teams have established details of the technique used by Fragonard that help to explain their longevity. The injection of the vessels was achieved by means of a mixture of mutton tallow and pine resin diluted in essence of turpentine and essential oils. This gave Fragonard a very high success rate. Above all, he did not add pigments to his mixture while injecting the veins, and this facilitated the procedure. The vessels were painted after preservation to give them the vivid colors that we can still see today. Another detail that explains their exceptional conservation is that the varnish used by Fragonard was composed of Venice turpentine, made from larch resin and known to repel insects., (2010 Wiley-Liss, Inc.)