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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.)

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.)