Search

Introduction: Per- and polyfluoroalkyl substances (PFAS) are prevalent environmental chemicals used extensively in consumer and industrial products. Distressing disruptions to sexual function are prevalent in reproductive-aged women, yet its etiology is incompletely characterized. PFAS could plausibly affect sexual function because they interfere with the production, metabolism, and secretion of reproductive hormones and have known neurotoxic properties. To our knowledge, however, no research to date has evaluated associations between PFAS exposure and female sexual function. Objective: To evaluate associations between PFAS biomarker concentrations and female sexual function. Methods: We used cross-sectional data from the Pregnancy Study Online (PRESTO; n=82), a preconception cohort study of female-identified pregnancy planners living in the United States or Canada, to estimate associations between PFAS biomarker concentrations and female sexual function, measured using 6 select items from the Female Sexual Function Index (FSFI). We summed scores from the FSFI items to create a sexual function score (range=0-30; median in PRESTO=22). Lower scores were indicative of worse sexual function. We measured concentrations of four PFAS (specifically PFOS, PFOA, PFNA, and PFHxS) in serum using isotope-dilution tandem mass spectrometry. We used multivariable linear regression to estimate mean differences in sexual function scores per interquartile range (IQR) increase in PFAS concentrations with 95% confidence intervals (CIs), adjusting for potential confounders. We stratified results by parity (parous vs. nulliparous) to evaluate the potential for effect modification by prior pregnancy, as placental transfer, menstruation, and lactation are known routes of PFAS elimination. Results: Median serum PFAS concentrations (ng/mL) were 1.3, 1.1, 0.3, and 0.7 for PFOS, PFOA, PFNA, and PFHxS, respectively. An IQR increase in PFHxS was associated with a 1.4-point decrease (95% CI -2.1, -0.6) in sexual function scores, reflecting a ~5% change. Among parous participants, there was a consistent trend of decreased sexual function scores per IQR increase in PFAS concentrations. The strongest association was observed for PFOS, where an IQR increase in serum concentration was associated with a 4.9-point decrease in sexual function scores (95% CI -9.1, -0.6). Conclusions: These preliminary findings indicate that higher serum PFAS concentrations are associated with decreased self-reported female sexual function. Prior research evaluating the relationship between environmental chemical exposures and sexual function have historically focused on male outcomes (e.g., semen quality). These fundings suggest value in expanding research focused on the sexual health consequences of endocrine disrupting chemicals to include female sexual function. Disclosure: Any of the authors act as a consultant, employee or shareholder of an industry for: LAW serves as a consultant to AbbVie, Inc. [ABSTRACT FROM AUTHOR]

Processed plant-based foods, particularly high carbohydrate-containing foods, are among the greatest contributors to dietary acrylamide, a probable human carcinogen, uptake. Between 2009 and 2020, five surveys were conducted to determine acrylamide in high carbohydrate-containing foods in Canada. These surveys included sampling of potato and sweet potato chips, French fries, and frozen potato/sweet potato products, as a follow-up to our earlier surveys from 2002 - 2008. Samples were analyzed using isotope dilution ( 13 C 3 -acrylamide) with LC-MS/MS. The highest mean acrylamide levels were found in sweet potato chips. Among potato chips (57 to 4660 ng g -1 ), one brand consistently showed the highest concentrations with wide variability. Acrylamide concentrations decreased over time in ready-to-eat French fries (from 480 to 358 ng g -1 ), and one brand showed a clear reduction temporally. Wide variations were observed among brands, among lots/outlets of same brands, and among different food chains. Acrylamide levels in potato chips decreased between 2009 and 2016 (504.3 ng g -1 ) relative to the period 2002 - 2008 (1096.9 ng g -1 ). The acrylamide trends observed in the products measured in the latest study indicate that food producers may have adopted mitigation strategies.

In 1998, Health Canada mandated folic acid fortification of white flour and enriched grain products to prevent neural tube defects. At the time, neither the Canadian Nutrient File (CNF) nor product labels reflected the actual folate content of foods. We aimed to assess if 20 years post-fortification, the CNF values for total folate and synthetic folic acid accurately reflect amounts determined by direct analysis. Using the 2001 Food Expenditure Survey and ACNielsen Company data, we identified 10-15 of the most purchased fortified foods across seven food categories in Canada. Total folate concentrations were determined by tri-enzyme digestion and microbial assay. Folic acid concentrations were determined using liquid chromatography-tandem mass spectrometry. Except for "cooked pastas", mean total folate content of foods ( n  = 89) were significantly higher than CNF values across categories ( p  < 0.05), reflecting 167% ± 54% of CNF values. Similarly, mean folic acid content of foods was higher than CNF values for all categories except "cooked pastas" ( p  < 0.05), with a mean of 188% ± 94% of CNF values; the latter CNF values included uncooked pasta. In sum, 20 years post-fortification, and 10 years since the last direct measurement, CNF and product label values still underestimate actual total folate and the folic acid content of foods. These findings emphasize that dietary estimates established using the CNF may significantly underestimate actual intakes and thus caution should be exercised when interpreting estimates of nutritional adequacy based on these values., Competing Interests: The authors have no conflicts of interest relevant to this article to disclose.

Background: Matrix effects are a known problem with immunoassays measuring serum 25-hydroxyvitamin D [25(OH)D]., Objectives: To determine if the inverse association between serum 25(OH)D and serum cholesterol concentrations is a function of assay method: Diasorin Liaison 25(OH) Vitamin D Total Assay (Liaison Total Assay), an immunoassay, compared with liquid chromatography tandem mass spectrometry (LC-MS/MS)., Methods: Canadian Health Measures Survey data and biobank serum (White males aged 20-79 y, n = 392) were evaluated for bias in serum 25(OH)D using Bland-Altman plots. Differences in serum 25(OH)D (Liaison Total Assay - LC-MS/MS) were compared among non-HDL-cholesterol <4.2 (n = 295) compared with ≥4.2 (n = 97) mmol/L and total cholesterol groups <5.2 (n = 256) compared with ≥5.2 (n = 136) mmol/L, and associations tested between 25(OH)D and non-HDL-cholesterol or total cholesterol concentrations, using regression., Results: Serum 25(OH)D measured using Liaison Total Assay ranged from 10.7 to 137.0 nmol/L and 14.4 to 137.9 nmol/L by LC-MS/MS. Liaison Total Assay - LC-MS/MS showed a negative bias of 5.5 (95% limits of agreement -23.8, 12.7) nmol/L. Differences in 25(OH)D were -4.0 ± 9.0 (±SD) nmol/L if non-HDL-cholesterol was <4.2 mmol/L and -10.2 ± 8.7 nmol/L if ≥4.2 mmol/L (P < 0.0001). Differences in 25(OH)D, if total cholesterol was <5.2 mmol/L, were -3.4 ± 8.6 nmol/L and -9.6 ± 9.3 nmol/L if ≥5.2 mmol/L (P < 0.0001). Serum non-HDL-cholesterol (beta -3.17, P = 0.0014) and total cholesterol (beta -2.77, P = 0.0046) were inversely associated with Liaison Total Assay 25(OH)D (adjusted for age, fasting, and body mass index), but not with LC-MS/MS measured 25(OH)D. Interference by these lipoproteins was not eliminated by standardization of the Liaison Total Assay. Similar associations were observed with triglycerides as for the lipoproteins., Conclusions: Total cholesterol inversely associates with 25(OH)D, which is likely due to elevated non-HDL-cholesterol lipoprotein or triglyceride interference with the Liaison Total Assay. This is important as elevated cholesterol is common, and an underestimation of vitamin D status could be an unnecessary cause for concern., (Crown Copyright © 2024. Published by Elsevier Inc. All rights reserved.)

The effect of genotype and environment on oat protein composition was analyzed through size exclusion-high-performance liquid chromatography (SE-HPLC) and liquid chromatography-mass spectrometry (LC-MS) to characterize oat protein isolate (OPI) extracted from three genotypes grown at three locations in the Canadian Prairies. SE-HPLC identified four fractions in OPI, including polymeric globulins, avenins, glutelins, and albumins, and smaller proteins. The protein composition was dependent on the environment, rather than the genotype. The proteins identified through LC-MS were grouped into eight categories, including globulins, prolamins/avenins, glutelins, enzymes/albumins, enzyme inhibitors, heat shock proteins, grain softness proteins, and allergenic proteins. Three main globulin protein types were also identified, including the P14812|SSG2-12S seed storage globulin, the Q6UJY8&#95;TRITU-globulin, and the M7ZQM3&#95;TRIUA-Globulin-1 S. Principal component analysis indicated that samples from Manitoba showed a positive association with the M7ZQM3&#95;TRIUA-Globulin-1 S allele and Q6UJY8&#95;TRITU-globulin, while samples from Alberta and Saskatchewan had a negative association with them. The results show that the influence of G × E on oat protein fractions and their relative composition is crucial to understanding genotypes' behavior in response to different environments.

• A high-risk screening study was performed for patients with chronic kidney disease. • Globotriaosylceramide (Gb 3) was analyzed in dried urine spots by LC-MS/MS. • A total of 397 participants were recruited in four centers across Canada. • No Fabry patients were detected in this study. • Chronic kidney disease might be associated with increased urinary Gb 3 concentrations. Fabry disease is an X-linked lysosomal storage disorder with a highly heterogeneous clinical presentation. This complex disease is caused by a deficient activity of the enzyme α-galactosidase A, which is involved in the catabolism of glycosphingolipids. The prevalence of Fabry disease is underestimated, due to the presence of atypical variants. High-risk screening protocols are particularly relevant for this disease due to the availability of treatments, such as enzyme replacement and chaperone therapies. As kidney manifestations are present in the majority of male and many female patients with Fabry disease, a high-risk screening protocol was performed for patients with chronic kidney disease of unknown etiology. Recruitment of 397 participants took place in four centers across Canada from 2011 to 2017. Globotriaosylceramide (Gb 3) was analyzed in dried urine spots by liquid chromatography/tandem mass spectrometry followed by globotriaosylsphingosine (lyso-Gb 3) on the repeat analysis. The collection and shipment of urine specimens on filter paper resulted in easier handling/shipment and significant cost-saving. No Fabry patients were detected in this study. Increased concentrations of urinary Gb 3 were observed in 13.6% of patients with chronic kidney disease suggesting that chronic kidney disease or other comorbidities might be associated with increased urinary Gb 3 concentrations. [ABSTRACT FROM AUTHOR]

The objectives of this study were to investigate the Fusarium damage-deoxynivalenol (FUS DMG-DON) relationship in various wheat growing locations in western Canada in 2016 and to compare the relationships to the Prairie-wide FUS DMG-DON assessment of that harvest year. Fusarium head blight was prevalent in spring wheat and durum grown in western Canada in 2016. Harvest survey samples for Canada Western Red Spring (CWRS) wheat and Canada Western Amber Durum (CWAD) were inspected for Fusarium damaged kernels, and analyzed using an enzyme-linked immunosorbent assay for the Fusarium-produced mycotoxin DON. For CWAD and most CWRS, there was a significant relationship between FUS DMG (represented as the mass percentage of Fusarium damaged kernels) and DON, whose presence is regulated in food products to minimize consumers' exposure. However, CWRS from south-central Alberta contained much lower DON than expected by the reported visual symptoms of FUS DMG of the samples. High throughput real-time PCR analysis showed that DON-producing Fusarium species were associated with less than 40% of the Fusarium damaged kernels in the CWRS. This was different from what was observed with CWAD grown in the same area in 2016. Multi-mycotoxin analysis by liquid chromatography with tandem mass spectrometry did not show an increased presence of mycotoxins produced by other Fusarium species, and therefore suggested that the observed damage in CWRS from south-central Alberta was not caused by Fusarium species. [ABSTRACT FROM AUTHOR]

Perchlorate is a low molecular weight highly soluble anion. It occurs naturally in the environment, primarily near potash deposits and in arid regions. The determination of perchlorate in human milk is of interest in vulnerable populations such as infants and pregnant women. In this study, a sensitive and selective isotope dilution ion chromatography/tandem mass spectrometry (ID IC-MS/MS) method was developed and validated for the determination of perchlorate in human milk samples collected from the Maternal-Infant Research on Environmental Chemicals (MIREC) Study. The limit of detection (LOD) was 0.27 µg·kg−1 for human milk. A total of 439 human milk samples were analysed with measurable levels of perchlorate in most of the milk samples, and the mean value was 7.62 ± 32.7 µg·kg−1. This project provided important information related to perchlorate levels in human milk collected across Canada and the extent to which pregnant women and their infants may be exposed to perchlorate. A dietary exposure assessment was also conducted in infants based on the measured values in human milk. The mean perchlorate probable daily intakes (PDIs) for infants consuming human milk were 0.31 ± 0.07 μg/kg bw/day for infants under 1 year and 0.17 ± 0.10 μg/kg bw/day for infants between 1 and 3 years old. None of the estimates exceeded the FAO/WHO provisional maximum tolerable daily intake (PMTDI) of 10 μg/kg bw/day. [ABSTRACT FROM AUTHOR]

Folic acid supplementation is recommended during pregnancy to support healthy fetal development; (6 S )-5-methyltetrahydrofolic acid ((6 S )-5-MTHF) is available in some commercial prenatal vitamins as an alternative to folic acid, but its effect on blood folate status during pregnancy is unknown. To address this, we randomised sixty pregnant individuals at 8-21 weeks' gestation to 0·6 mg/d folic acid or (6 S )-5-MTHF × 16 weeks. Fasting blood specimens were collected at baseline and after 16 weeks (endline). Erythrocyte and serum folate were quantified via microbiological assay (as globally recommended) and plasma unmetabolised folic acid (UMFA) via LC-MS/MS. Differences in biochemical folate markers between groups were explored using multivariable linear/quantile regression, adjusting for baseline concentrations, dietary folate intake and gestational weeks. At endline ( n 54), the mean values and standard deviations (or median, inter-quartile range) of erythrocyte folate, serum folate and plasma UMFA (nmol/l) in those supplemented with (6 S )-5-MTHF v . folic acid, respectively, were 1826 (sd 471) and 1998 (sd 421); 70 (sd 13) and 78 (sd 17); 0·5 (0·4, 0·8) and 1·3 (0·9, 2·1). In regression analyses, erythrocyte and serum folate did not differ by treatment group; however, concentrations of plasma UMFA in pregnancy were 0·6 nmol/l higher (95 % CI 0·2, 1·1) in those supplementing with folic acid as compared with (6 S )-5-MTHF. In conclusion, supplementation with (6 S )-5-MTHF may reduce plasma UMFA by ∼50 % as compared with supplementation with folic acid, the biological relevance of which is unclear. As folate is currently available for purchase in both forms, the impact of circulating maternal UMFA on perinatal outcomes needs to be determined.

Human exposure to pesticides commands the implementation of food safety control, but few studies have provided a comparative assessment of conventional and organic products. This study set out to examine 22 pesticides in four distinct commodities (lettuce, apples, grapes, and tomatoes) from conventional and organic agriculture available to consumers. A multiresidue procedure based on QuEChERS extraction and ultra-high-performance liquid chromatography tandem mass spectrometry (UHPLC-MS/MS) was first validated for its robustness. Suitable determination coefficients (R2 > 0.99) and recoveries generally between 70 and 110% were obtained. Intraday and interday variations were <20% and low matrix effects were noted with sample-to-sample variation. Method limits of detection (LOD) in the overall range of 0.05–2 μg kg−1 were obtained. The validated method was applied to 133 fruit and vegetable samples purchased in Canada, including conventional and organic culture samples. Overall, 47% of the 133 samples had levels above the LOD for at least one pesticide. Neonicotinoid insecticides were detected in all four product types. Imidacloprid (0.08–29 μg kg−1), acetamiprid (0.11–108 μg kg−1), and clothianidin (0.13–141 μg kg−1) were the most recurrent. Atrazine was reported in approximately a third of the lettuce samples (0.25–7.5 μg kg−1). For varieties with samples available from both organic and conventional agriculture, the proportion of insecticide levels > LOD was significantly higher (p < 0.05) for samples from conventional agriculture (9.7%) than from organic agriculture (2.0%). Measured levels were compliant to Canadian Maximum Residue Limits (MRLs), but a thorough human health risk assessment has yet to be conducted for many of these pesticides. • Multiclass pesticides were analyzed by QuEChERS–LC-MS/MS in fruits and vegetables. • Testing of 133 real samples indicated 47% of positives to at least one pesticide. • Multiple pesticide residues were detected in about half of these positive samples. • Recurrent pesticides were imidacloprid, acetamiprid, clothianidin, and atrazine. • Higher pesticide occurrence was noted in varieties of conventional vs. organic culture. [ABSTRACT FROM AUTHOR]

Failure to attain and sustain long term glycemic control is an ongoing challenge in diabetes therapy. The trend to use a combined therapy and the risk of drug-drug interaction (DDI) are elevated and thus the need for sensitive analytical methods is of great significance. Herein, a simple, robust, and sensitive reverse phase high performance liquid chromatography–electrospray ionization-tandem mass spectrometry (ESI-MS/MS) method for simultaneous determination of metformin (MET) and pioglitazone (PGT) in rat plasma using canagliflozin (CAN) as internal standards (IS) was developed and fully validated. Prior Chromatographic separation on an Agilent Eclipse Plus C18 (4.6 × 100 mm, 3.5 μm) using gradient mobile phase system consisting of ammonium formate pH 4.5 and acetonitrile at a flow rate of 0.5 mL min−1, within a run time of 14 min, the antidiabetic drugs were extracted from rat plasma using acetonitrile-induced protein precipitation technique. Multiple reaction monitoring in positive ion mode was used for quantitation of precursor to production at m / z 130.1 → 71.0 & 60 for MET, 357.2 → 134.2 for PGT, and 462.16 → 191.1 for CAN. Method linearity was obeyed in the range of 1 to 5000 and 1 to 2500 ng mL−1 for MET and PGT, respectively. The developed method was validated in terms of accuracy, precision, selectivity, recovery, matrix effects, and stability as per US-FDA bioanalytical guidelines and successfully applied to clinical pharmacokinetic and DDI studies with a single oral administration of target compounds. The peak plasma concentrations (C max) and area under the concentration-time curve (AUC) of MET was significantly influenced by the concomitant administration of PGT at equal concentration and vice versa. PGT affected the absorption and elimination rate of MET via inhibition of organic cationic transporter (OCT). Molecular modeling study revealed the significant interaction of PGT with OCT. A potential DDI in type 2 diabetic patient receiving chronic treatment with MET and PGT deserves further attention and study to improve drug therapy and prevent adverse effects. • An HPLC-MS/MS assay for simultaneous determination of metformin and pioglitazone in rat plasma • The method fully validated and applied for pharmacokinetic and drug-drug interaction studies. • Pioglitazone affects C max and AUC of MET when co-administered orally. • The study shows for the first time the drug interaction of pioglitazone and metformin. [ABSTRACT FROM AUTHOR]

Nunavimmiut (Inuit of Nunavik, Northern Quebec, Canada) exhibit a high selenium (Se) status because of their frequent consumption of marine mammal foods. Indirect evidence from our previous studies had suggested that selenoneine – a novel selenocompound – may be accumulating in the blood of Nunavimmiut. We used a liquid-chromatography/inductively coupled tandem mass spectrometry (LC-ICP-MS/MS) method to measure concentrations of selenoneine and its methylated metabolite Se-methylselenoneine in archived red blood cells (RBC) obtained from 210 Nunavimmiut living in communities along the Hudson Strait, where marine mammal hunting and consumption are most frequent in Nunavik. This method was adapted to quantify selenoneine and its methylated metabolite in beluga mattaaq, an Inuit delicacy consisting of the skin with the underlying layer of fat and the major dietary source of Se for Nunavimmiut. Total selenium concentration was also measured in RBC and beluga mattaaq samples by isotope dilution ICP-MS/MS. The median selenoneine concentration in RBC was 413 μg Se/L (range = 3.20–3230 μg Se/L), representing 54% (median) of total Se content (range = 1.6–91%). Quantification of selenoneine in five beluga mattaaq samples (skin layer) from Nunavik revealed a median concentration of 1.8 μg Se/g wet wt (range = 1.2–7.4 μg Se/g), constituting 54% (median) of the total Se content (range = 44–74%). Se-methylselenoneine was also detected in Inuit RBC but not in beluga mattaaq, suggesting that selenoneine undergoes methylation in humans. Selenoneine may protect Nunavimmiut from methylmecury toxicity by increasing its demethylation in RBC and in turn decreasing its distribution to target organs. Image 1 • LC-ICP-MS/MS was used to quantify selenoneine and Se-methylselenoneine in RBCs. • Selenoneine represented 54% of total Se content in Inuit RBCs. • Selenoneine was also the major Se species in beluga mattaaq – an Inuit delicacy. • Selenoneine may protect Inuit against methylmercury toxicity. [ABSTRACT FROM AUTHOR]

Perfluoroalkyl substances (PFASs) are known to be toxic, bioaccumulative, and persistent. However, exposure routes and toxic effects to humans are still widely unknown. Our objectives were to evaluate potential correlations between concentrations of PFASs in maternal plasma and infant cord blood with home characteristics and developmental effects, including wheezing. The concentrations of 17 PFASs were measured in plasma from prenatal women (n = 414), postnatal women (n = 247), and cord blood (n = 50) from a subset of participants in a population-based birth cohort in Winnipeg, Manitoba, Canada, using online solid phase extraction (SPE) with liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Multiple linear regression and principal component analysis (PCA) were used to evaluate possible associations with PFAS concentrations. Surveys were used to collect information regarding maternal characteristics (e.g. age, parity, duration of breastfeeding), infant characteristics (e.g. birth weight, birth length, head circumference, gestational age, and incidence of recurrent wheezing), and home characteristics (e.g. home age,carpet coverage in the most used room, presence of new furniture, or recent home renovations). PFASs in plasma were associated with maternal characteristics but not home characteristics or early childhood wheezing. PFASs were not associated with developmental effects, with the exception that perfluoroundecanoic acid (PFUA) was negatively associated with birth weight. Further studies investigating the potential influences of PFUA on birth weight are warranted. Image 1 • PFASs in pre- and postnatal blood were associated with maternal characteristics. • PFASs in pre- and postnatal blood were not associated with home characteristics. • Perfluoroundecanoic acid (PFUA) was negatively associated with birth weight. • No correlations between PFASs in blood and incidence of recurrent wheeze in infants. • Perfluoropentanoic acid (PFPA) was among the higher measuring analytes in blood. Principal component analysis showed that PFASs in maternal blood were related to maternal characteristics and, for the most part, not home characteristics or developmental effects. [ABSTRACT FROM AUTHOR]

Highlights • A fast analysis of 14 EPA-priority endocrine disruptors was validated in water. • On-line pre-concentration and LC–MS/MS conditions were carefully optimized. • The total analysis time was <16 min with LOD at sub part-per-trillion levels. • Quantification performances were compliant with EPA method 539.1 requirements. • Method demonstration to real drinking water, surface water, and wastewater samples. Abstract 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 (R2) 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. [ABSTRACT FROM AUTHOR]

• Polarity switching for simultaneous mass analysis in positive and negative ESI. • Quantitation of organic UV filters in chlorinated waters. • SPE allows for preconcentration of low level analytes in swimming pools. Ultraviolet filters (UVFs) absorb UV light and are comprised of numerous classes of compounds including inorganic and organic. They have been used for decades in protecting humans from skin damage and cancer. Recent studies have shown that UVFs are found in many phases of abiotic and biotic systems with their physical-chemical characteristics determining environmental fate and potential biological impacts such as bioaccumulation. This study developed a unified method to quantify eight UVFs (avobenzone, dioxybenzone, homosalate, octinoxate, octisalate, octocrylene, oxybenzone, and sulisobenzone) by solid phase extraction and ultra-high performance liquid chromatography-tandem mass spectrometry using polarity switching. The validated method resulted in accuracies ranging from 75 to 112%, MLD/MLQs of 0.00015/ 0.00049 to 0.0020/ 0.0067 ng mL−1, and precisions of 1.8 to 22.6% (intraday) and 1.3 to 17.2% (interday). The method was applied to chlorinated outdoor pool waters in the City of Winnipeg, Manitoba, Canada. This method could be adapted for a variety of chlorinated and unchlorinated waters such as drinking water, wastewater, and surface waters. [ABSTRACT FROM AUTHOR]

Metabolomics based on high-resolution mass spectrometry has become a powerful technique in biomedical research. The development of various analytical tools and online libraries has promoted the identification of biomarkers. However, how to make mass spectrometry collect more data information is an important but underestimated research topic. Herein, we combined full-scan and data-dependent acquisition (DDA) modes to develop a new targeted DDA based on the inclusion list of differential and preidentified ions (dpDDA). In this workflow, the MS 1 datasets for statistical analysis and metabolite preidentification were first obtained using full-scan, and then, the MS/MS datasets for metabolite identification were obtained using targeted DDA of quality control samples based on the inclusion list. Compared with the current methods (DDA, data-independent acquisition, targeted DDA with time-staggered precursor ion list, and iterative exclusion DDA), dpDDA showed better stability, higher characteristic ion coverage, higher differential metabolites' MS/MS coverage, and higher quality MS/MS spectra. Moreover, the same trend was verified in the analysis of large-scale clinical samples. More surprisingly, dpDDA can distinguish patients with different severities of coronary heart disease (CHD) based on the Canadian Cardiovascular Society angina classification, which we cannot distinguish through conventional metabolomics data collection. Finally, dpDDA was employed to differentiate CHD from healthy control, and targeted metabolomics confirmed that dpDDA could identify a more complete metabolic pathway network. At the same time, four unreported potential CHD biomarkers were identified, and the area under the receiver operating characteristic curve was greater than 0.85. These results showed that dpDDA would expand the discovery of biomarkers based on metabolomics, more comprehensively explore the key metabolites and their association with diseases, and promote the development of precision medicine.

The increasing variability of the illicit drug market has imposed serious health risks for people who use drugs (PWUD), particularly due to the increasing co-occurrence of opioids and etizolam (or other benzodiazepines) in some jurisdictions. A miniature mass spectrometer (MS) equipped with paper capillary spray ionization was evaluated for its ability to quantify fentanyl, fluorofentanyl, carfentanil, and etizolam in illicit drug samples. Prior to testing actual drug samples, inter- and intra-day reproducibility, calibration linearity, and analytical sensitivity were assessed. The development of a continuous spray solvent delivery system improved MS/MS quantitation by prolonging ionization stability. A simple, rapid and quantitative tandem mass spectrometry method was developed and employed for the analysis of real-world illicit drug samples provided by PWUD at a harm reduction site in Victoria, British Columbia, Canada. Limits of detection ranged from 0.001 to 0.24% w/w of illicit analyte in the original solid drug samples. Target analytes were detected and quantified via the miniature MS system for samples where conventional on-site drug checking technologies were not always effective. These promising results demonstrate the potential role for miniature mass spectrometer systems for on-site drug checking services that can be both sensitive to trace, toxic levels as well as adaptable/selective for new drug threats as they appear in the illicit drug supply. [Display omitted] • The increased variability of the illicit drug market has imposed serious health risks for people who use drugs (PWUD). • A rapid & quantitative miniature MS method was developed and employed for the analysis of real-world illicit drug samples. • Target analytes were quantified via miniature MS, where other on-site drug checking technologies were not always effective. • Miniature MS systems for on-site drug checking services are sensitive, adaptable and selective for new drug threats. [ABSTRACT FROM AUTHOR]

Background: Prognostication is very important to clinicians and families during the early management of severe traumatic brain injury (sTBI), however, there are no gold standard biomarkers to determine prognosis in sTBI. As has been demonstrated in several diseases, early measurement of serum metabolomic profiles can be used as sensitive and specific biomarkers to predict outcomes., Methods: We prospectively enrolled 59 adults with sTBI (Glasgow coma scale, GCS ≤ 8) in a multicenter Canadian TBI (CanTBI) study. Serum samples were drawn for metabolomic profiling on the 1st and 4th days following injury. The Glasgow outcome scale extended (GOSE) was collected at 3- and 12-months post-injury. Targeted direct infusion liquid chromatography-tandem mass spectrometry (DI/LC-MS/MS) and untargeted proton nuclear magnetic resonance spectroscopy ( 1 H-NMR) were used to profile serum metabolites. Multivariate analysis was used to determine the association between serum metabolomics and GOSE, dichotomized into favorable (GOSE 5-8) and unfavorable (GOSE 1-4), outcomes., Results: Serum metabolic profiles on days 1 and 4 post-injury were highly predictive (Q 2  > 0.4-0.5) and highly accurate (AUC > 0.99) to predict GOSE outcome at 3- and 12-months post-injury and mortality at 3 months. The metabolic profiles on day 4 were more predictive (Q 2  > 0.55) than those measured on day 1 post-injury. Unfavorable outcomes were associated with considerable metabolite changes from day 1 to day 4 compared to favorable outcomes. Increased lysophosphatidylcholines, acylcarnitines, energy-related metabolites (glucose, lactate), aromatic amino acids, and glutamate were associated with poor outcomes and mortality., Discussion: Metabolomic profiles were strongly associated with the prognosis of GOSE outcome at 3 and 12 months and mortality following sTBI in adults. The metabolic phenotypes on day 4 post-injury were more predictive and significant for predicting the sTBI outcome compared to the day 1 sample. This may reflect the larger contribution of secondary brain injury (day 4) to sTBI outcome. Patients with unfavorable outcomes demonstrated more metabolite changes from day 1 to day 4 post-injury. These findings highlighted increased concentration of neurobiomarkers such as N-acetylaspartate (NAA) and tyrosine, decreased concentrations of ketone bodies, and decreased urea cycle metabolites on day 4 presenting potential metabolites to predict the outcome. The current findings strongly support the use of serum metabolomics, that are shown to be better than clinical data, in determining prognosis in adults with sTBI in the early days post-injury. Our findings, however, require validation in a larger cohort of adults with sTBI to be used for clinical practice., (© 2023. The Author(s).)

Organophosphate esters (OPEs) are widely used in numerous consumer products for their flame retardant and plasticizing properties. Despite potential widespread exposure, biomonitoring data during critical windows of development are scarce and limited to the most widely studied metabolites. We quantified urinary concentrations of multiple OPE metabolites in a vulnerable Canadian population. Using data and biobanked specimens from the Maternal-Infant Research on Environmental Chemicals (MIREC) study (2008-2011), we measured first trimester urinary concentrations of 15 OPE metabolites as well as one flame retardant metabolite and quantified associations with sociodemographic and sample collection characteristics in 1865 pregnant participants. We applied 2 different analytical methods to quantify OPEs, one using UItra-Performance Liquid Chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) and the other using Atmospheric Pressure Gas Chromatography coupled to mass spectrometry (APGC-MS/MS) with sensitive limits of detection (0.008-0.1 μg/L). We modelled associations between sociodemographic and sample collection characteristics and specific gravity-standardized chemical concentrations. Six OPE metabolites were detected in the majority (68.1-97.4 %) of participants. Bis-(2-chloroethyl) hydrogen phosphate had the highest detection rate (97.4 %). Diphenyl phosphate had the highest geometric mean concentration (0.657 μg/L). Metabolites of tricresyl phosphate were detected in few participants. Associations between sociodemographic characteristics varied according to each OPE metabolite. Pre-pregnancy body mass index tended to be positively associated with OPE metabolite concentrations whereas age tended to be inversely associated with OPE concentrations. OPE concentrations were, on average, higher in urine samples collected in the summer than other seasons the winter. We present the largest biomonitoring study of OPE metabolites in pregnant people to date. These findings demonstrate widespread exposure to OPEs and their metabolites and identify subpopulations who may experience heightened 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., (Crown Copyright © 2023. Published by Elsevier B.V. All rights reserved.)

Background: Glyphosate is the most widely applied herbicide in agriculture. Glufosinate is a broad spectrum herbicide used to manage glyphosate-resistant weeds. Despite the widespread use of these herbicides, biomonitoring data - which inform risk assessment and management - are sparse., Objectives: To identify determinants of urinary concentrations of these herbicides and their metabolites in pregnancy., Methods: We measured urinary concentrations of glyphosate, glufosinate, and their primary metabolites aminomethylphosphonic acid (AMPA) and 3-methylphosphinicopropionic acid (3-MPPA) in a single spot urine specimen collected during the first trimester of pregnancy from the Maternal-Infant Research on Environmental Chemicals (MIREC) study. MIREC recruited about 2000 pregnant women from 10 Canadian cities between 2008 and 2011. We used UItra-Performance Liquid Chromatography coupled to tandem mass spectrometry (UPLC-MS/MS) with sensitive limits of detection to quantify analyte concentrations. We examined urinary concentrations according to maternal sociodemographics, sample collection characteristics, reported pesticide use, and consumption of fruits, vegetables, legumes, and grain products. We used ANOVA models with specific gravity-standardized chemical concentrations as the dependent variable to determine associations with maternal and sample determinants., Results: Among women with biobanked urine samples (n = 1829-1854), 74% and 72% had detectable concentrations of glyphosate and AMPA, respectively. In contrast, one and six percent of women had detectable concentrations of glufosinate and 3-MPPA, respectively. The specific gravity-standardized geometric mean (95% CI) concentrations of glyphosate and AMPA were 0.112 (0.099-0.127) μg/L and 0.159 (0.147-0.172) μg/L, respectively. We observed a dose-response relationship between consumption of whole grain bread and higher urinary glyphosate concentrations. Season of urine collection and self-reported pesticide use were not associated with increased concentrations of any analyte., Conclusions: We detected glyphosate and AMPA in the majority of pregnant women from this predominantly urban Canadian cohort. Diet was a probable route of exposure., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:Warren G. Foster reports a relationship with Hollingsworth LLC that includes: paid expert testimony., (Crown Copyright © 2022. Published by Elsevier Inc. All rights reserved.)

Glycidyl fatty acid esters (GEs) are processing contaminants formed during refining steps of vegetable oils. 'In vivo' hydrolysis of GEs releases potentially carcinogenic and genotoxic glycidol (2,3-epoxy-1-propanol). Occurrence of GEs in vegetable oils used for infant formula manufacturing may pose a potential health concern for formula-fed infants. Refined oils are commonly used as the main fat ingredient in formula manufacturing. For this study, different infant formula products (powders, concentrates and ready-to-feed formula products) were purchased and analysed in 2015 (35 samples) and 2019 (33 samples). Seven individual GEs were analysed by LC-MS/MS via direct approach by stable isotope dilution analysis, and total bound glycidol concentrations were calculated. Concentrations of bound glycidol in reconstituted formula reached maxima of 40.3 ng/g in the 2015 samples and 31.5 ng/g in the samples collected in 2019, with respective means of 8.7 ng/g and 6.7 ng/g. The analysed bound glycidol concentrations are comparable with concentration ranges from other studies, but are higher than observed in studies from the European market. Temporal trend data show a reduction of bound glycidol concentrations in 2019. GE concentrations were compared across different manufacturers.

Abstract: Phthalate metabolites are often measured in biomonitoring studies to evaluate a population's exposure to ubiquitous phthalates. During the course of national biomonitoring studies in Canada, we identified an issue with the accuracy of several commercial phthalate metabolite standards that are commonly used in such studies. The validity of the results from these studies was then questioned. Altogether, three (3) large studies were affected, involving a total of 9302 samples and 105000 individual phthalate metabolite measurements. Data from our previous investigation suggested that the inaccuracies in the commercially-available phthalate metabolite standards were compound- and lot-specific. Therefore, an approach was developed to derive correction factors for each lot of phthalate metabolite standard and was applied to the previously-acquired measurements with the goal of obtaining accurate and comparable data. A statistical analysis was performed to support the approach. It is expected that the corrected phthalate metabolite data from all three Canadian biomonitoring studies are comparable to one another. However, caution is still advised when comparing data obtained from biomonitoring studies for which the calibration standards have not been investigated for their accuracy. Suggestions are made based on quality assurance aspects to improve the validity of phthalate metabolite measurements. [Copyright &y& Elsevier]

Background: The human milk proteome comprises a vast number of proteins with immunomodulatory functions, but it is not clear how this relates to allergy of the mother or allergy development in the breastfed infant. This study aimed to explore the relation between the human milk proteome and allergy of both mother and child., Methods: Proteins were analyzed in milk samples from a subset of 300 mother-child dyads from the Canadian CHILD Cohort Study, selected based on maternal and child allergy phenotypes. For this selection, the definition of "allergy" included food allergy, eczema, allergic rhinitis, and asthma. Proteins were analyzed with non-targeted shotgun proteomics using filter-aided sample preparation (FASP) and nanoLC-Orbitrap-MS/MS. Protein abundances, based on label-free quantification, were compared using multiple statistical approaches, including univariate, multivariate, and network analyses., Results: Using univariate analysis, we observed a trend that milk for infants who develop an allergy by 3 years of age contains higher abundances of immunoglobulin chains, irrespective of the allergy status of the mother. This observation suggests a difference in the milk's immunological potential, which might be related to the development of the infant's immune system. Furthermore, network analysis showed overall increased connectivity of proteins in the milk of allergic mothers and milk for infants who ultimately develop an allergy. This difference in connectivity was especially noted for proteins involved in the protein translation machinery and may be due to the physiological status of the mother, which is reflected in the interconnectedness of proteins in her milk. In addition, it was shown that network analysis complements the other methods for data analysis by revealing complex associations between the milk proteome and mother-child allergy status., Conclusion: Together, these findings give new insights into how the human milk proteome, through differences in the abundance of individual proteins and protein-protein associations, relates to the allergy status of mother and child. In addition, these results inspire new research directions into the complex interplay of the mother-milk-infant triad and allergy., Competing Interests: MA holds a Tier 2 Canada Research Chair in the Developmental Origins of Chronic Disease at the University of Manitoba and is a Fellow in the Canadian Institutes for Advanced Research (CIFAR) Humans and the Microbiome Program. She receives research funding from the Canadian Institutes of Health Research, Research Manitoba, the Canada Foundation for Innovation, the Bill and Melinda Gates Foundation, the Manitoba Children’s Hospital Foundation, Prolacta Biosciences, Mitacs, CIFAR, the Garfield Weston Foundation, Health Data Research UK, and Canadian COVID Immunity Task Force. She regularly speaks at conferences and workshops on infant nutrition, some sponsored by Prolacta Biosciences, and has spoken at a conference sponsored by AstraZeneca. She has contributed without remuneration to online courses on breast milk and the infant microbiome produced by Microbiome Courses. She serves in a volunteer capacity for the International Society for Research on Human Milk and Lactation and as a member of the US Canada Joint Human Milk Initiative. She has consulted for DSM Nutritional Products and serves on the Malaika Vx Scientific Advisory Board. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Dekker, Azad, Boeren, Mandhane, Moraes, Simons, Subbarao, Turvey, Saccenti and Hettinga.)

Airports are identified hotspots for air pollution, notably for fine particles (PM 2.5 ) that are pivotal in aerosol-cloud interaction processes of climate change and human health. We herein studied the field observation and statistical analysis of 10-year data of PM 2.5 and selected emitted co-pollutants (CO, NO x , and O 3 ), in the vicinity of three major Canadian airports, with moderate to cold climates. The decadal data analysis indicated that in colder climate airports, pollutants like PM 2.5 and CO accumulate disproportionally to their emissions in fall and winter, in comparison to airports in milder climates. Decadal daily averages and standard errors of PM 2.5 concentrations were as follows: Vancouver, 5.31 ± 0.017; Toronto, 6.71 ± 0.199; and Montreal, 7.52 ± 0.023 μg/m 3 . The smallest and the coldest airport with the least flights/passengers had the highest PM 2.5 concentration. QQQ-ICP-MS/MS and HR-S/TEM analysis of aerosols near Montreal Airport indicated a wide range of emerging contaminants (Cd, Mo, Co, As, Ni, Cr, and Pb) ranging from 0.90 to 622 μg/L, which were also observed in the atmosphere. During the lockdown, a pronounced decrease in the concentrations of PM 2.5 and submicron particles, including nanoparticles , in residential areas close to airports was observed, conforming with the recommended workplace health thresholds (~ 2 × 10 4  cm -3 ), while before the lockdown, condensable particles were up to ~ 1 × 10 5  cm -3 . Targeted reduction of PM 2.5 emission is recommended for cold climate regions., (© 2022. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

Abstract: Over the past 20 years, oil sands exploration and processing in Canada have grown steadily, leading to the development of intensive large-scale operations in Alberta, Canada. Naphthenic acids (NAs), a complex mixture of aliphatic and alicyclic carboxylic acids, are by-products of oil sands processing and are known to be toxic. While oil sands processing water (OSPW) is contained in tailings ponds, potential seepage and leaking of OSPW and its contaminants into surrounding surface water systems is a concern. The ability to quantify NAs and their isomers in OSPW surrounding water is essential for monitoring these spills. Unfortunately, quantification of NAs and their isomers is challenging due to the complexity of the NA mixtures, the lack of commercially available standards, and interference from naturally occurring NA compounds. Techniques such as FT-IR and GC/MS are currently used to analyse NAs, but are limited by poor sensitivity and specificity in the case of FT-IR and long sample preparation and instrument run time for GC/MS. To tackle these issues, a rapid LC/MS method was developed which can quickly quantify NAs in surface water with much better sensitivity and specificity than current methods. This method uses large volume injection, ESI negative mode and a Poroshell LC column to improve the method limits of detection (LOD) and quantitation (LOQ). The method is robust and has no complicated sample preparation steps. The method detection limit (MDL) is 0.01mg/L (10ppb) and low limit of quantitation (LLOQ) of 0.1mg/L (100ppb), both for surface water. The developed method was tested with samples from the oil sands producing region, and demonstrated its applicability for fast screening of surface water samples before resorting to costly high accuracy and high resolution mass spectrometry determination. This is the first very rapid LC/MS method using large volume single column direct injection for quantitative determination of naphthenic acids in surface water. [Copyright &y& Elsevier]

Abstract: The presence of cyanotoxins in benthic Lyngbya wollei algae samples collected in a fluvial lake along the St. Lawrence River, Canada, was investigated using a multi-toxins method. Hydrophilic interaction liquid chromatography (HILIC) and reverse phased liquid chromatography (RPLC) were coupled to triple quadrupole mass spectrometry (LC-QqQMS) for quantification and to quadrupole-time of flight mass spectrometry (LC-QqTOFMS) for screening and confirmation. The presence of two saxitoxin analogues, LWTX-1 and LWTX-6, was confirmed in benthic Lyngbya wollei algae samples. Concentration of LWTX-1 was between 209±5 and 279±9μgg−1. No other targeted cyanotoxin (such as anatoxin-a, nodularin, microcystin-LR, microcystins-RR and saxitoxin) was found in the samples. The presence of LWTX-6 was observed by using a screening approach based on an in-house database of cyanotoxins, an algorithm of identification and high resolution mass spectrometry measurements on the precursor and product ions. This work demonstrates the need for more research on the fate of benthic cyanotoxins in aquatic ecosystems such the St. Lawrence River. [Copyright &y& Elsevier]

Analytical methods are generally developed and optimized for specific commodities. Total Diet Studies, representing typical food products 'as consumed', pose an analytical challenge since every food product is different. In order to address this technical challenge, a selective and sensitive analytical method was developed suitable for the quantitation of ochratoxin A (OTA) in Canadian Total Diet Study composites. The method uses an acidified solvent extraction, an immunoaffinity column (IAC) for clean-up, liquid chromatography-tandem mass spectrometry (LC-MS/MS) for identification and quantification, and a uniformly stable isotope-labelled OTA (U-[13C20]-OTA) as an internal recovery standard. Results are corrected for this standard. The method is accurate (101% average recovery) and precise (5.5% relative standard deviation (RSD)) based on 17 duplicate analysis of various food products over 2 years. A total of 140 diet composites were analysed for OTA as part of the Canadian Total Diet Study. Samples were collected at retail level from two Canadian cities, Quebec City and Calgary, in 2008 and 2009, respectively. The results indicate that 73% (102/140) of the samples had detectable levels of OTA, with some of the highest levels of OTA contamination found in the Canadian bread supply. [ABSTRACT FROM AUTHOR]

The multitude of food recalls in 2007 clearly demonstrated that total nitrogen-content (Σ N) determination by means of near-infrared spectroscopy (NIRS) and Kjeldahl-based measurements can be deceived, and should no longer be regarded as a complete quality assurance program for nutritive-protein evaluations. Furthermore, contemporary Canadian-employed analytical tools are precariously limited in their ability to effectively assure a product where there is no a priori knowledge of the environmental toxin(s) involved. In light of these challenges, this study explored a number of analytical techniques used to assess and furthermore assure the quality of vegetable protein products (VPPs). Using liquid chromatography with tandem mass spectrometry (LC/MS/MS) technologies, a combination of VPP-based samples was analyzed for the presence of nitrogen-bearing environmental toxicants. Of the 52 samples tested, involving an assortment of matrices, melamine and cyanuric acid were positively identified (>1 ng/mL) in 22 and 17 samples, respectively. Subsequent high pressure liquid chromatography with ultraviolet/visible (HPLC-UV) amino acid profiling further confirmed the adulteration of those materials contaminated with melamine and melamine-related compounds. Based on the evidence presented herein, LC/MS/MS in combination with HPLC-UV provides for a reliable food safety detection system as applied to VPPs. Moreover, HPLC-UV is indispensable as a stand-alone 1st level of screening to assess the integrity of a VPP or any nutritive protein-based sample. Based on the evidence presented herein, LC/MS/MS in combination with HPLC-UV can provide a reliable food safety monitoring program as applied to VPPs. HPLC-UV is indispensable as a stand-alone 1st level of screening to assess the integrity of a VPP or any nutritive protein-based sample. Future research and development is required to bring the associated instrumentation costs down to a level where they can be adopted on a widespread basis. [ABSTRACT FROM AUTHOR]

Abstract: Several freshwater cyanobacteria species have the capability to produce toxic compounds, frequently referred to as cyanotoxins. The most prevalent of these cyanotoxins is microcystin LR. Recognizing the potential health risk, France, Italy, Poland, Australia, Canada, and Brazil have set either standards or guidelines for the amount of microcystin LR permissible in drinking water based on the World Health Organization guideline of one μg/L of microcystin LR. Recently, the United States Environmental Protection Agency has begun to evaluate the occurrence and health effects of cyanotoxins and their susceptibility to water treatment under the Safe Drinking Water Act through the Contaminant Candidate List (CCL). A recent update of the Contaminant Candidate List focuses research and data collection on the cyanotoxins microcystin LR, anatoxin-a, and cylindrospermopsin. Liquid Chromatography/Tandem-Mass Spectrometry (LC/MS/MS) is a powerful tool for the analysis of various analytes in a wide variety of matrices because of its sensitivity and selectivity. The use of smaller column media (sub 2μm particles) was investigated to both improve the speed, sensitivity and resolution, and to quantify the CCL cyanotoxins, in a single analysis, using Ultra-Performance Liquid Chromatography (UPLC®) combined with tandem mass spectrometry. Natural waters and spiked samples were analyzed to show proof-of-performance. The presented method was able to clearly resolve each of the cyanotoxins in less than eight minutes with specificity and high spike recoveries. [Copyright &y& Elsevier]

Sulfonylurea herbicides are widely used in crop production on the Canadian prairies and a portion of these herbicides applied to cropland are inevitably lost to surrounding aquatic ecosystems. Little is known regarding the presence of sulfonylurea herbicides in wetlands located amongst cropland. This paper describes a new analytical method for the extraction and the determination of seven sulfonylurea herbicides (thifensulfuron-methyl, tribenuron-methyl, ethametsulfuron-methyl, metsulfuron-methyl, rimsulfuron, nicosulfuron and sulfosulfuron) in wetland sediment. The method provided > 85% analyte recovery from fortified sediment for six of the seven sulfonylurea herbicides with a limit of quantification (LOQ) of 1.0 μ g kg- 1. Tribenuron-methyl had significantly lower recovery compared to the other six sulfonylurea herbicides (LOQ = 2 μ g kg- 1). Mean recovery standard deviations were < 10%. This methodology was used to quantify sulfonylurea herbicide residues in sediment samples collected from prairie wetlands situated within the agricultural landscape of Saskatchewan and Manitoba, Canada. This is the first-known detection of sulfonylurea herbicide residues in prairie wetland sediments. Ethametsulfuron-methyl, sulfosulfuron and metsulfuron-methyl, the three most environmentally persistent of the seven sulfonylurea herbicides monitored in the surveillance component of this study, were most frequently detected in wetland sediment with mean concentrations ranging from 1.2 to 10 μ g kg- 1. [ABSTRACT FROM AUTHOR]

Abstract: In recent times, there has been an increased concern over the appearance of human estrogens in marine ecosystem and their effects on the marine habitat. Discharge of raw sewage has been identified as one of the most important sources of human estrogens in the marine environment. Therefore, we have developed a gas chromatography–(ion-trap) mass spectrometry/mass spectrometry method for the analysis of natural estrogens estrone (E1), and 17β-estradiol (E2) and synthetic estrogens 17α-ethynylestradiol (EE2) and diethylstilbestrol (DES) in sewage effluents, seawater and mussels. Recovery of target analytes from mussels (n =3) was above 60% with RSD ranging from 8% to 13%. For aqueous samples (n =3) recoveries were above 80% with RSD ranging from 3% to 7%. Method detection limits for the target analytes ranged from 0.1ngg−1 to 1.0ng/g for mussel sample analysis and from 0.5ngL−1 to 1.2ngL−1 for water sample analysis. The usefulness of the method was demonstrated by analyzing environmental samples from St. John’s and Halifax, Canada, where raw sewage is directly discharged into the harbors. Estrone and 17 β-estradiol were found at 1.5ngL−1 and 1.8ngL−1 in seawater samples collected from St. John’s harbor, while trace amounts of estrone was measured in some mussels collected from Halifax harbor. [Copyright &y& Elsevier]

Non-targeted screening (NTS) in mass spectrometry (MS) helps alleviate the shortcoming of targeted analysis such as missing the presence of concerning compounds that are not monitored and its lack of retrospective analysis to subsequently look for new contaminants. Most NTS workflows include high resolution tandem mass spectrometry (HRMS2) and structure annotation with libraries which are still limited. However, in silico combinatorial fragmentation tools that simulate MS2 spectra are available to help close the gap of missing compounds in empirical libraries. Three NTS tools were combined and used to detect and identify unknown contaminants at ultra-trace levels in surface waters in real samples in this qualitative study. Two of them were based on combinatorial fragmentation databases, MetFrag and the Similar Partition Searching algorithm (SPS), and the third, the Global Natural Products Social Networking (GNPS), was an ensemble of empirical databases. The three NTS tools were applied to the analysis of real samples from a local river. A total of 253 contaminants were identified by combining all three tools: 209 were assigned a probable structure and 44 were confirmed using reference standards. The two major classes of contaminants observed were pharmaceuticals and consumer product additives. Among the confirmed compounds, octylphenol ethoxylates, denatonium, irbesartan and telmisartan are reported for the first time in surface waters in Canada. The workflow presented in this work uses three highly complementary NTS tools and it is a powerful approach to help identify and strategically select contaminants and their transformation products for subsequent targeted analysis and uncover new trends in surface water contamination. [Display omitted] • Hybrid NTS method based on combinatorial and empirical fragmentation databases. • 209 compounds were identified as probable structures and 44 as confirmed structures. • More than 100 compounds were pharmaceuticals and illicit drugs. • Octylphenol ethoxylates, denatonium and telmisartan were confirmed for the first time in surface waters in Canada. [ABSTRACT FROM AUTHOR]

Infancy is a period of rapid bone growth and mineral accretion; nonetheless, reference data remain scarce for this age group. The purpose of this report is to generate reference data for bone mass in breastfed vitamin D replete infants and investigate patterns of bone mineral accretion and sex differences. This is a secondary analysis from a double-blinded randomized controlled trial (NCT00381914). Healthy term breastfed (exclusively or mixed) infants were randomized to different doses of oral vitamin D supplementation (400-1600 IU/d) and followed prospectively from 1 to 12 mo. Plasma 25-hydroxyvitamin D (LC-MS/MS), bone mineral content (BMC; whole body (WB) and lumbar spine (LS)) and bone mineral density (BMD; LS) were measured at 1, 3, 6, 9, and 12 mo by dual-energy x-ray absorptiometry (Hologic Discovery 4500A) with no effect of supplementation on bone outcomes. For the purpose of this analysis, 63 infants with adequate plasma 25-hydroxyvitamin D ≥ 50 nmol/L at baseline, were included. Differences over time and between sexes were tested using mixed model repeated measures ANOVA. Infants (31 males, 32 females) were 39.5 ± 1.1 wk gestational age at birth and appropriate for gestational age. WB BMC, LS BMC, and LS BMD increased by 143.2%, 116.8%, and 31.1% respectively across infancy. WB BMC was higher (4.2% - 9.4%; p = 0.03) in males than in females across the study. After adjusting WB BMC for weight, length or head BMC, sex differences were not evident. LS BMC and LS BMD did not vary by sex. LS BMD growth charts for both sexes combined, were generated using LMS chartmaker. WB BMC more than doubles during the first year of life confirming the importance of skeletal growth and the need for age-specific reference data in infancy. Sex differences in BMC, if any, are mostly driven by differences in body size., (Crown Copyright © 2021. Published by Elsevier Inc. 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 (R2 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. Image 1 • On-line SPE was successfully coupled with HILIC-MS/MS to analyze water samples. • First on-line workflow for ultra-trace detection of the polar anticancer drug 5-FU. • Combinations of 5 SPE x 12 analytical columns were screened for 8 anticancer drugs. • Two HILIC & RPLC-MS/MS methods presented suitable LODs (0.5–5 ng L−1) in wastewater. • dFdU, CYT, GEM, MTX, IFO, CYC & CAP were detected in hospital & urban wastewaters. [ABSTRACT FROM AUTHOR]

The plant parasitic fungus Claviceps purpurea sensu lato produces sclerotia containing toxic ergot alkaloids and uncharacterized indole diterpenoids in grasses including cereals. The aim of this study was to detect as many peptide ergot alkaloids and indole diterpenoids in ergot sclerotia as possible by using a liquid chromatography-high-resolution mass spectrometry (LC-HRMS/MS) approach and applying filtering of diagnostic fragment ions for data extraction. The sample set consisted of 66 Claviceps sclerotia from four different geographic locations in southeastern Norway as well as Saskatchewan, Canada. The host plants included both wild grasses and important cereal grains such as rye. DNA sequencing showed that the sclerotia were from three Claviceps species, i.e., Claviceps purpurea sensu stricto (s.s.), Claviceps humidiphila , and Claviceps arundinis (former C. purpurea genotypes G1, G2, and G2a, respectively). All sclerotia from cereal grains were from C. purpurea s.s. Diagnostic fragment filtering was based on detecting specific product ions in MS/MS data sets that are well-conserved across the different ergot alkaloid subgroups and indole diterpenoids of the paspaline/paxilline type. The approach extracted mass spectra from 67 peptide ergot alkaloids (including C-8 epimers and lactam variants) and five indole diterpenoids. In addition, three clavines were detected by using targeted analysis. The sum of the peak areas for ergot alkaloids, which have been assigned as "major" analogues by the European Food Safety Authority (ergometrine, ergosine, ergotamine, α-ergocryptine, ergocornine, ergocristine, and their 8- S epimers), accounted for at least 50% of the extracted total ergot alkaloid metabolome. Univariate and multivariate statistical analyses showed that several of the alkaloids were specific for certain species within the C. purpurea species complex and could be used as chemotaxonomic markers for species assignment.

Determination of pesticides in cannabis facilities is increasingly important as medicinal and recreational uses of cannabis products expand rapidly. We report a method involving wipe sampling, liquid chromatography separation, and tandem mass spectrometry, which enables determination of 82 pesticides out of the 96 regulated by Health Canada. To demonstrate an application of the method, we sampled and measured pesticides in two cannabis growing facilities, representing a non-certified and a certified site. We detected 41 pesticides in surface wipe samples at the non-certified site and 6 at the certified site. This study provides the first evidence showing pesticide occurrence on common surfaces in cannabis growing facilities and points to a need for routine monitoring and strict control of pesticide use in cannabis facilities., (Copyright © 2020. Published by Elsevier B.V.)

Soxhlet (SE), microwave-assisted (MAE) and ultrasound-assisted (UAE) extraction were compared using ten extraction solvents for their efficiency to extract phenolic and flavonoid antioxidants from Eastern Canada propolis. Extracts were compared for total phenolic (TPC) and total flavonoid (TFC) content, and radical scavenging activities. Anti-inflammatory activity through inhibition of 5-lipoxygenase (5-LO) products biosynthesis in HEK293 cells was also evaluated. The results showed that SE extracts using polar solvents had the highest TPC and TFC. Extracts obtained with ethanol, methanol and acetone were effective free radical scavengers, and showed 5-LO inhibition similar to zileuton. UAE was an effective extraction method since the extracts obtained were comparable to those using SE and the MAE while being done at room temperature. With UAE, extracts of less polar solvents showed similar free radical scavenging and 5-LO inhibition to extracts of much more polar solvents such as methanol or ethanol. Reversed-phase liquid chromatography tandem mass spectrometry confirmed the presence of 21 natural compounds in the propolis extracts based on the comparison of intact mass, chromatographic retention time and fragmentation patterns derived from commercial analytical standards. The current study is the first of its kind to concurrently investigate solvent polarity as well as extraction techniques of propolis. [ABSTRACT FROM AUTHOR]

Contamination of drinking water by per- and polyfluoroalkyl substances (PFASs) emitted from manufacturing plants, fire-fighting foams, and urban waste streams has received considerable attention due to concerns over toxicity and environmental persistence; however, PFASs in ambient air remain poorly understood, especially in the United States (US). We measured PFAS concentrations in ambient fine particulate matter (PM 2.5 ) at 5 locations across North Carolina over a 1 year period in 2019. Thirty-four PFASs, including perfluoroalkyl carboxylic, perfluoroalkane sulfonic, perfluoroalkyl ether carboxylic and sulfonic acids were analyzed by UHPLC/ESI-MS/MS. Quarterly averaged concentrations ranged from <0.004-14.1 pg m -3 . Perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) ranged from <0.18 to 14.1 pg m -3 , comparable to previous PM 2.5 measurements from Canada and Europe (<0.02-3.5 pg m -3 ). Concentrations above 1 pg m -3 were observed in July-September at Charlotte (14.1 pg m -3 , PFOA), Wilmington (4.75 pg m -3 , PFOS), and Research Triangle Park (1.37 pg m -3 , PFOS). Notably, PM 2.5 has a short atmospheric lifetime (<2 weeks), and thus, the presence of PFOS in these samples raises questions about their sources, since PFOS production was phased out in the US ∼20 years ago. This is the first US study to provide insights into ambient PFAS concentrations in PM 2.5 .

The goal of this work was to investigate the occurrence of contaminants of emerging interest (CEI) in source surface water (SW; river water) and drinking water (DW; tap water) from five drinking water treatment plants (DWTPs) in the Province of Québec, Canada. A total of 28 sampling campaigns were conducted to collect SW and DW samples from each DWTP from June 2016 to July 2017. The seven targeted CEI, including acetaminophen, salicylic acid, caffeine, carbamazepine, ibuprofen, sulfamethoxazole and drospirenone, were analyzed using solid-phase extraction-ultra pressure liquid chromatography-mass spectrometry (SPE-UPLC-MS/MS) for all collected water samples. The selected CEI were detected in all SW and DW samples, with the exception of drospirenone, which occurred in amounts that were below the limit of detection in one DWTP in June and July 2016. In all the SW samples, caffeine was detected and had the highest median concentration range (12.3-91.0 ng/L), followed by acetaminophen (7.9-85.0 ng/L) and salicylic acid (21.6-39.0 ng/L). In the DW samples, salicylic acid was detected and had the highest median concentration range (20.5-50 ng/L), followed by caffeine (5.2-21.8 ng/L), and acetaminophen (5.0-7.7 ng/L). Carbamazepine, ibuprofen, and sulfamethoxazole primarily occurred in amounts between the limit of detection and limit of quantification in SW and occurred below the limit of detection in DW. All the DWTPs exhibited a similar trend in the removal of CEI, which include acetaminophen (≤97.6%), followed by caffeine (71.0-86.5%) and salicylic acid (<50.0%). Varying levels of efficiencies were observed among the removal strategies for CEI under study, which were mainly associated with the contaminant concentration in SW in the case of acetaminophen, and with the treatment processes in the case of caffeine and salicylic acid., 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.)

Objectives: To examine alleged drug-impaired driving in the province of Quebec (Canada), including drug use profile amongst suspected impaired drivers, prior to recreational cannabis legalization and major modifications to the legislation regarding driving under the influence of drugs (DUID)., Methods: The Laboratoire de sciences judiciaires et de médecine légale (LSJML) performs toxicological analyses on all biological samples collected during a Drug Evaluation and Classification Program (DECP) evaluation by a Drug Recognition Expert (DRE). A targeted analysis of 137 drugs and metabolites by liquid chromatography - tandem mass spectrometry (LC-MS/MS) is systematically carried out, enhanced by gas chromatography - mass spectrometry (GC-MS) general unknown screening if deemed necessary. Data from all DECP cases analyzed from January 2014 to December 2018 was compiled and summarized., Results: In the 5-year period studied, a total of 2 982 DECP cases underwent toxicological analysis. Age of the intercepted drivers varied between 14-82 years old (average 33 years old), with 79 % men and 21 % women. At least one substance with impairing potential was detected in 98 % of cases. In 89 % of cases (n = 2 640), at least one substance detected matched a category of drug suspected of causing impairment. At the other end of the spectrum, there were 270 cases (9%) where the findings did not match any of the categorie(s) suspected by the DRE, 66 negative cases (2%) and 6 incomplete evaluations. Substances most commonly detected belonged to the central nervous system (CNS) stimulants (72 %), CNS depressants (61 %) and cannabis (48 %) categories. Most prevalent substances were methamphetamine (54%), cannabis (11-nor-9-carboxy-tetrahydrocannabinol or THC-COOH, 48 %), cocaine (29 %) and gamma-hydroxybutyrate (GHB, 24 %). Polydrug consumption was common, with two or more substances with impairing potential detected in 79 % of cases. There were 113 occurrences of new psychoactive substances (NPS), the most prevalent being rolicyclidine (PCPy, 47 %), methylenedioxypyrovalerone (MDPV, 17 %), methylbenzylpiperazine (MBZP, 13 %) and flubromazolam (10 %). Drug prevalence patterns varied geographically, as well as with age and gender. Indeed, methamphetamine and GHB were more popular amongst women, whereas cannabis and cocaine were more prevalent amongst men. Cannabis and CNS stimulants were more common amongst younger drivers (14-34 years old); CNS depressants, dissociative anesthetics and non-psychoactive drugs prevalence increased with age., Conclusions: An up-to-date database of DUID cases is a powerful tool in identifying trends and threats, focusing resources and orienting research and development activities. Such a database, combined with the data presented in the current study, will be key in evaluating the impact of new regulations, i.e., recreational cannabis legalization and modifications to the DUID legislation., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Background: Synthetic musk compounds are widely used as fragrances in many consumer products; however, information on human exposure and health effects is limited. Also, analytical methods for their quantification in biological matrices are limited., Objective: In this study, an integrated method was developed and validated for the analysis of selected synthetic musk compounds in human serum., Method: The method is based on liquid-liquid extraction (LLE), sample clean-up by solid-phase extraction (SPE), and separation and detection by gas chromatography coupled with tandem mass spectrometry (GC-MS/MS)., Results: The method demonstrated good recoveries (86-105%) and high sensitivity, with low method detection limits (MDLs) ranging from 0.04 to 0.17 µg/L. The method was applied to the analysis of 10 synthetic musk compounds in 40 serum samples collected from Canadian women aged 20-44 years (20 individual samples collected in 2014 and 20 pooled samples collected in 2006). The most commonly detected compound was Galaxolide (HHCB), with median concentrations of 0.59 µg/L in samples collected in 2006, and 0.34 µg/L for samples collected in 2014. Musk ketone (MK) was not detected in any of the samples collected in 2006, but was detected in 60% of the samples collected in 2014 with a median concentration of 0.29 µg/L. Tonalide (AHTN) was detected in only one sample above its MDL (0.12 µg/L)., Conclusions: This is the first study in Canada to report levels of synthetic musks in human. The data generated from this study has been used in risk screening assessment by Environment and Climate Change Canada and Health Canada., (© AOAC INTERNATIONAL 2020. All rights reserved. For permissions, please email: journals.permissions@oup.com.)

A sensitive and selective high-performance liquid chromatographic method coupled to tandem mass spectrometry was developed and validated for the quantification of morphine, hydromorphone, fentanyl, midazolam and propofol and their metabolites morphine-3-β-d-glucuronide, morphine-6-β-d-glucuronide, hydromorphone-3-β-d-glucuronide, 1'-hydroxymidazolam-β-d-glucuronide, α-hydroxymidazolam and 4-hydroxymidazolam in human plasma using potassium oxalate/sodium fluoride mixture as anticoagulant. Human plasma samples (0.4 mL) to which were added a mixture of eleven deuterated internal standards were subjected to solid phase extraction using a mixed-mode polymeric Oasis PRiME MCX in 96-well format. Propofol was selectively eluted and further derivatized using 2-Fluoro-1-methylpyridinium p-toluenesulfonate, whereas the remaining 10 analytes were eluted separately and further concentrated. The derivatized propofol was analyzed separately in a second injection. The analytes were chromatographically separated on a Kinetex phenyl-hexyl analytical column in gradient elution mode, using a mobile phase consisting of aqueous ammonium formate/formic acid buffer and methanol. The overall run time was 8 min. Detection was performed using an AB/SCIEX 4000 QTRAP instrument with positive electrospray ionization employing scheduled multiple reaction monitoring mode. The lower limits of quantification ranged from 0.02 to 5 ng/mL depending on the analyte. Calibration curves covered a concentration range of 1000× in all cases but 1'-hydroxymidazolam-β-d-glucuronide where it covered a range of 500 × . The validated method was accurate and precise, the intra-day accuracy and precision of quality control samples (4 concentration levels, n = 6 each) being within 91.5-112 % and 1.3-13.2 % (coefficient of variation), respectively, and inter-day (n = 24; 4 days) accuracy and precision of quality control samples (3 concentration levels) being within 94.8-103.5 % and 3.2-11.2 % (coefficient of variation). Mean absolute extraction recoveries were above 60 % for all compounds, except for hydromorphone-3-β-d-glucuronide (44 %) and for 1'-hydroxymidazolam-β-d-glucuronide (33 %). Internal standard corrected matrix effect ranged from -4.8 to 3.8 % in normal plasma and in plasma containing 1 % hemolyzed blood. Analytes were stable (above 90 %) in plasma and blood for 19 h at 22 °C, in blood for 90 h at 5 °C, in plasma for 60 days at -20 °C, for 4 months at -70 °C and after three freeze-thaw cycles, and in the injection solvent for at least 3 days in the autosampler. The present method is successfully being applied in a multicenter clinical study for the analysis of plasma samples from patients in intensive care units from a number of Canadian hospitals., Competing Interests: Declaration of Competing Interest The authors declare no other competing interests. No writing assistance was utilized in the production of this manuscript., (Copyright © 2020 Elsevier B.V. All rights reserved.)

A retrospective analysis of a comprehensive series of high-volume air samples ( n = 70) collected during 2010-2011 in Toronto (Canada) was performed. Seven UV compounds were analyzed by gas chromatography-tandem mass spectrometry (GC-MS/MS) with sum of concentrations (gas + particle phase) ranging from 80 to 2030 pg/m 3 . Homosalate (HMS) was the most prevalent organic UV-filter in air (47% of the total concentration), followed by 2-ethylhexyl salicylate (EHS, ∼29%), E- and Z-2-ethylhexyl 4-methoxycinnamate (EHMC, ∼17%). Ambient air (gas + particle phase) concentrations of organic UV-filters showed a strong seasonality, with peak levels during the summer. An analysis of Clausius-Clapeyron slopes indicated that much of the ambient burden of organic UV-filters are explained by volatilization from terrestrial and aquatic surfaces and supplemented with human activities and use of lotions and sunscreens, containing organic UV-filters, in addition to its use in plastics, textiles, paints, and pesticides. The results showed that organic UV-filters exist mainly in the gas phase with some exceptions, for instance, octocrylene (OCR), which was associated with both gas and particle phases, and avobenzone (AVB), which was predominantly in the particle phase. Lastly, this study revealed the need for basic physical chemical property data for organic UV-filters, including information on transformation rates and products, for better evaluating their environmental fate and effects.

A liquid chromatography-negative ion electrospray ionization-tandem mass spectrometry method was developed for the simultaneous analysis of bisphenol A, 4-octylphenol, 4-nonylphenol, diethylstilbestrol, 17β-estradiol, estriol, estrone, 17α-ethinylestradiol, prednisone, and prednisolone. This method used solid-phase extraction with an elution solvent of acetonitrile to improve the stability of the analytes. To maintain the stability of analytes analyses were completed within five days. The recoveries ranged from 84 to 112% and the relative standard deviation of analysis of duplicate samples was <10%. The limits of quantitation were 1-10 ng/L. Surface water and wastewater were obtained from five wastewater treatment plants in Saskatchewan. Matrix effects were moderate to severe. Using standard addition calibration, all analytes except diethylstilbestrol and 17α-ethinyl estradiol were detected. There was a low frequency of detection of the target analytes in upstream and downstream water, indicating good removal efficiency during the wastewater treatment process. Bisphenol A and 4-nonylphenol were the only analytes detected downstream. Bisphenol A was the most frequently detected in raw wastewater (133 to 403 ng/L). Estriol was detected more often in raw wastewater than estrone or 17β-estradiol. This is the first Canadian study with the detection of prednisone and prednisolone with concentrations at 198-350 ng/L in raw wastewater at 60% of the wastewater treatment plants.

This study presents the first reported detections and concentrations of alkyl phenoxy-benzenesulfonate surfactants (APBS) in municipal wastewater. A semi quantitative direct injection LC/MS/MS method was developed. Samples of raw influent and final effluent were obtained from fourteen municipal wastewater treatment plants (WWTPs) at various locations in Canada and were analyzed for APBS, including five homologues of monoalkyldiphenylether disulfonates (MADS) and one monoalkyldiphenylether sulfonate (MAMS) homologue. APBS were detected in all 42 of the wastewater raw influent samples and in 37 of the 42 wastewater final effluent samples; the other 5 final effluent samples had trace levels below the minimum detection limit. In the samples of raw influent from the fourteen municipal treatment plants, the dissolved concentrations of APBS (total) ranged from 0.9 to 13.6 μg/L. In samples of final effluent from the same plants the total APBS ranged from below detection to 4 μg/L. The APBS were more resistant to loss during wastewater treatment compared to previous studies of linear alkylbenzene sulfonates in wastewaters. The most effective wastewater treatments for removal of APBS were those that involved either secondary treatment with aeration or advanced treatment including biological nutrient removal. Available information on ecotoxicity is lacking for evaluating the impacts of APBS surfactants when released to the environment., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Crown Copyright © 2020. Published by Elsevier Ltd. All rights reserved.)

Underlying the risk management of pesticides to protect human health and to facilitate trade among nations are sound scientific data on the levels of compliance with standards set by governments and internationally from monitoring of the levels of pesticides in foods. Although glyphosate is among the universally used pesticides in the world, monitoring has been hampered by the analytical difficulties in dealing with this highly polar compound. Starting in 2015, using liquid chromatography/tandem mass spectrometry (LC-MS/MS) that permits accurate and reproducible determination of glyphosate, the prevalence, concentrations, and compliance rates were determined. In this work, the glyphosate residues contents of 7955 samples of fresh fruits and vegetables, milled grain products, pulse products, and finished foods collected from April 2015 to March 2017 in the Canadian retail market are reported. A total of 3366 samples (42.3%) contained detectable glyphosate residues. The compliance rate with Canadian regulations was 99.4%. There were 46 noncompliant samples. Health Canada determined that there was no long-term health risk to Canadian consumers from exposure to the levels of glyphosate found in the samples of a variety of foods surveyed. The high level of compliance (99.4% of samples with the Canadian regulatory limits) and the lack of a health risk for noncompliant samples indicate that, with respect to glyphosates, the food available for sale in Canada is safe.

Background: Aberrancies in fetal DNA methylation programming may modify disease susceptibility of the offspring. Maternal folate status has potential to alter fetal DNA methylation., Objectives: We examined the association of maternal and cord blood concentrations of folate and unmetabolized folic acid (UMFA), vitamin B-12, vitamin B-6, and choline with fetal DNA methylation and hydroxymethylation and assessed potential modifying effects of 38 fetal genetic variants in 22 genes., Methods: Nutrient blood concentrations were measured in 368 pregnant women in early pregnancy (12-16 wk of gestation) and at delivery (37-42 wk of gestation) and in cord blood. DNA methylation and hydroxymethylation in cord blood mononuclear cells were quantified by LC-MS/MS. Pearson partial correlations were used to determine the association between individual nutrients and DNA methylation and hydroxymethylation., Results: Serum and RBC folate and plasma UMFA concentrations (primary outcomes) in early pregnancy, at delivery, and in cord blood were not significantly associated with fetal DNA methylation. In contrast, maternal RBC folate in early pregnancy (r = -0.16, P = 0.04) and cord plasma UMFA (r = -0.23, P = 0.004) were inversely correlated with fetal DNA hydroxymethylation. Neither maternal and cord blood concentrations of other nutrients nor fetal genotypes (secondary outcomes) were significantly associated with fetal DNA methylation or hydroxymethylation. Infants born to mothers with RBC folate concentrations in the highest quartile and serum vitamin B-12 concentrations in the lowest quartile in early pregnancy had significantly lower fetal DNA methylation and higher birth weight compared with those born to mothers with lower RBC folate and higher serum vitamin B-12 concentrations (P = 0.01)., Conclusions: Maternal and cord blood folate concentrations are associated with fetal DNA hydroxymethylation, but not DNA methylation, in a cohort of pregnant Canadian women. The observation that high folate and low vitamin B-12 maternal status in early pregnancy may be associated with decreased fetal DNA methylation and higher birth weight warrants further investigation. This trial was registered at clinicaltrials.gov as NCT02244684., (Copyright © American Society for Nutrition 2019.)

In response to the Canadian federal government's Cannabis Tracking and Licensing System compliance standards, a quantitative method was created for cannabis analysis, and validated using Eurachem V.2 (2014) guidelines. Cannabinol, cannabidiol, cannabigerol, cannabichromene, cannabidiolic acid, cannabigerolic acid, Δ-9-tetrahydrocannabinol, and Δ-9-tetrahydrocannabinolic acid A were all analysed by scheduled multiple reaction monitoring (MRM) via LC-MS/MS and isotope dilution. In addition, aflatoxins B1, B2, G1, and G2 were also analysed by scheduled MRM via LC-MS/MS and matrix matched calibration curves in order to achieve the reporting limits (≤2 μg kg -1 ) set out by the European Pharmacopoeia. The LODs/LOQs were 0.50/1.7, 2.0/6.7, 0.59/2.0, and 0.53/1.8 μg kg -1 , for B1, B2, G1, and G2 respectively. Thirty one terpenes were analysed by selected reaction monitoring via GC-MS/MS and isotope dilution using β-myrcene-d 6 as a surrogate. All quantitative analyses can be accomplished using less than 1 g of material, with minimal solvent and consumable use, on low resolution instruments in less than 30 min of instrument time. Of important note is this method's power of selectivity, working ranges, and lack of need for extraction consumables such as SPE or QuEChERS, thereby minimising analytical costs and time., (Copyright © 2019 Elsevier B.V. All rights reserved.)

A high resolution mass spectrometry method was developed for the environmental impact monitoring of oil spill dispersants. Previously reported instability of dioctyl sulfosuccinate (DOSS) dispersant tracer was addressed by the new procedure. The method monitors both DOSS and its degradation product, monooctyl sulfosuccinate (MOSS), by liquid chromatography time-of-flight mass spectrometry. The related isomer, 4-(2-ethylhexyl) 2-sulfobutanedioate, was chromatographically resolved from MOSS but was not a product of DOSS degradation. Using this direct injection method (10 μL), the practical lower limit of quantitation was 0.5 nM for each analyte, a concentration equivalent to 0.22 ng mL -1 , or 0.30 ng mL -1 including initial dilution factor with acetonitrile. The method was shown applicable to analysis of the dispersants Corexit® EC9500 A, Finasol OSR 52, Slickgone NS, and Slickgone EW for which DOSS is an active ingredient. A marine microcosm study of Corexit EC9500A, together with diluted bitumen (dilbit), at 15 ± 1 °C, provided evidence of the stoichiometric conversion of DOSS to MOSS under conditions reflecting a western Canadian marine environment. The advantage of the developed method is in its ability to extend environmental seawater sample collection time from 4 days for DOSS alone, to 14 days when both DOSS and MOSS are simultaneously analysed and results combined. The collection time is likely extended beyond the 14 day period with cooler temperatures. Preservation of collected seawater samples using sodium hydroxide, converting DOSS into MOSS in situ, was rejected due to stability issues. Addition of disodium ethylenediaminetetraacetic acid did not improve hold times, thus eliminating the theory of cation induced micelle effects causing DOSS loss., (Copyright © 2019. Published by Elsevier B.V.)

Background: Total nicotine equivalents (TNE), the sum of nicotine and metabolites in urine, is a valuable tool for evaluating nicotine exposure. Most methods for measuring TNE involve two-step enzymatic hydrolysis for indirect quantification of glucuronide metabolites. Here, we describe a rapid, low-cost direct LC/MS assay. Methods: In 139 smokers' urine samples, Bland-Altman, correlation, and regression analyses were used to investigate differences in quantification of nicotine and metabolites, TNE, and nicotine metabolite ratio (NMR) between direct and indirect LC/MS methods. DNA from a subset ( n = 97 smokers) was genotyped for UGT2B10*2 and UGT2B17*2 , and the known impact of these variants was evaluated using urinary ratios determined by the direct versus indirect method. Results: The direct method showed high accuracy (0%-9% bias) and precision (3%-14% coefficient of variation) with similar distribution of nicotine metabolites to literary estimates and good agreement between the direct and indirect methods for nicotine, cotinine, and 3-hydroxycotinine (ratios 0.99-1.07), but less agreement for their respective glucuronides (ratios 1.16-4.17). The direct method identified urinary 3HC+3HC-GLUC/COT as having the highest concordance with plasma NMR and provided substantially better estimations of the established genetic impact of glucuronidation variants compared with the indirect method. Conclusions: Direct quantification of nicotine and metabolites is less time-consuming and less costly, and provides accurate estimates of nicotine intake, metabolism rate, and the impact of genetic variation in smokers. Impact: Lower cost and maintenance combined with high accuracy and reproducibility make the direct method ideal for smoking biomarker, NMR, and pharmacogenomics studies. Cancer Epidemiol Biomarkers Prev; 27(8); 882-91. ©2018 AACR ., (©2018 American Association for Cancer Research.)