Data supporting the optimization of liquid chromatography tandem mass spectrometry conditions to analyze EPA-priority hormones and bisphenol A in water samples

This database presents the optimization of ultra-high-performance liquid chromatography electrospray ionization tandem mass spectrometry (UHPLC-MS/MS) for the analysis of EPA-priority endocrine disruptor compounds (13 hormones and bisphenol A). Various method parameters were tested and compared for improved sensitivity. Data related to the selection of the ionization source (heated-ESI vs. APCI) are presented, including optimization results of source parameters. Compound-dependent responses when varying the UHPLC mobile phase salt concentration of ammonium fluoride (NH4F) are supplied. Details on the chromatographic gradient program and chromatographic data demonstrating the separation of alpha-estradiol and beta-estradiol are provided. In addition, we supply the details on mass spectrometry parameters under the optimized conditions, relative responses of quantification and confirmation MS/MS transitions (QT/CT), and number of points present in UHPLC-MS/MS spectra. The sample preparation and instrumental analysis procedures under the retained conditions are also described. The herein dataset supports the research "Analysis of Environmental Protection Agency priority endocrine disruptor hormones and bisphenol A in tap, surface and wastewater by online concentration liquid chromatography tandem mass spectrometry" Goeury et al., 2019

Caractérisation physico-chimique de laques de Mongolie du Ier siècle ap. J.-C.

Cette étude a porté sur des écailles de laque trouvées lors de la fouille d'une nécropole du début de notre ère en Mongolie. L'objectif était de vérifier qu'il s'agissait de laque végétale (obtenue par polymérisation de la résine de l'arbre Rhus vernicifera), de caractériser et de comparer les différents fragments. L'examen au microscope électronique à balayage a révélé qu'ils comportaient pour la plupart au moins 2 couches et que l'on pouvait différencier les deux faces : celle contre le support, d'aspect granuleux et celle visible, d'aspect lisse. La fluorescence X et la diffraction X ont permis de montrer que le pigment rouge utilisé pour colorer certains échantillons était du cinabre, HgS. Des spectres infrarouges des échantillons anciens et de laque végétale moderne, issue de Rhus vernicifera ont été réalisés. Ils présentent la même allure générale et sont en accord avec des spectres de la littérature. La chromatographie en phase gazeuse couplée à la spectrométrie de masse a été utilisée après deux méthodes de préparation de l'échantillon. La méthanolyse acide suivie d'une silylation permet de caractériser la partie polysaccharidique dans tous les échantillons et la partie catéchols dans les laques modernes non polymérisées. La pyrolyse permet d'observer des marqueurs spécifiques des polymères obtenus à partir des catéchols, aussi bien dans les échantillons modernes que dans les échantillons archéologiques. Tous les résultats issus de ces premières analyses tendent à montrer qu'il s'agit bien de laque végétale, fabriquée à partir de résine de Rhus vernicifera, dont certains échantillons sont teintés en rouge avec du cinabre.The paper deals with the study of flakes of lacquer found during the excavation of a necropolis from the beginning of our era in Mongolia. Our purpose was to check if these flakes were actually made of lacquer (obtained by polymerisation of a vegetal resin extracted from the tree Rhus vernicifera) to characterize them and to compare the different fragments. The observation with a scanning electron microscope revealed that most of them were made of at least two coats and that both sides could be distinguished : the side against the support being grainy and the visible one smooth. Fluorescence X and diffraction X made it possible to know the nature of the red pigment used to colour certain lacquers, namely cinnabar, HgS. Infrared spectra of the ancient samples and of modem vegetal lacquer, made from the resin of Rhus vernicifera were run. They look the same and agree with those presented in the literature. Gas chromatography-mass spectrometry was used after two different methods of sample preparation. Acid methanolysis and silylation made it possible to characterize the polysaccharide part in all the samples and the catechol part in modern, non-polymerised, lacquers. Pyrolysis allowed us to observe specific markers of polymers obtained from catechols, as well in the modern samples as in the archaeological ones. All these results seem to prove that archaeological samples are really vegetal lacquers, made from resin of Rhus vernicifera, some of them being tinted in red with cinnabar

Adopt a Lake: Successfully Tracking Harmful Cyanobacterial Blooms in Canadian Surface Waters Through Citizen Science

The proliferation of harmful waterborne cyanobacterial algal blooms, some of which can produce potent toxins, poses severe risks to environmental and human health. Academic and governmental monitoring efforts may be constrained by budget, time, and staff, and thus miss otherwise significant pollution events. Here, we report on the implementation of a citizen science project to track harmful cyanobacterial blooms in lakes and waterways across Canada. Through both crowdsourcing and crowdfunding, the Adopt a Lake (Adopt a Lake 2022) campaign aimed to document the potential presence of cyanobacteria and toxins with the assistance of participants, thus improving public awareness of the issue of water quality preservation. Using social media, participants were encouraged to participate in the initiative by collecting samples during a bloom from a nearby pond or by making a financial contribution to support the initiative. Adopt a Lake benefitted from the analytical platform of Algal Blooms Treatment, Risk Assessment, Predictions, and Prevention (ATRAPP), a research project focused on the prediction and management of harmful cyanobacterial blooms. The presence of cyanotoxins, which can confirm whether a lake has a toxic bloom, was determined through high-resolution mass spectrometry analyses. This paper presents an overview of the implementation of the Adopt a Lake initiative, the campaign’s status, and the lessons learned, and it argues the importance of continual monitoring of cyanobacterial blooms

β-D-glucuronidase activity triggered monitoring of fecal contamination using microbial and chemical source tracking markers at drinking water intakes

ABSTRACT: ntense rainfall and snowmelt events may affect the safety of drinking water, as large quantities of fecal material can be discharged from storm or sewage overflows or washed from the catchment into drinking water sources. This study used β-D-glucuronidase activity (GLUC) with microbial source tracking (MST) markers: human, bovine, porcine mitochondrial DNA markers (mtDNA) and human-associated Bacteroidales HF183 and chemical source tracking (CST) markers including caffeine, carbamazepine, theophylline and acetaminophen, pathogens (Giardia, Cryptosporidium, adenovirus, rotavirus and enterovirus), water quality indicators (Escherichia coli, turbidity) and hydrometeorological data (flowrate, precipitation) to assess the vulnerability of 3 drinking water intakes (DWIs) and identify sources of fecal contamination. Water samples were collected under baseline, snow and rain events conditions in urban and agricultural catchments (Québec, Canada). Dynamics of E. coli, HF183 and WWMPs were similar during contamination events, and concentrations generally varied over 1 order of magnitude during each event. Elevated human-associated marker levels during events demonstrated that urban DWIs were impacted by recent contamination from an upstream municipal water resource recovery facility (WRRF). In the agricultural catchment, mixed fecal pollution was observed with the occurrences and increases of enteric viruses, human bovine and porcine mtDNA during peak contaminating events. Bovine mtDNA qPCR concentrations were indicative of runoff of cattle-derived fecal pollutants to the DWI from diffuse sources following rain events. This study demonstrated that the suitability of a given MST or CST indicator depend on river and catchment characteristics. The sampling strategy using continuous online GLUC activity coupled with MST and CST markers analysis was a more reliable source indicator than turbidity to identify peak events at drinking water intakes

Safety and efficacy of fluoxetine on functional outcome after acute stroke (AFFINITY): a randomised, double-blind, placebo-controlled trial

Background Trials of fluoxetine for recovery after stroke report conflicting results. The Assessment oF FluoxetINe In sTroke recoverY (AFFINITY) trial aimed to show if daily oral fluoxetine for 6 months after stroke improves functional outcome in an ethnically diverse population. Methods AFFINITY was a randomised, parallel-group, double-blind, placebo-controlled trial done in 43 hospital stroke units in Australia (n=29), New Zealand (four), and Vietnam (ten). Eligible patients were adults (aged ≥18 years) with a clinical diagnosis of acute stroke in the previous 2–15 days, brain imaging consistent with ischaemic or haemorrhagic stroke, and a persisting neurological deficit that produced a modified Rankin Scale (mRS) score of 1 or more. Patients were randomly assigned 1:1 via a web-based system using a minimisation algorithm to once daily, oral fluoxetine 20 mg capsules or matching placebo for 6 months. Patients, carers, investigators, and outcome assessors were masked to the treatment allocation. The primary outcome was functional status, measured by the mRS, at 6 months. The primary analysis was an ordinal logistic regression of the mRS at 6 months, adjusted for minimisation variables. Primary and safety analyses were done according to the patient's treatment allocation. The trial is registered with the Australian New Zealand Clinical Trials Registry, ACTRN12611000774921. Findings Between Jan 11, 2013, and June 30, 2019, 1280 patients were recruited in Australia (n=532), New Zealand (n=42), and Vietnam (n=706), of whom 642 were randomly assigned to fluoxetine and 638 were randomly assigned to placebo. Mean duration of trial treatment was 167 days (SD 48·1). At 6 months, mRS data were available in 624 (97%) patients in the fluoxetine group and 632 (99%) in the placebo group. The distribution of mRS categories was similar in the fluoxetine and placebo groups (adjusted common odds ratio 0·94, 95% CI 0·76–1·15; p=0·53). Compared with patients in the placebo group, patients in the fluoxetine group had more falls (20 [3%] vs seven [1%]; p=0·018), bone fractures (19 [3%] vs six [1%]; p=0·014), and epileptic seizures (ten [2%] vs two [<1%]; p=0·038) at 6 months. Interpretation Oral fluoxetine 20 mg daily for 6 months after acute stroke did not improve functional outcome and increased the risk of falls, bone fractures, and epileptic seizures. These results do not support the use of fluoxetine to improve functional outcome after stroke

Mise au point de méthodes analytiques pour la caractérisation de la matière organique constituante d'objets du patrimoine culturel

Ce travail de thèse a consisté à mettre au point une méthodologie permettant de caractériser les substances naturelles organiques présentes dans les objets du patrimoine culturel, à l aide du couplage CPG/SM, bien adapté à l analyse de mélanges complexes disponibles en faibles quantités. Nous nous sommes particulièrement intéressés à la caractérisation des gommes, gommes-résines, résines, huiles, graisses et cires, et des polyphénols (laques asiatiques). Ces substances renferment des composés présentant des caractéristiques physico-chimiques très différentes et nous avons évalué l intérêt de plusieurs techniques de préparation de l échantillon pour les mettre en évidence : la SPME pour les composés volatils, la dérivation (méthylation ou silylation) pour les composés semi-volatils et des méthodes de dépolymérisation ou de coupure comme la méthanolyse (acide ou basique) et la pyrolyse pour les polysaccharides, les polyphénols et les triglycérides. Pour certaines classes de composés importants comme les acides gras insaturés, des réactions de dérivation spécifiques (DMOX) ont également été utilisées afin d obtenir des spectres de masse IE permettant de différencier les isomères de position. Dans chaque cas de figure, les méthodes de séparation chromatographique ont été optimisées pour obtenir le maximum d informations. Les différentes méthodes ont d abord été mises au point à l aide de substances naturelles de référence représentatives. Elles ont ensuite été appliquées à l analyse de prélèvements provenant de trois types d objets : les écorchés de Fragonard, des polychromies portugaises du XVIIème siècle, des objets laqués d extrême orient anciens ou modernes.The aim of this thesis was to develop an analytical procedure for the characterization of organic materials present in objects from the Cultural Heritage. Gas chromatography-mass spectrometry (GC/MS), well adapted to the analysis of complex mixtures available in small amounts, is the appropriate technique for this purpose. The work was focused on the characterization of gums, gum-resins, resins, oils, fats, wax and polyphenols (coming from oriental lacquers). Theses substances contain compounds with very different physicochemical properties which require different sample preparation strategies: SPME to extract volatile analytes, derivatisation (methylation or silylation) to improve the detection of semi-volatile compounds and depolymerisation or cutting methods like methanolysis (acidic or basic) and pyrolysis to analyse polysaccharides, polyphenols and triglycerides. For some classes of important compounds like unsaturated fatty acid, specific derivatives (DMOX) were prepared in order to obtain characteristic EI mass spectra and differentiate the positional isomers. In each case, the chromatographic separation method was optimised in order to obtain maximum information. The different methods have first been developed with representative natural reference substances. They were then applied to the analysis of samples coming from anatomical models of Fragonard, Portuguese polychrome sculptures of the 17th century and ancient or modern oriental lacquer objects.ORSAY-PARIS 11-BU Sciences (914712101) / SudocSudocFranceF