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International audience; The assessment of micropollutants in urban wet weather discharges is essential to improve the knowledge of the impact of such discharges on receiving waters. This study assessed the quality of combined sewer overflows (CSOs) in Ecully (residential catchment) and stormwater runoff in Chassieu (industrial catchment) during rain events by providing data on occurrence and total event mean concentrations (EMCt) of 34 priority substances (PS) (9metals, 13 pesticides, 6 PAHs, 4 alkylphenols and 2 chlorobenzenes) in dissolved and particulate fractions. Over 34 substances monitored, 3 were quantified in urban wet weather discharges of both catchments. For both catchments, 9 metals and 6 PAHs monitored were always quantified, reflecting their ubiquitous presence. For other organic pollutants, only 5 pesticides were quantified and only 2 alkyphenols were measured solely in dissolved fraction. A significant site-to-site difference was observed for metals, PAHs and alkylphenols. The highest concentrations were measured in stormwater runoff in Chassieu vs. Ecully. On the contrary, the diuron concentrations were highest in CSO discharges in Ecully. Distribution of the PS between particulate and dissolved fractions provides information for urban stormwater practitioners. Most PS in urban wet weather discharges were mainly linked to particles (PAHs, Pb, Ti for example). The comparison between daily flows of wastewater treatment plants during dry weather and CSOs daily flows in Ecully showed that stormwater was the most important source of contamination for fluoranthene, benzo(b)fluoranthene and benzo(k)fluoranthene and 7 metals (As, Cr, Co, Cu, Pb, Ti and Zn) in receiving water bodies, but not for pesticides and alkylphenols.

International audience; The present work describes the development and validation of a sensitive method for the determination of traces of diverse groups of pharmaceuticals and endocrine disruptors in surface water. Thirty-seven substances have been selected, including 10 pesticides, 6 hormonal steroids and assimilates, 12 pharmaceuticals, 5 alkylphenols, 1 chlorophenol and 3 other well-known human contaminants, 1 UV filter and 2 plasticisers. An automated online solid-phase extraction (SPE) is directly coupled to liquid chromatography–tandem mass spectrometry. Different SPE columns have been tested, and the injection volume has been optimised. The developed analytical methodology is based on the direct injection of 2.5 mL of water sample acidified at pH 1.6 on an Oasis HLB loading column (20 × 2.1 mm) with 5-µm particles. Then, the chromatographic separation is achieved on a Kinetex XB C18 (100 × 2.1 mm; 1.7 µm) column, and the quantification is realised in multiple-reaction monitoring mode. The online SPE step warrants minimal sample handling, low solvent consumption, high sample throughput, saving time and costs. This method allows the quantification of the target analytes in the lower ng/L concentration range, with limits of quantification (LQs) between 100 pg/L and 10 ng/L, 26 compounds having LQ lower than 1 ng/L. The monitoring of two selected MS/MS transitions for each compound allows the reliable confirmation of positive findings even at the LQ level. The developed and validated methodology has been applied to the analysis of various real samples from two French rivers. Twelve target compounds have been detected in the environmental samples, and the major pollutants are pharmaceuticals usually used by humans (paracetamol, carbamazepine, oxazepam, ketoprofen, trimethoprim). The pesticides atrazine and carbendazim have been ubiquitously detected in real samples too. Metronidazole, sulfamethoxazole and diuron were also frequently quantified in the water samples.

International audience; To collect a large data set regarding the occurrence of organic substances in sediment, this study presents the examination of 20 micropollutants, as a national survey. The list of target compounds contains two alkylphenols, three polycyclic aromatic hydrocarbons (PAHs) not commonly included in monitoring programmes, six pesticides or metabolites, five pharmaceutical compounds, two hormones, one UV filter and bisphenol A. The selective and sensitive analytical methods, based on quick, easy, cheap, effective, rugged, and safe (QuEChERS) sample preparation followed by liquid chromatography-tandem mass spectrometry (LC-MS/MS) or gas chromatography-time-of-flight mass spectrometry (GC-ToF-MS), allow the quantification at limits comprised between 0.5 and 23 ng/g, depending on the compound. The paper summarizes the analytical results from 154 sampling points. Of the 20 target compounds, 9 were determined at least once, and the sediments contained a maximum of 7 substances. The most frequently detected were PAHs (frequency, 77 %; max., 1,400 ng/g). The pharmaceutical compounds, hormones and pesticides were rarely detected in the samples; the most frequently detected was carbamazepine (frequency, 6 %; max., 31 ng/g). In some cases, the levels of PAHs and bisphenol A exceed the predicted no-effect concentration (PNEC) values.

The authors wish to acknowledge INERIS (Institut National de l'Environnement Industriel et des Risques) for their technical support and the field technicians for the providing the samples.; International audience; To collect a complete dataset regarding the occurrence of organic substances in groundwater, this study presents the examination of 66 organic contaminants in the groundwater of overseas departments, including pesticides, pharmaceutical compounds, hormones and some industrial substances. The selective and sensitive analytical methods are described. These techniques begin with solid-phase extraction (SPE) followed by analysis using liquid chromatography-tandem mass spectrometry (LC-MS/MS) and gas chromatographymass spectrometry (GC-ToF-MS). The paper summarises the analytical results from 40 sampling points collected during two campaigns in Guadeloupe, Martinique, Reunion, Mayotte and Guiana, representing 80 samples. Of the 66 target substances, 36 were determined at least once. Among the most frequently detected are bisphenol A (frequency, 96 %; max., 7,400 ng/L), caffeine (frequency, 91 %; max., 1,240 ng/L), pentachlorophenol (frequency, 55 %; max., 418 ng/L), and carbamazepine (frequency, 56 %; max., 22 ng/L). The results do not put in evidence that the origin of the sample or climatic characteristics of these regions influence the dilution and release of micropollutants.

International audience; Numerous chemical products are dispersed in our environment. Many of them are recognized as harmful to humans and the ecosystem. Among these harmful substances are antibiotics and steroid hormones. Currently, very few data are available on the presence and fate of these substances in the environment, in particular for solid matrices, mainly due to a lack of analytical methodologies. Indeed, soil is a very complex matrix, and the nature and composition of the soil has a significant impact on the extraction efficiency and the sensitivity of the method. For this reason a statistical approach was performed to study the influence of soil parameters (clay, silt, sand and organic carbon percentages and cation exchange capacity (CEC)) on recoveries and matrix effects of various pharmaceuticals and steroids. Thus, an analysis of covariance (ANCOVA) was performed when several substances were analyzed simultaneously, whereas a Pearson correlation was used to study the compounds individually. To the best of our knowledge, this study is the first time such an experiment was performed. The results showed that clay and organic carbon percentages as well as the CEC have an impact on the recoveries of most of the target substances, the variables being anti-correlated. This result suggests that the compounds are trapped in soils with high levels of clay and organic carbon and a high CEC. For the matrix effects, it was shown that the organic carbon content has a significant effect on steroid hormones and penicillin G matrix effects (positive correlation). Finally, interaction effects (first order) were evaluated. This latter point corresponds to the crossed effects that occur between explanatory variables (soil parameters). Indeed, the value taken by an explanatory variable can have an influence on the effect that another explanatory variable has on a dependent variable. For instance, it was shown that some parameters (silt, sand) have an impact on the effect that clay content has on recoveries. Besides, CEC and silt affect the influence that organic carbon percentage has on matrix effect. This original approach provides a better understanding of the complex interactions that occur in soil and could be useful to understand and predict the performance of an analytical method.

International audience; A large number of polyphenols are consumed with the diet and may contribute to the prevention of chronic diseases such as cardiovascular diseases, diabetes, cancers, and neurodegenerative diseases. More comprehensive methods are needed to measure exposure to this complex family of bioactive plant compounds in epidemiological studies. We report here a novel method enabling the simultaneous measurement in urine of 38 polyphenols representative of the main classes and subclasses found in the diet. This method is based on differential C-12-/C-13-isotope labeling of polyphenols through derivatization with isotopic dansyl chloride reagents and on the analysis of the labeled polyphenols by tandem mass spectrometry. This derivatization approach overcomes the need for costly labeled standards. Different conditions for enzyme hydrolysis of polyphenol glucuronides and sulfate esters, extraction, and dansylation of unconjugated aglycones were tested and optimized. Limits of quantification varied from 0.01 to 1.1 mu M depending on polyphenols. Intrabatch coefficients of variation varied between 3.9% and 9.6%. Interbatch variations were lower than 15% for 31 compounds and lower than 29% for 6 additional polyphenols out of the 38 tested. Thirty seven polyphenols were validated and then analyzed in 475, 24 h urine samples from the European Prospective Investigation on Cancer and Nutrition (EPIC) study. Thirty four polyphenols could be detected and successfully estimated and showed large interindividual variations of concentrations (2-3 orders of magnitude depending on the compound), with median concentrations spanning from 0.01 to over 1000 mu M for all 34 compounds.

International audience; Contaminants in urban wet weather discharges originate from a number of sources such as materials from wet and dry atmospheric deposition, wastewaters, urban surface erosion, traffic-related activities, in-sewer deposits, etc. In the current study, four contributions (rainwater, dry atmospheric deposition, dry weather discharge and catchment surface + possible erosion of in-sewer deposits) to the total concentrations of priority substances have been assessed at the outlet of two urban catchments (one residential catchment with a combined system and one industrial area with a separate stormwater system) for 12 storm events (six for each catchment). Mass balances were calculated for seven metals and four pesticides, as well as for total suspended solids and chemical oxygen demand. The respective contributions of dry and wet atmospheric deposition, wastewater and catchment surface differ for each pollutant type, corresponding to different land use, activities, environments and sewer systems. For most of the pollutants, the catchment surface appears to be the main contribution, with significant storm event variability, excepted for atrazine in one catchment.

International audience; Reproductive functions are controlled by a finely tuned balance between estrogens and androgens. To further characterize the gonadal pathways leading to hormonal balance disruption by atrazine, vinclozolin, methoxychlor, and bisphenol A in rat, we investigated their effects in male and female young adult animals. Specifically, we assessed reproductive tract alterations, sex hormone balance in serum and gonads, tissue dosimetry, and mRNA expression. Remarkably, we observed different aromatase regulation profiles between animals with similar estrogen-to-androgen ratios but with different chemical treatments. For example, increased estrogen-to-androgen ratios in atrazine-treated females could be partly linked to aromatase upregulation, while in methoxychlor- and bisphenol A-treated females, peripheral mechanisms such as conjugation/deconjugation processes might be more likely to elevate estrogen levels. In vinclozolin-treated animals, the decreased estrogen-to-androgen ratios reported might be due to an increase of peripheral (adrenal) steroidogenesis. Thus, measurement of many endpoints is necessary for good risk assessment. Highlights Hormonal balance as a relevant endpoint for reproductive toxicology assessment. Characterization of gonadal pathways involved in endocrine disruption. Discrepancy between in vitro chemicals classification and in vivo reality. Several well chosen complementary endpoints are required for good risk assessment.

International audience; The uptake kinetics of 27 emerging pollutants on the polar C18 Chemcatcher have been investigated. This investigation determined the sampling rates of 20 compounds, including 16 endocrine disruptors and 4 pharmaceuticals, which were used as overall pollution indicators. Calibrations were completed in a 50-L flow-through microcosm with continuous renewal of tap water spiked with approximately 3 μg/L of each pollutant and with sampling times at 1, 3, 6 and 12 h and 1, 3, 7, 14, 21 and 28 days. Exponential regressions for the accumulation kinetics were plotted to confirm the maximum linear uptake times for each molecule using the half time of equilibrium (t1/2) criteria. Of the compounds tested, 17 were accumulated linearly for up to 14 or 21 days with an R2 above 0.98 for linear correlations. The evaluation of the release kinetics of a C18 Chemcatcher spiked with 20 deuterated compounds identified 3 potential performance reference compounds (PRCs) with exponential desorption rates showing relatively good isotropic exchange. Highlights Uptake kinetics of 27 emerging pollutants were investigated on the polar C18 Chemcatcher. Sampling rates of 20 endocrine disruptors were determined. 17 compounds accumulated linearly up to 14 or 21 days. 3 potential PRCs on C18 Chemcatcher were identified.

International audience; Atmospheric deposition plays an important role in environmental pollution and human health. However, very few information is available on the presence, in atmospheric particles, of organic priority substances in contrast to inorganic fraction. A method for the extraction and quantification of 20 priority organic substances listed in the European Water Framework Directive in atmospheric particles was developed. This method consists in a combination of gas chromatography coupled with mass spectrometry and ultra-high-pressure liquid chromatography coupled with tandem mass spectrometry and fluorescence. Optimized pressurized liquid extraction using a hexane/dichloromethane/isopropanol mixture was used as extraction procedure from atmospheric particulate matter. The influence of several extraction experimental factors related to the PLE was investigated. The optimized extraction method (80°C, 40bar, 10min, 1 cycle) exhibited average recoveries of target analytes higher than 62%. The method detection limits (MDL) were between 0.3ngg(-1) and 83ngg(-1). This extraction method, combined with sensitive analytical techniques, leads to satisfactory reliability, sensitivity, and accuracy. The method was applied to real samples, collected from two urban sites by an atmospheric sampling prototype developed in this study. The first results reveal a systematic presence of PAHs at high levels (ranging from 500ngg(-1) to 10μgg(-1)) and a variable and lower presence of pesticides at concentrations below 50ngg(-1) in the samples.

International audience; To simultaneously measure some targeted endocrine disruptors and several forms of sex hormones in rat serum, an accurate analytical procedure was developed. First, a comparison between a polymeric-based solid-phase extraction (SPE) and a micro-extraction by packed sorbent was performed to choose the optimal method to extract and concentrate the analytes: bisphenol A, atrazine, vinclozolin metabolite, testosterone, androstenedione, estrone, estradiol, estrone-sulfate and glucuronide and estradiol-sulfate and glucuronide. The analyses were then performed by high-performance liquid chromatography coupled to tandem mass spectrometry (LC–MS/MS) with electrospray ionisation in positive and negative modes. The protocol based on SPE was validated using the ICH/2005 guidelines. The validation demonstrated good performance in terms of linearity (R2 > 0.99), recovery (71–90%) and repeatability (relative standard deviation: 1–18%). The method was sensitive with LOQ comprised between 0.1 and 0.4 ng/ml for androgens and between 0.098 and 10.2 ng/ml for estrogens. The results obtained on the serum of rats exposed to the targeted endocrine disruptors showed the suitability of this analytical strategy.

International audience; Polymer items are extensively present in the human environment. Humans may be consequently exposed to some compounds, such as additives, incorporated in these items. The objective of this work is to assess the human exposure to the main additives such as those authorized in the packaging for pharmaceutical products. The urinary matrix was selected to optimally answer this challenge because it has already been proven that the exposure to chemicals can be revealed by the analysis of this biological matrix. A multi-residue analytical method for the trace analysis at ng/mL in human urine was developed, and consisted of an extraction of analytes from urine by solid phase extraction (SPE) and an analysis by ultra-high performance liquid chromatography coupled to a tandem mass spectrometer (UHPLC–MS/MS). Even if the quantification of these compounds was an analytical challenge because of (i) the presence of these substances in the analytical process, (ii) the diversity of their physicochemical properties, and (iii) the complexity of the matrix, the optimized method exhibited quantification limits lower than 25 ng/mL and recoveries between 51% and 120% for all compounds. The method was validated and applied to 52 human urines. To the best of our knowledge, this work presents the first study allowing the assessment of the occurrence of more than twenty polymer additives at ng/mL in human urine.

International audience; The efficacy of a fluidized powdered activated carbon (PAC) pilot (CarboPlus®) was studied in both nominal (total nitrification + post denitrification) and degraded (partial nitrification + no denitrification) configuration of the Seine Centre WWTP (Colombes, France). In addition to conventional wastewater parameters 54 pharmaceuticals and hormones (PhPHs) and 59 other emerging pollutants were monitored in influents and effluents of the pilot. Thus, the impacts of the WWTP configuration, the process operation and the physico-chemical properties of the studied compounds were assessed in this article.Among the 26 PhPHs quantified in nominal WWTP configuration influents, 8 have high dissolved concentrations (>100 ng/L), 11 have an intermediary concentration (10–100 ng/L) and 7 are quantified below 10 ng/L. Sulfamethoxazole is predominant (about 30% of the sum of the PhPHs). Overall, 6 PhPHs are poorly to moderately removed (80%), i.e. beta blockers, carbamazepine or trimethoprim, and 11 are well eliminated (60–80%), i.e. diclofenac, naproxen or sulfamethoxazole.In degraded WWTP configuration, higher levels of organic matter and higher concentrations of most pollutants are observed. Consequently, most PhPHs are substantially less removed in percentages but the removed flux is higher. Thus, the PAC dose required to achieve a given removal percentage is higher in degraded WWTP configuration. For the other micropollutants (34 quantified), artificial sweeteners and phthalates are found at particularly high concentrations in degraded WWTP configuration influents, up to μg/L range. Only pesticides, bisphenol A and parabens are largely eliminated (50–95%), while perfluorinated acids, PAHs, triclosan and sweeteners are not or weakly removed (

International audience; Due to industrialization and the use of chemical products in everyday life, various types of drugs and pesticides are present in our environment, which threaten and cause negative impacts on aquatic ecosystems. The consequences of these pollutants are gradually becoming visible. Recent evidence confirms that long term exposure to environmental pharmaceutical concentrations can induce adverse effects in aquatic vertebrates and invertebrates such as reproductive impairments and collapse wild populations. Consequently, one of the challenges of environmental science is to evaluate the associated risks.In this context, a new methodology has been developed using nano-LC-nano-ESI MS/MS to quantify traces of two pharmaceuticals (a neuropharmaceutical drug, fluoxetine, and an anticonvulsant drug, carbamazepine) in two molluscs. Potamopyrgus antipodarum and Valvata piscinalis, which are both prosobranch gastropods. A simple and quick extraction method was developed based on a modified and miniaturized version of the QuEChERS method. The procedure involves the extraction of approximately 10 mg of wet mollusc tissue by 500 mu L of a mixture of acetonitrile/water/hexane (50/20/30) and 100 mg of buffer salt. Thus, the extraction step was carried out on an individual scale.The sensitivity of this method allowed for the detection of levels as low as 18 ng/g and 128 ng/g for carbamazepine and fluoxetine, respectively, with recoveries of greater than 85% for the two targeted compounds. This method was then applied to both gastropod species exposed to fluoxetine under laboratory conditions. The results provide evidence of bioaccumulation in both P. antipodarum and V. piscinalis and reveal the inter-species differences.

The presented work proposes a new methodology based on proteomics techniques to identify proteins in old art paintings. The main challenging tasks of this work were (i) to find appropriate conditions for extracting proteins from the binding media without protein hydrolysis in amino acids and (ii) to develop analytical methods adapted to the small sample quantity available. Starting from microsamples of painting models (ovalbumin-based, which is the major egg white protein, and egg-based paintings), multiple extraction solutions (HCl, HCOOH, NH3, NaOH) and conditions (ultrasonic bath, mortar and pestle, grinding resin) were evaluated. The best results were obtained using a commercial kit including a synthetic resin, mortar and pestle to grind the sample in an aqueous solution acidified with trifluoroacetic acid at 1% with additional multiple steps of ultrasonic baths. The resulting supernatant was analyzed by MALDI-TOF in linear mode to verify the efficiency of the extraction solution. An enzymatic hydrolysis step was also performed for protein identification; the peptide mixture was analyzed by nanoLC/nanoESI/Q-q-TOF MS/MS with an adapted chromatographic run for the low sample quantity. Finally, the developed methodology was successfully applied to Renaissance art painting microsamples of approximately 10 microg from Benedetto Bonfigli's triptych, The Virgin and Child, St. John the Baptist, St. Sebastian (XVth century), and Niccolo di Pietro Gerini's painting, The Virgin and Child (XIVth century), identifying, for the first time and without ambiguity, the presence of whole egg proteins (egg yolk and egg white) in a painting binder.

The idea of a novel two-dimensional (2D) nanoelectrospray ionization emitter tip with the shape of a nib is explored here. This novel planar design is studied as an alternative to the needle-like standard emitter tips that suffer from a lack of reproducibility and robustness and from an inherent incompatibility with high-throughput analysis. The composition of the micro-nib sources is analogous to the working of a simple fountain pen, with a liquid reservoir linked to a micro-nib tip from which the sample is electrosprayed via a capillary slot. The micro-nib prototypes described here were fabricated using microtechnology techniques and using the epoxy-based negative photoresist SU-8. The resulting free-standing micro-nib structure was supported by a silicon wafer. We present here two series of such micro-nib sources, the latter series exhibiting improved characteristics such as a 8 pm source width of the nib tip. They were tested in mass spectrometry experiments on an ion trap mass spectrometer (LCQ Deca XP+, Thermo Finnigan) using standard peptide samples having concentrations down to 1 μM and with a high voltage (HV) supply around 1 kV for the second series of micro-nib sources. In addition to the stability of the spray, the obtained mass spectra showed the reliability of these sources for peptide analysis; the signal of the spectra was as intense and the signal-to-noise ratio (S/N) as high as that obtained with the use of standard emitter tips.

The effects of catechin metabolites and methylated analogues on LDL oxidation were studied in vitro using either a water-soluble initiator or copper ions to induce lipid peroxidation. Direct addition of catechin O-methylated analogues to the oxidation mixture led to a clear protective effect during lag phase and for the metabolites during both lag and propagation phases. The structure-activity relationships obtained with these selectively O-methylated compounds allowed determination of catechin active moietie: the catechol B-ring. Based on physical chemical studies, these results suggest that the mechanism implied in the scavenging properties of flavan-3-ols is not only hydrogen transfer, as generally described, but mainly an electronic transfer from the phenolate, and that 3'- and 4'-O-methylcatechin seem, moreover, to act as amphiphilic chain-breaking antioxidants. However, the plasma concentration of flavan-3-ols necessary to protect LDL is far greater than those usually found in human plasma. Therefore, the data do not support a direct physiological relevance of flavan-3-ols as antioxidants in lipid processes. Future research should focus on other effects besides simple antioxidant ones.

(-)-Epigallocatechin (EGC), one of green tea polyphenols, has been shown to inhibit growth of cancer cells. However its mechanism of action is poorly known. We show here that EGC strongly inhibited the growth of breast cancer cell lines (MCF-7 and MDA-MB-231) but not that of normal breast epithelial cells. The inhibition of breast cancer cell growth was due to an induction of apoptosis, without any change in cell cycle progression. MCF-7 cells are known to express a wild-type p53 whereas MDA-MB-231 cells express a mutated p53. The fact that EGC induced apoptosis in both these cell lines suggests that the EGC-triggered apoptosis is independent of p53 status. Moreover, neutralizing antibodies against the death receptor Fas and inhibitors of caspases, such as caspase-8 and -10, efficiently inhibited the EGC-triggered apoptosis. In addition, immunoblotting revealed that EGC treatment was correlated with a decrease in Bcl-2 and an increase in Bax level. These results suggest that EGC-triggered apoptosis in breast cancer cells requires Fas signaling.

The 13 C NMR studies of catechin and epicatechin upon addition of base are reported. These flavan-3-ols show an interesting deprotonation behavior, dramatically different from the other type of flavonoids: catechin and epicatechin exhibit competitive deprotonation on B and A ring leading to a mixture of different monophenolates.

International audience; Aquatic ecosystems are continuously contaminated by agricultural and industrial sources. Although the consequences of this pollution are gradually becoming visible, their potential impacts on aquatic ecosystems are poorly known, particularly regarding the risk of bioaccumulation in different trophic levels. To establish a causality relationship between bioaccumulation and disease, experiments on biotic matrices must be performed. In this context, a multi-residue method for the analysis of 35 emerging pollutants in three benthic invertebrates (Potamopyrgus antipodarum, Gammarus fossarum, and Chironomus riparius) has been developed. Because the variation in response of each individual must be taken into account in ecotoxicological studies, the entire analytical chain was miniaturised, thereby reducing the required sample size to a minimum of one individual and scaling the method accordingly. A new extraction strategy based on a modified, optimised and miniaturised "QuEChERS" approach is reported. The procedure involves salting out liquid-liquid extraction of approximately 10-20 mg of matrix followed by nano-liquid chromatography-nano electospray ionisation coupled with tandem mass spectrometry. The validated analytical procedure exhibited recoveries between 40 and 98% for all the target compounds and enabled the determination of pollutants on an individual scale in the ng g(-1) concentration. The method was subsequently applied to determine the levels of target analytes in several encaged organisms which were exposed upstream and downstream of an effluent discharge. The results highlighted a bioaccumulation of certain targeted emerging pollutants in three freshwater invertebrates, as well as inter-species differences. 18 out of 35 compounds were detected and eight were quantified. The highest concentrations were measured for ibuprofen in G. fossarum, reaching up to 105 ng g(-1).

International audience; Veterinary antibiotics and steroid hormones can be present at low levels in soil. Analytical methodologies are therefore necessary to analyse these compounds at the trace level in such a complex matrix.The goal of this work was to compare Pressurised Liquid Extraction (PLE), which is usually used to extract drugs from soil, and a modified-QuEChERS (Quick, Easy, Cheap, Effective, Rugged and Safe) method. Furthermore, several clean-up methods were evaluated. Selective Pressurised Liquid Extraction (SPLE) and Dispersive Solid Phase Extraction (dSPE) used after PLE and QuEChERS, respectively, were tested. These techniques permit a fast and simple purification step. SPE, which is frequently used, was also evaluated. To perform this comparison, both recoveries and matrix effects were compared and the analyses were performed using liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS).SPLE and dSPE did not significantly decrease matrix effects. A tandem SPE using SAX and Strata-X cartridges offered the best efficiency. Regarding the comparison between PLE and QuEChERS, the modified-QuEChERS led to better recoveries for certain substances. No significant differences were noted in term of matrix effects. Therefore, the modified-QuEChERS method is recommended.

International audience; Numerous chemical products are dispersed into the environment, and the consequences can be sometimes harmful to humans and ecosystems. Pharmaceutical compounds and hormone steroids are among these substances that concern the scientific community. Currently, little data are available on the presence and fate of these compounds in the environment and, in particular, for solid matrices. Therefore, the aim of this work was to perform soil column experiments to evaluate the accumulation, transfer and degradation of these substances in soil. The analyses were based on efficient sample preparation followed by sensitive and selective liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). For this purpose, 23 compounds were chosen including both pharmaceutical compounds as well as steroid hormones. In addition, this experiment was performed on two soils with different properties (% clay, pH, etc.). To the best of our knowledge, no soil column experiments have been performed previously on a large number of pharmaceutical compounds and steroid hormones. Significant transfer was observed only for sulphonamides that can be justified by their polarity (log K ow < 3). Furthermore, some compounds have a cationic characteristic and are likely to be not much mobiles in soil due to cation exchange process. However, it was observed that the migration of the substances depends on the soil characteristics, such as the amount of clay and the pH values. Regarding the degradation, it was noticed that substances degraded rapidly in the two soils. Indeed, for most substances, their half-lives were lower than 20 days. Furthermore, it was observed that the degradation rate depended on the soil.

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International audience; Emerging contaminants are suspected to cause adverse effects in humans and wildlife. Aquatic ecosystems are continuously contaminated by agricultural and industrial sources. To establish a causality relationship between the occurrence of contaminants in the environment and disease, experiments including all environmental matrices must be performed. Consequently, the current analytical tools must be improved. A new multi-residue method for analysing 15 emerging pollutants in sediments based on the Quick, Easy, Cheap, Effective, Rugged and Safe approach is reported. The development of such a multirisque, inter-family method for sediment including pharmaceuticals, pesticides, personal care products and plasticizers is reported for the first time. The procedure involves salting-out liquid-liquid extraction using acetonitrile and clean-up with dispersive solid phase extraction, followed by liquid chromatography coupled with tandem mass spectrometry. The validated analytical procedure exhibited recoveries between 40 and 98 % for every target compound. This methodology facilitated the determination of pollutant contents at nanogram-per-gram concentrations.

International audience; The use of polymer materials in industry for product packaging is increasing. The presence of additives in the polymer matrix enables the modification or improvement of the properties and performance of the polymer, but these industries are concerned regarding the extractability of these additives. The quantification of these additives is particularly challenging because of the presence of these substances as contaminants in all the analytical equipment and the diversity of their physicochemical properties. In this context, a multi-residue analytical method was developed for the trace analysis of the twenty main additives (and their degradation products) authorized in plastic products such as pharmaceutical packaging (e.g., antioxidants, release agents, and light absorbers). This analytical method consisted of a solid phase extraction (SPE) followed by an analysis using ultra-high performance liquid chromatography coupled to a tandem mass spectrometer (UHPLC-MS/MS). A comparison of two ionization interfaces and the optimization of the extraction procedure were discussed. The influence of the quality of the solvent type (distilled versus not distilled) and the nature of the SPE cartridges (Polypropylene versus Teflon®) were demonstrated. The optimized method exhibited a quantification limit lower than 20 ng mL−1 and recoveries between 70 % and 120 % for all compounds. Finally, the method was validated according to the ICH directive and was subsequently applied to the extraction of polymers under different pH conditions and storage temperatures. To the best of our knowledge, this study presents the first methodology allowing the simultaneous quantification of 24 additives at low ng mL−1.

International audience; Metabonomics has become a very valuable tool and many research fields rely on results coming out from this combination of analytical techniques, chemometric strategies, and biological interpretation. Moreover, the matrices are more and more complex and the implications of the results are often of major importance. In this context, the need for pertinent validation strategies comes naturally. The choice of the appropriate chemometric method remains nevertheless a difficult task due to particularities such as: the number of measured variables, the complexity of the matrix and the purposes of the study. Consequently, this paper presents a detailed metabonomic study on human urine with a special emphasis on the importance of assessing the data's quality. It also describes, step by step, the statistical tools currently used and offers a critical view on some of their limits. In this work, 29 urine samples among which 15 samples obtained from tetrahydrocannabinol (delta-9-tetrahydrocannabinol)-consuming athletes, 5 samples provided by volunteers, and 9 samples obtained from athletes were submitted to untargeted analysis by means of ultra high-pressure liquid chromatography-electrospray ionization-time-of-flight mass spectrometry. Next, the quality of the obtained data was assessed and the results were compared to those found in databases. Then, unsupervised (principal component analysis (PCA)) and supervised (ANOVA/PCA, partial least-square-discriminant analysis (PLS-DA), orthogonal PLS-DA) univariate and multivariate statistical methods were applied.

Chemical and microbial contaminations of urban waters including stormwater runoff, wastewaters, and combined sewer overflow waters have been shown for a number of years. It is clearly demonstrated, for example, that metallic ions, polycyclic aromatic hydrocarbons (PAH), pesticides, and microbial pathogens can be conveyed by such waters, and they have been found strongly associated with suspended matters. The “Water Framework Directive” (WFD) led to the launching of several research initiatives toward the “Best Management Practices – BMP,” through novel or improved technologies aiming at reducing the ecotoxicological impacts and health risks associated with these waters. Some of these techniques consist at keeping these waters for a certain amount of time in a confined system in order to favor settling of their suspended particles and lead, in part, to the natural biological degradation of their contaminants. These systems are typically impervious basins that can receive stormwaters, e.g. detention basins, biofilters, artificial wetlands, or combined sewer overflows, e.g. stabilization ponds of wastewater treatment lagoons. Several key mechanisms occur in these systems (Fig. 1). The deposits formed constitute areas of high levels of contamination. These structures (basins) are ecosystems with an important biological diversity. They can represent a high risk of contamination of the connected surfaces, streams, or groundwater environments into which they are discharged. Investigations regarding their efficiency at retaining and transforming pollutants and killing undesirable microbes are thus required. When landscaped, these structures may lead to the development of urban public spaces. In this context, they are subjected to social practices generally associated with public gardens, practices which accidentally or regularly expose the public to their contaminants. In addition, these structures require maintenance and specific management, exposing workers to their contaminants. It is therefore essential that the chemical and microbiological contaminants present in these systems are accurately characterized and measured (i.e. which chemical forms and microbial species and genotypes, and how much?), and their health hazards and risks be inferred or estimated. In this context, several biofilters, detention basins, and stabilization ponds have been monitored and investigated around the world. The CABRRES project (Chemical, microbiological, spatial characteristics and impacts of contaminants from urban stormwater detention basins: Assessment and Management of Environmental and Human Health Risks, http://www.graie. org/cabrres), funded by the French National Research Agency (ANR), is one of these research initiatives. It is an interdisciplinary research project (Fig. 2) aiming at better defining the interactions between chemical pollutants (including toxic Responsible editor: Philippe Garrigues

Selective protection of the catechol ring of catechin has been achieved. From this key compound, catechin analogues protected either on the catechol or the resorcinol rings were synthesized. From these analogues, phenoxyl radicals on the catechol or on the resorcinol rings were produced by photo-oxidation (direct irradiation at 308 nm) of the phenolate and by H-abstraction experiments. Spectra of the radicals were recorded at short times before any further chemical evolution. Investigation of catechin behavior itself and comparison with the reactivity of models show that H-abstraction is unselective, whereas photo-oxidation is selective on the catechol ring monoanion establishing that this ring has the lowest pKa.

Fluoxetine is a widely used antidepressant frequently found in wastewater treatment plant effluent and in aquatic ecosystems at concentrations below μg/L. Numerous studies have explored the sensitivity of invertebrates to waterborne fluoxetine showing marked differences of sensitivity. In a previous study, the New-Zealand mudsnail, Potamopyrgus antipodarum, and the European valve snail, Valvata piscinalis, were exposed to waterborne fluoxetine (3.7-100 μg/L) during 42 days. While effects were observed on the mudsnail reproduction and F1, the valve snail was not affected. Several assumptions were proposed to explain these results including dissimilar metabolic capacities or bioavailability of fluoxetine for the snails. The aim of this study was to asses if differential sensitivity of gastropods snails to fluoxetine could be explained by its bioaccumulation and metabolism into norfluoxetine.

International audience; REACH regulation requires ecotoxicological data to characterize industrial chemicals. To limit in vivo testing, Quantitative Structure-Activity Relationships (QSARs) are advocated to predict toxicity of a molecule. In this context, the topic of this work was to develop a reliable QSAR explaining the experimental acute toxicity of organic solvents for fish trophic level. Toxicity was expressed as log(LC50), the concentration in mmol.L-1 producing the 50% death of fish. The 141 chemically heterogeneous solvents of the dataset were described by physico-chemical descriptors and quantum theoretical parameters calculated via Density Functional Theory. The best subsets of solvent descriptors for LC50 prediction were chosen both through the Kubinyi function associated with Enhanced Replacement Method and a stepwise forward multiple linear regressions. The 4-parameters selected in the model were the octanol-water partition coefficient, LUMO energy, dielectric constant and surface tension. The predictive power and robustness of the QSAR developed were assessed by internal and external validations. Several techniques for training sets selection were evaluated: a random selection, a LC50-based selection, a balanced selection in terms of toxic and non-toxic solvents, a solvent profile-based selection with a space filling technique and a D-optimality onions-based selection. A comparison with fish LC50 predicted by ECOSAR model validated for neutral organics confirmed the interest of the QSAR developed for the prediction of organic solvent aquatic toxicity regardless of the mechanism of toxic action involved.

International audience; We have detected differences in metabolite levels between doped athletes, clean athletes, and volunteers (non athletes). This outcome is obtained by comparing results of measurements from two analytical platforms: UHPLC-QTOF/MS and FT-ICR/MS. Twenty-seven urine samples tested positive for glucocorticoids or beta-2-agonists and twenty samples coming from volunteers and clean athletes were analyzed with the two different mass spectrometry approaches using both positive and negative electrospray ionization modes. Urine is a highly complex matrix containing thousands of metabolites having different chemical properties and a high dynamic range. We used multivariate analysis techniques to unravel this huge data set. Thus, the several groups we created were studied by Principal Components Analysis (PCA) and Partial Least Square regression (PLS-DA and OPLS) in the search of discriminating m/z values. The selected variables were annotated and placed on pathway by using MassTRIX.

International audience; Fish are often exposed to various molecules like pesticides. Some of these compounds get biomagnified within aquatic food web, inducing health hazards of consumers. However, behaviors of many pesticides are still unknown. This work aims to study the uptake and the elimination of some of them in muscle tissue of edible fish (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop, and thifensulfuron-methyl). Two freshwater fish species (Perca fluviatilis and Cyprinus carpio) were exposed to a mixture of these 13 pesticides, via multi-contaminated pellets, and then, eliminated. Compounds were measured in food, water and muscle tissue using multi-residues methods. Kinetics, biomagnification factors (BMFs) and half-lives (t1/2) were estimated and they did not show a large difference between the species. Muscular BMFs ranged from 2 x 10(-6) (mesosulfuron-methyl in perch) to 1 x 10(-3) (isoproturon and napropamid in perch) and t1/2 ranged from 0.8 (mesosulfuronmethyl in perch) to 40.3 d (napropamid in carp). BMFs were also modeled as a function of K-ow value. All BMF values were explained by the model, except for diflufenican which had a BMF lower than that expected by our modeling work, probably due to an efficient metabolism. Results led to the conclusion that none of these chemicals would probably be biomagnified within aquatic food webs.

The literature increasingly reports sampling rates (Rs) for Polar Organic Chemical Integrative Samplers (POCIS) but the data obtained come from various calibration systems that are not always well-defined (agitation, temperature, measured micropollutant concentrations in water,y). In order to obtain accurate laboratory Rs for priority and emerging substances, POCIS need to be exposed in a robust and well-defined calibration system. Thus, we built a flow-through calibration system containing tap water spiked with 56 organic micropollutants (alkylphenols and phenols, hormones, pesticides, pharmaceuticals, UV filter). POCIS were immersed for up to 28 days. Tap water micropollutant concentrations and additional parameters (temperature, pH, conductivity, dissolved organic carbon, flow velocities) were kept constant and controlled throughout the calibration experiment. Based on the observed uptake kinetics, we distinguished four types of micropollutant accumulation patterns: curvilinear accumulation (30 molecules, group 1), accumulation with an inflexion point (13 molecules, group 2), random accumulation (eight molecules, group 3), and no or very low accumulation (five molecules, group 4). Rs was calculated for 43 out of 56 micropollutants (groups 1 and 2). Calculated Rs values ranged from 0.030 L/d to 0.398 L/d. POCIS can supply TWA concentrations for hormones, pesticides, several pharmaceuticals, a few alkylphenols, and the UV filter. Our Rs results are generally less than two fold-different (higher or lower depending on target molecule) to the literature data using the same type of calibration system or for micropollutants with log Kow42.65. We found a quadratic correlation between Rs and log D for betablockers, herbicides and hormones.

International audience; Residues of pesticides in fish farming productions from barrage ponds are seldom studied in spite of increasing health questionings and environmental concerns. The purpose of this study is to establish the pesticide contamination profiles of sediments and edible fish from five ponds in Northeastern France. Multi-residues method and liquid chromatography-tandem mass spectrometry analysis were used to quantify 13 pesticides (azoxystrobin, carbendazim, clomazone, diflufenican, dimethachlor, fluroxypyr, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl). Ten sediments and 143 muscles samples were analysed, corresponding to two successive fishing campaigns (first fishing date and second fishing date (P2), about 1 year later) on five sites (noted C-0, C-25, C-45, C-75 and C-85 to express the increasing gradient of crop area). Isoproturon was present in all sediments samples (1.8-56.4 mu g/kg dry weight). During P2 period, carbendazim was quantified in the fish of site C-0 (0.09 +/- 0.02, 0.2 +/- 0.1 and 0.17 +/- 0.06 mu g/kg wet weight (ww) for roach, carp and perch, respectively). Metazachlor was only quantified in perch of the site C-25 (0.13 +/- 0.02 mu g/kg ww). Concentrations of isoproturon were similar for the sites C-45 and C-75 with 0.4 +/- 0.1 and 0.75 +/- 0.06 mu g/kg ww for carp and perch, respectively. Contamination of fish reflected generally concentrations in surroundings. Isoproturon was the most concentrated and its main source was water for perch while carp was exposed through both water and sediments, highlighting their life strategies in pond.

International audience; Reproductive function is controlled by a finely tuned balance of androgens and estrogens. Environmental toxicants, notably endocrine disrupting chemicals (EDCs), appear to be involved in the disruption of hormonal balance in several studies. To further describe the effects of selected EDCs on steroid secretion in female rats, we aim to simultaneously investigate the EDC concentration and the sex hormone balance in the ovaries. Therefore, an effective method has been developed for the quantification of the sex steroid hormones (testosterone, androstenedione, estradiol, and estrone) and four endocrine disrupting chemicals (bisphenol A, atrazine, and the active metabolites of methoxychlor and vinclozolin) in rat ovaries. The sample preparation procedure is based on the so-called "quick, easy, cheap, effective, rugged, and safe" approach, and an analytical method was developed to quantify these compounds with low detection limits by liquid chromatography coupled with a tandem mass spectrometer. This analytical method, applied to rat ovary samples following subacute EDC exposure, revealed some new findings for toxicological evaluation. In particular, we showed that EDCs with the same described in vitro mechanisms of action have different effects on the gonadal steroid balance. These results highlight the need to develop an integrative evaluation with the simultaneous measurement of EDCs and numerous steroids for good risk assessment.

International audience; Endocrine disrupting compounds (EDCs) are suspected to be responsible for many disorders of the human reproductive system. To establish a causality relationship between exposure to endocrine disruptors and disease, experiments on animals must be performed with improved or new analytical tools. Therefore, a simple, rapid, and effective multi-residue method was developed for the determination of four steroid hormones (i.e., testosterone, androstenedione, estrone, and estradiol), glucuronide and sulfate conjugates of estrone and estradiol and four endocrine disruptors in rat testis (i.e., bisphenol A, atrazine, and active metabolites of methoxychlor and vinclozolin). The sample preparation procedure was based on the Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) approach. An analytical method was then developed to quantify these compounds at ultra-trace levels by liquid chromatography coupled to tandem mass spectrometry. The QuEChERS extraction was optimized with regard to the acetonitrile/water ratio used in the extraction step, the choice of the cleanup method and the acetonitrile/hexane ratio used in the cleanup step. The optimized extraction method exhibited recoveries between 89% and 108% for all tested compounds except the conjugates (31% to 58%). The detection limits of all compounds were below 20 ng g(-1) of wet weight of testis. The method was subsequently applied to determine the levels of hormones and EDCs in seven rat testis samples.

International audience; The aim of this study was to develop an analytical method for the analysis of traces of hormonal steroids and veterinary and human drugs in soil. Thus, 31 substances were selected, including 14 veterinary products, 11 hormonal steroids and 6 other well-known human contaminant compounds. The procedure inspired by the quick, easy, cheap, effective, rugged and safe (QuEChERS) extraction method was developed. First the acetonitrile-based extraction was optimized. This step was followed by a solid-phase extraction (SPE) clean-up using both a strong anion-exchange cartridge and a polymeric cartridge. The analysis was then performed using liquid chromatography coupled to a triple quadrupole analyser operated with tandem mass spectrometry. This analytical procedure was validated using the ICH/2005 standard by evaluating the linearity (from 0.01 ng/g to 1000 ng/g - R2 > 0.99), the intra-day precision (relative standard deviation (RSD) < 20%), the inter-day precision (RSD < 30%), recoveries (40-110% for most of the compounds) and limits of detection and quantification. This method allowed for the determination of the target analytes in the lower ng/g concentration range. The methodology was then applied to real soil samples collected in several areas of France that received different manure or sludge treatments. Some target compounds were detected at very low level (inferior to the ng/g). Veterinary antibiotics, mainly from the sulfonamide family, were found in soils treated by manure (0.02-0.12 ng/g). On the other hand, pharmaceuticals usually used by humans (carbamazepine, ibuprofen) were detected in soils treated by domestic sludge. Highlights A multi-residues multi-families method for the analysis of 31 emerging pollutants. An innovative, rapid and simple sample extraction based on QuEChERS. Analytical method allowing the determination of the analytes at the low ng/g range. Application of the method to real soil samples

International audience; A multiresidue method was developed for screening, quantification, and confirmation of nine natural androgen steroids and their metabolites in urine. Steroids were first extracted from urine by solid phase extraction, enzymatically deglucuronated, re-extracted using a liquid/liquid extraction for purification, and finally acetylated for GC/MS and GC/FID analysis. Each step of sample preparation, as well as analysis, was optimized: solid phase extraction, liquid/liquid extraction, and derivatization reaction ... Therefore, a rugged sample preparation procedure was developed leading to extracts of sufficient purity (recoveries >66% and few matrix compounds). The whole methodology allowed reliable detection and quantification of the nine steroids at low concentration levels. Linearity and repeatability were established and were found to be satisfactory (R-2 > 0.996, RSD < 11%). Finally, the method was applied to quantify compounds of interest in real samples collected from healthy volunteers and patients treated with 4-androstenedione or dehydroepiandrosterone.

International audience; A novel multiresidue method was developed for the simultaneous analysis of 34 organochlorines, including chlorobenzenes, chlorophenols, chlorinated hydrocarbons and chlorinated olefins, in soil by GC-MS, using a QuEChERS-based extraction. The conventional QuEChERS method was optimised and, for the first time, the use of a non miscible-water solvent was required. The method was compared to ASE extraction, versatile technique widely used for the soils' extraction and QuEChERS-based method was shown to be the most efficient in terms of recoveries, simplicity and rapidity. For ASE, recoveries between 42% and 85% were obtained for the majority of the compounds. However, due to the high pressure, all volatile compounds were lost. In opposite, QuEChERS extraction allowed detection and quantification of all the compounds with recoveries between 60% and 100%. Moreover, no additional clean up by dispersive SPE on PSA was necessary, which allowed reducing the cost of the analysis. Performance of the method was assessed. The method was linear over the range of concentration of 10-5000 μg kg−1. Precision, expressed as intra-day precision and inter-day variation was verified at three concentrations. Limits of detection were from 2 to 50 μg kg−1 and limits of quantification from 7 to 170 μg kg−1 for the majority of the compounds (chlorobenzenes and chlorinated hydrocarbons and olefins), except for chlorophenols. The method was further applied to different soils coming from a contaminated industrial site, where a new environmental remediation process, using phytoremediation, was tested. The results showed that the method could be applied to any kind of soils (mineral or organic) and was appropriate to very volatile compounds which were not available with conventional technique.

communication par affiche; La réglementation REACH a pour objectif d'améliorer le niveau de protection de la santé et de l'environnement. Ainsi, depuis le 1er juin 2007, les substances sont classées selon leurs propriétés physico-chimiques, toxicologiques et environnementales. Leur pouvoir de bioaccumulation, leur persistance dans l'environnement, ou encore leur toxicité pour la reproduction sont alors étudiés. Dans ce sens, certaines substances sont qualifiées de perturbateurs endocriniens. Ce terme désigne en fait des substances qui interférent avec les fonctions du système hormonal. Selon REACH, ces substances sont considérées comme des substances extrêmement préoccupantes du fait de leur toxicité pour la reproduction. Ainsi, certains composés tels que le bisphénol A, l'atrazine, la vinclozoline ou encore l'HPTE sont suspectés d'être des perturbateurs endocriniens. Afin d'étudier directement ces derniers, des études sont menées pour établir une relation de causalité entre l'exposition aux perturbateurs endocriniens et certaines maladies. Dans ce contexte, en collaboration avec l'INERIS (Institut National de l'Environnement industriel et des RISques), l'impact de ces perturbateurs endocriniens (bisphénol A, atrazine, vinclozoline, HPTE) sur le système hormonal est étudié par la mesure in vivo de la balance androgènes / oestrogènes. Pour cela, les fractions libres et les fractions conjuguées des hormones sexuelles dans le sérum sont détectées et quantifiées par LC-MS/MS. Les molécules recherchées sont alors la testostérone (T) et l'androstènedione (A) pour les androgènes, l'oestrone (E1) et la 17-ß-oestradiol (E2) pour les oestrogènes ainsi que les métabolites sulfo- et glucuro-conjugués de ces derniers. De plus, les pesticides auxquels sont exposés les espèces d'études (rats adultes mâles et femelles) sont aussi dosés pour établir la relation de causalité supposée. Deux techniques d'extraction ont alors été développées : la première innovante permet de minimiser les quantités de matrice et solvants, il s'agit des MEPS (C18) (Micro- Extraction sur Phase Solide) et la seconde plus classique, la SPE (Oasis HLB). Le choix de la méthode d'extraction repose sur divers critères, à savoir, les rendements, la linéarité, la LOD-LOQ et l'effet matrice. Les deux techniques permettent de travailler sur une large gamme de linéarité (de 1 à 2000 ppb) et présentent des LOD allant de 0,2 à 1 ppb et des LOQ de 1 ppb à 20 ppb. Des rendements de 60% à 84% ont été obtenus sur SPE pour tous les composés, les résultats sont similaires avec les MEPS à l'exception des métabolites conjugués (13 à 40 %). Afin de pouvoir étudier sélectivement ces métabolites glucuronidés et sulfatés, de nouvelles phases MEPS devront être développées. Les effets de matrice constatés sont corrigés par étalonnage interne. Cette comparaison permet donc de choisir la méthode d'extraction optimale par SPE, fiable et répétable, qui sera appliquée aux 400 échantillons de sérum de rats adultes.

International audience; Pesticides residues in aquatic ecosystems are an environmental concern which requires efficient analytical methods. In this study, we proposed a generic method for the quantification of 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in three environmental matrices. Pesticides from water were extracted using a solid phase extraction system and a single solid-liquid extraction method was optimized for sediment and fish muscle, followed by a unique analysis by liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Limits of quantification were below 5 ng L−1 for water (except for fluroxypyr and iprodion) and ranged between 0.1 ng g−1 and 57.7 ng g−1 for sediments and regarding fish, were below 1 ng g−1 for 8 molecules and were determined between 5 and 49 ng g−1 for the 5 other compounds. This method was finally used as a new routine practice for environmental research.

International audience; The levels of a wide variety of pharmaceuticals and hormones, in source and potable-water supplies of French drinking water treatment plants, were assessed. In surface waters, 27 of the 51 target compounds were determined at least once. Paracetamol, salicylic acid and carbamazepine were quantified in more than 80% of samples. The highest concentration of 71 ng/L was observed for paracetamol. Twelve other substances were widely found in the surface waters studied, contaminating between 33 and 80% of the samples. These compounds include analgesics, psychotropic drugs, antibiotics and beta-blockers consistent with the French consumption, as well as natural hormones (oestrone, progesterone and androgens) and synthetic progestatives. In drinking water supplies, 25 compounds were also present, salicylic acid being the most frequently detected. Carbamazepine and the β-blocker atenolol found at lower levels (maximum 2 ng/L), are also present in more than 30% of the contaminated drinking waters. The pharmaceuticals exhibit different reactivity towards the treatments, while progestagens and androgens seem resistant to most of them. The effectiveness of the treatments is discussed, as well as the consequences of the presence of all these compounds on human health. This is the first time that such a long list of compounds (51) is proposed to assessment, and consequently this study provides the first data on pharmaceuticals and steroids occurrences in French drinking waters and represents a basis for the assessment of risks for humans. Moreover, at the international level, this is the first time that so many substances are quantified in drinking water, due to the very low detection limits, especially in the case of the hormones.

International audience; As part of a regional screening to evaluate the risk, for the health of populations, to certain classes of emerging substances, several families of pharmaceuticals and hormones were looked for in waters intended to drinking. Thus, 52 substances were investigated in 71 surface waters and 70 groundwaters. Results indicate that no water was free of pollutants, regardless of its origin (surface or groundwater) and the season of collect. The pharmaceuticals most frequently detected and with the highest concentration levels were salicylic acid, carbamazepine and acetaminophen. Among hormones, testosterone, androstenedione and progesterone were detected in almost all the samples. Globally the groundwaters were less contaminated than surface waters in regards pharmaceuticals frequencies and levels. On the other side, androgens and progestagens were present with comparable frequencies and levels in both compartments. The risk linked to the presence of these substances on human health is discussed.

International audience; Pesticide residues in fish muscle are an environmental and a health safety concern which requires analytical methods presenting high sensitivity and low limits of quantification. In this study, adapted QuEChERS method, coupled to liquid chromatography tandem mass spectrometry (Scheduled MRM-5500 QTRAP), was developed to quantify 13 pesticides (azoxystrobin, clomazone, diflufenican, dimethachlor, carbendazim, iprodion, isoproturon, mesosulfuron-methyl, metazachlor, napropamid, quizalofop and thifensulfuron-methyl) in muscle of fish. Quantification limits were below 1 ng g−1 except for clomazone (1.8 ng g−1) and quizalofop (7.4 ng g−1). Best recoveries were observed for perch (>80%) and roach (>68%), except for thifensulfuron-methyl. Lower recoveries had been observed for carp (6% to 86%). Relative standard deviation was lower than 28% for intra-day and 29% for inter-day analysis, respectively. This method was successfully tested on three fish species, naturally or orally exposed: roach (Rutilus rutilus), perch (Perca fluviatilis) and carp (Cyprinus carpio). Few levels were observed in fish naturally exposed, but carp and perch orally contaminated showed measurable levels in their muscles.

International audience; A metabonomic strategy based on LC-MS was employed to investigate the metabolic profile of urine samples from 20 athletes who had been tested positive for corticoids and anabolic steroids and 29 controls. In this aim, different sample preparations and chromatographic conditions were compared. The acquired LC-MS data of doped athletes and controls were subjected to analysis of variance (ANOVA) and principal component analysis (PCA). Using this approach, molecular signature of human urine was obtained showing that metabonomics could be a complementary tool to discriminate different urinary profiles and to track down metabolic changes in humans.