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Background: The increasing diversity of psychoactive substances on the unregulated drug market poses significant health, psychological, and social risks to people who use drugs (PWUD). To address these risks, various harm reduction (HR) policies have been implemented, including drug checking services (DCS). Many analytical methods are used for DCS. While qualitative methods (e.g., thin layer chromatography, spectroscopy) are easier to implement, they are not as accurate as quantitative methods (e.g., LC-UV, LC-MS). Some HR programmes have implemented high-performance liquid chromatography coupled with UV detection (LC-UV). This article presents the cross-validation of this quantitative method with a reference liquid chromatography coupled with high resolution mass spectrometry (LC-HRMS) method., Methods: Drug samples were provided by PWUD to a DCS called DrugLab in Marseille, France. The samples were weighed and prepared through dissolution in methanol, followed by ultrasonic bathing. Samples were analysed onsite using LC-UV analysis. They were then subsequently analysed with the reference LC-HRMS method. The LC-UV instrument in DrugLab was calibrated after being purchased; analysis of standard solutions was routinely performed once a month and after maintenance operations. For the LC-HRMS instrument, calibration and quality control procedures followed European Medicines Agency (EMA) guidelines. Statistical analyses were conducted including Spearman correlation tests using IBM ® SPSS ® Statistics version 20., Results: A total of 102 samples representing different product classes and cutting agents were cross-validated. Differences between both analyses methods for each molecule analysed were ≤ 20%, with significant correlations between both methods' results for most substances. Notably, LC-HRMS provided lower concentration values for cocaine and acetaminophen, whereas it provided higher values for other substances. Correlations were significant for cocaine, ketamine, MDMA, heroin, amphetamine, caffeine, acetaminophen, and levamisole., Conclusions: This study demonstrates that the results provided by DrugLab were accurate and reliable, making LC-UV an adaptable, stable, and suitable analytical method for simple matrices like drugs in a DCS context. However, this cross validation does not guarantee accuracy over time. A proficiency test project in HR laboratories across France is currently under development in order to address potential drifts in LC-UV accuracy., (© 2024. The Author(s).)

The headspace volatile organic compound (VOC) fingerprints (volatilome) of French wine brandies were investigated by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS). Protonated ethanol chemical ionization was used with dedicated experimental conditions that were previously validated for model wines. These included a reference vial containing a hydro-alcoholic solution with the same ethanol content (20% v/v) as the diluted sample spirits, which was used to establish steady-state ionization conditions. A low electric field strength to number density ratio E/N (85 Td) was used in the drift tube in order to limit the fragmentation of the protonated analytes. The obtained headspace fingerprints were used to investigate the origin of French brandies produced within a limited geographic production area. Brandies of two different vintages (one freshly distilled and one aged for 14 years in French oak barrels) were successfully classified according to their growth areas using unsupervised (principal component analysis, PCA) and supervised (partial least squares regression discriminant analysis, PLS-DA) multivariate analyses. The models obtained by PLS-DA allowed the identification of discriminant volatile compounds that were mainly characterised as key aroma compounds of wine brandies. The discrimination was supported by sensory evaluation conducted with free sorting tasks. The results showed that this ethanol ionization method was suitable for direct headspace analysis of brandies. They also demonstrated its ability to distinguish French brandies according to their growth areas, and this effect on brandy VOC composition was confirmed at a perceptive level.

Origin verification of 240 French wines from four regions of France was undertaken using isotope and elemental analyses. Our aim was to identify and differentiate the geographical origin of these red wines, and more importantly, to build a classification tool that can be used to verify geographic origin of French red wines using machine learning models. Multivariate analyses of the isotopic and elemental data revealed that it is possible to determine the geographical origin of French wines with a high level of confidence for most regions analyzed in this study. The wine verification accuracy of four French wine producing regions of Bordeaux, Burgundy, Languedoc-Roussillon and Rhone using an Artificial Neural Network (ANN) method was 98.2%. The results also show that ANN is more suitable than Discriminant Analysis for this verification purpose. The most important variables for French wine regional traceability were Mg, Mn, Na, Sr, Ti and Rb., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The origin of funerary practices has important implications for the emergence of so-called modern cognitive capacities and behaviour. We provide new multidisciplinary information on the archaeological context of the La Ferrassie 8 Neandertal skeleton (grand abri of La Ferrassie, Dordogne, France), including geochronological data - 14 C and OSL-, ZooMS and ancient DNA data, geological and stratigraphic information from the surrounding context, complete taphonomic study of the skeleton and associated remains, spatial information from the 1968-1973 excavations, and new (2014) fieldwork data. Our results show that a pit was dug in a sterile sediment layer and the corpse of a two-year-old child was laid there. A hominin bone from this context, identified through Zooarchaeology by Mass Spectrometry (ZooMS) and associated with Neandertal based on its mitochondrial DNA, yielded a direct 14 C age of 41.7-40.8 ka cal BP (95%), younger than the 14 C dates of the overlying archaeopaleontological layers and the OSL age of the surrounding sediment. This age makes the bone one of the most recent directly dated Neandertals. It is consistent with the age range for the Châtelperronian in the site and in this region and represents the third association of Neandertal taxa to Initial Upper Palaeolithic lithic technocomplex in Western Europe. A detailed multidisciplinary approach, as presented here, is essential to advance understanding of Neandertal behavior, including funerary practices.

The glucosinolate (GL) profiles of wild and cultivated Brassica montana Pourret (seed, stem, leaf, root) from southern France were established using LC-MS analysis. In this investigation we have confirmed the presence of 9 known GLs: but-3-enyl- ( 1 ), prop-2-enyl- ( 2 ), pent-4-enyl- ( 3 ), (2 R )-2-hydroxybut-3-enyl- ( 4 ), 4-hydroxyindol-3-ylmethyl- ( 5 ), 4-(methylsulfinyl)butyl- ( 6 ), 4-(methylsulfanyl)butyl- ( 7 ), 1-methoxyindol-3-ylmethyl- ( 8 ), and indol-3-ylmethyl ( 9 ) GL. In addition, we tentatively identified for the first time the presence in the plant of 1-methylpropyl GL ( 10 ) in all plant parts. In addition, we have pointed out differences in GL profiles between plant organs and between wild and cultivated B. montana .

The original manuscript of Casanova's Memoirs is stored at the Bibliothèque Nationale de France in Paris. We have gained access to it and explored the surfaces of chapters one and two (via the ethylene vinyl acetate [EVA] film technology, i.e., of diskettes of ethylene vinyl acetate with embedded strong cation and anion exchangers and C8 resins) in search of potential diseases of the author, especially of the gonorrhea bacterium, since Casanova reported that he had several bouts of this pathology along his adventurous life. Although the bacterium was not found, we have detected high levels of HgS as red spots along the lines of the manuscript, suggesting that Casanova was using this chemical as a cure for his venereal disease. Additionally, among the several bacteria identified on the surface via mass spectrometry, we could detect traces of Streptococcus uberis, a typical animal infection, found also in humans, together with a few strains of Lactobacilli, probably present in his saliva. The EVA film technology appears to open new horizons for investigating the world Cultural Heritage., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

There is justification for limiting lead (Pb) exposure as much as possible, given its impact on health at low concentrations. Consequently, the aim of this study was to measure blood lead levels (BLL) and examine exposure factors related to BLL variations in the general adult population of northern France, a current and past industrial area. Two thousand inhabitants of northern France, aged between 20 and 59 years, were recruited using the quota method with caution. Blood lead levels were quantified by inductively coupled plasma-mass spectroscopy (ICP-MS), and variation factors were studied separately in men and women using multivariate stepwise linear and logistic regression models. The geometric mean of the BLL was 18.8 μg/L (95% confidence interval [CI]: 18.3-19.3). Occupational factors affected BLL only in men and represented 14% of total explained variance of BLL. External occupational factors significantly increasing mean levels of BLL were tobacco, consumption of some beverages (wine, coffee, tea, and/or tap water), raw vegetables, housing characteristics (built prior to 1948, Pb piping in the home) and do-it-yourself or leisure activities (paint stripping or rifle shooting). Consumption habits accounted together for 25% and 18% of the total explained variance, respectively, in men and women. Industrial environment did not significantly contribute to BLL variations. Blood lead levels observed in the general population of this industrial part of France did not appear to be excessively elevated compared to values found internationally. Nonetheless, these BLL remain a public health issue in regard to nonthreshold toxicity attributed to Pb.

The pigments responsible for the yellow-orange coloration of apple juices have remained largely unknown up to now. Four French cider apple juices were produced in conditions similar to those used in the cider-making industry. The oxidized juices, characterized using the CIE L a b parameters, displayed various colors depending on the apple variety and native phenolic composition. HPLC-DAD-MS revealed contrasting pigment profiles related to oxidized tanning and nontanning molecules. The latter were divided into two groups according to their polarity and their visible spectra. With regard to phenolic classes, flavanol monomers and hydroxycinnamic acids played an essential role in the formation of oxidation products. Interestingly, dihydrochalcones appeared to include precursors of some yellow compounds. Indeed, the yellow pigment phloretin xyloglucoside oxidation product (PXGOPj), derived from phloretin xyloglucoside, was clearly identified in apple juices as a xyloglucose analogue of the yellow pigment phloridzin oxidation product (POPj), previously characterized in a model solution by Le Guernevé et al. (Tetrahedron Lett. 2004, 45 (35), 6673-6677).

Since the early 1970's, investigators at Station Biologique de Roscoff (SBR), France, have been using marine organisms as models to describe molecular pathways conserved through evolution in mammalian cells (e.g. the cyclin-dependent kinases involved in the control of the cell division cycle). Some kinases are misregulated in various human pathologies, including cancers. Using a specialized screening approach, chemical libraries were analysed, using on-site facilities at Roscoff, in order to identify small chemical inhibitors of protein kinases. Eight chemical scaffolds produced by marine organisms were characterized as candidate drugs by our screening facility, some of which are being considered as chemical tools to pinpoint specific cellular functions of the targeted kinases. In this review, we describe our existing screening facilities and we discuss new perspectives related to marine bioprospecting., (© 2015 médecine/sciences – Inserm.)

Tandem mass spectrometry allows to screen many inherited metabolic diseases within a single blood spot. It is possible to screen newborns for amino and organic acid, fatty acid oxidation disorders and lysosomal diseases. Tandem mass spectrometry neonatal screening is not yet realized in France in 2014.

An analytic method was developed and validated for the analysis of chlordecone in the three main types of French West Indies soils: Ferralsol, Andosol and Nitisol with and without the addition of Daramend® and compost amendment used in a remediation process. The method consists in analysis by gas chromatography coupled with triple quadrupole mass spectrometry after pressurised liquid extraction. The high natural content of organic matter in the soils coupled with the additional exogenous organic matter from the amendments tested lead to a complex extract. Trans-nonachlor was used as surrogate to correct the results for extraction efficiency, and (13)C chlordecone was added as internal standard to mimic as closely as possible the behaviour of chlordecone and suppress possible side effects during its analysis. The key parameters of the method (linearity, repeatability, interday precision, specificity, extraction efficiency and limit of quantification) were validated in accordance with the NF T 90-210 standard method. The limit of quantification is 0.03 mg/kg. Uncertainty (k = 2) was 40 % for concentrations lower than or equal to 1 mg/kg, and 30 % for concentrations greater than 1 mg/kg.

Rice is a staple food for nearly half the world's population. The discrimination of geographical origin of rice in order to its authenticity is essential to prevent mislabeling and adulteration problems. The multi-element fingerprinting has a great potential for the differentiation of rice grains. A study of the capability of the high resolution inductively coupled plasma mass spectrometry (HR-ICP-MS) methodology for multi-element fingerprinting of rice has been carried out. A total of 31 Thai jasmine rice and 5 foreign (France, India, Italy, Japan and Pakistan) rice samples were analysed by high resolution ICP-MS after acid digestion. Accuracy of the whole procedure was verified by the analysis of rice flour standard reference material (NIST SRM 1568a). The concentrations of 21 elements were evaluated and used as chemical indicator to discriminate the origin of rice samples. The classification of rice samples was carried out based on elemental composition by a radar plot and multivariate data analysis, including principal component analysis (PCA) and discriminant analysis (DA). Thai jasmine rice can be differentiated from foreign rice samples by radar plots and multivariate data analysis. Furthermore, the DA can differentiate Thai jasmine rice samples according to each region of origin (northern, northeastern or central regions of Thailand). Therefore, multi-element fingerprinting combined with the use of multivariate statistical techniques can be considered as a powerful tool for rice authentication., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

In two outbreaks of food-borne botulism in France, Clostridium botulinum type A was isolated and characterized from incriminated foods. Botulinum neurotoxin type A was detected in the patients' sera by mouse bioassay and in vitro endopeptidase assay with an immunocapture step and identification of the cleavage products by mass spectrometry.

Species of the genus Cystoseira are particularly hard to discriminate, due to the complexity of their morphology, which can be influenced by their phenological state and ecological parameters. Our study emphasized on the relevance of two kinds of analytical tools, (1) LC/ESI-MS(n) and (2) (1)H HR-MAS NMR, also called in vivo NMR, to identify Cystoseira specimens at the specific level and discuss their taxonomy. For these analyses, samples were collected at several locations in Brittany (France), where Cystoseira baccata, C. foeniculacea, C. humilis, C. nodicaulis and C. tamariscifolia were previously reported. To validate our chemical procedure, the sequence of the ITS2 has been obtained for each species to investigate their phylogenetic relationships at a molecular level. Our study highlighted the consistency of the two physico-chemical methods, compared to "classical" molecular approach, in studying taxonomy within the genus Cystoseira. Especially, LC/ESI-MS(n) and phylogenetic analyses converged into the discrimination of two taxonomical groups among the 5 species. The occurrence of some specific signals in the (1)H HR-MAS NMR spectra and/or some characteristic chemical compounds during LC/ESI-MS(n) analysis could be regarded as discriminating factors. LC/ESI-MS(n) and (1)H HR-MAS NMR turned out to be two relevant and innovative techniques to discriminate taxonomically this complex genus., (Copyright © 2010 Elsevier B.V. All rights reserved.)

An analytical method was developed for the determination of nine antiviral drugs (acyclovir, abacavir, lamivudine, nevirapine oseltamivir, penciclovir, ribavirin, stavudine, zidovudine) and one active metabolite (oseltamivir carboxylate) in raw and treated wastewater as well as in surface water using LC/ESI tandem MS detection. Relative recoveries exceeded 80% and limits of quantification ranged between 0.2 and 10 ng L(-1). Matrix effects were compensated by the use of stable isotope labeled surrogate standards and optimized chromatographic separation on a Hydro-RP column. All antiviral drugs, except ribavirin, were detected in raw wastewater. A significant reduction in concentrations was observed for acyclovir, lamivudine, and abacavir in treated wastewater indicating a substantial removal, while nevirapine, zidovudine and oseltamivir were found in similar concentrations in raw and treated wastewater. Concentrations in river waters were in the lower ng L(-1)-range, with a maximum of 190 and 170 ng L(-1) for acyclovir and zidovudine, respectively in the Hessian Ried. Estimated total compound loads in the Ruhr river ranged between <0.1 and 16.5 g d(-1) while for the Rhine river values between 370 and 1800 g d(-1) were determined. The ratios of oseltamivir to oseltamivir carboxylate were approximately a factor of 10 higher for the Rhine than for the other rivers and streams indicating a significant contribution from other sources such as discharges from manufacturing facilities.

An imaging mass spectrometric method using laser ablation inductively coupled plasma spectrometry (LA-ICP-MS) was developed to determine Cu, Zn, Cd, Hg and Pb and metal distribution in longitudinal tissue sections of the marine snail Nassarius reticulatus (Gastropoda, Prosobranchia). Snails were sampled in northern Brittany (France) at three stations with different contamination levels. The quantification of metal distribution (imaging or mapping) in a thin slice of the snail tissue was carried out using different strategies: by one-point calibration and via matrix-matched laboratory standards using different biological materials (BCR 278, snail tissue, and rat brain). Together with the imaging of metals the distribution of two non-metals (carbon and sulfur) was analyzed. The imaging LA-ICP-MS analysis yielded an inhomogeneous distribution for all elements investigated. The detection limits for the distribution analysis of Cu, Zn, Cd, Hg and Pb measured by LA-ICP-MS were in the low microg g(-1) range.

In the northeastern part of France, around the city of Metz, lichens (Hypogymnia physodes) have been transplanted from a single reference site to five different sites: (i) the reference site itself, (ii and iii) two peri-urban sites, (iv) a site in the proximity of a highway, and (v) a final one close to an industrial site. The dynamics of two different system set-ups (one covered and one uncovered) were evaluated. Samples have been collected 14, 34, and 68 days after transplantation. Lead concentrations already accumulated in the thallus, and the corresponding Pb isotopic compositions have been measured by quadrupole-based ICP-mass spectrometry. A systematic difference between the two setups is found for Pb concentrations, with the higher concentrations measured in lichens from the uncovered devices. Lead concentrations in lichens from the covered devices were found to be lower than or equal to the original concentration. Also the Pb isotopic compositions show a systematic difference between the devices, with the Pb isotopic composition present in lichens from the uncovered device being more radiogenic. Substantial changes in the isotopic composition of Pb are recorded for lichens from the uncovered device (from about 1.15 up to 1.22 for the 206Pb/207Pb ratio), in some cases already after only 34 days of exposure. The increases in the Pb concentration and the 206pb/207Pb ratio and the differences between the devices are explained by hypothesizing that (i) different Pb sources give rise to a different size distribution of aerosol particles and (ii) in the lichens present in the covered setup, a part of the aerosol particles cannot be incorporated. Also the influence of the source of the aerosols to lichens after transplantation is evaluated and the potential influence of biological reactions is discussed.

A harmonized approach for the validation of analytical methods based on accuracy profile was introduced by a SFSTP commission on the validation of analytical procedure. This fourth and last document aims at illustrating this methodology and the statistics used. Therefore the validation of real case methods are proposed such as methods for the quality control of drugs, for the quantitation of impurities in drug substances, for bioanalysis or for the determination of nutriments. Furthermore, different types of analytical methods are used in order to demonstrate the applicability of the proposed approach to a wide range of methods such as liquid chromatography (LC-UV, LC-MS), spectrophotometry or ELISA.

This study was undertaken to investigate the relevance of using the pyrolysis-MS (Py-MS) technique to discriminate the production area of oysters harvested over two years and to assess from the data of the second year of harvest the potential of an alternative MS-based technique, the solid phase microextraction-MS (SPME-MS), to perform this discrimination. Oysters were harvested in various areas of France, and models of discrimination according to harvest season were built from Py-MS fingerprints and from virtual SPME-MS fingerprints obtained by summing the mass spectra generated by the SPME-GC-MS system. The treatment of the Py-MS data by a 21-12-3 artificial neural networks led to a correct classification of only 89.2% of the oyster samples according to shoreline. The misclassifications thus did not allow use of the Py-MS technique as a relevant tool for authentication of oyster origin. The assessment of the potential of the virtual SPME-MS fingerprints to discriminate the production area of oysters was undertaken on a part of the sample set. The virtual SPME-MS data were pretreated according to two methods, filtering of raw data (FRD) and comprehensive combinatory standard correction (CCSC), a recently developed chemometric method used for the correction of instrumental signal drifts in MS systems. The results obtained with the virtual SPME-MS fingerprints are promising because this technique, when the data were pretreated by the CCSC method, led to a successful discrimination of the oyster samples not only according to shoreline but also according to production region. This study confirms that an efficient correction method (CCSC) of instrumental drifts can considerably increase the discriminative information contained in the volatile fraction of food products.

An analytical methodology was developed for the determination of 21 trace elements in suspended particulate matter (PM) using a microwave digestion procedure associated with an inductively coupled plasma mass spectrometry (ICP-MS). The dynamic reaction cell (DRC) of the instrument was carefully optimized to eliminate polyatomic species causing spectral interferences for three specified elements (Cr, Fe, Mn). With this method, the detection limits based on the analysis of seven quartz fibre filters (QFF) considering a one-week sample (250 m3) varied between 0.2 and 650 pg m(-3) for trace elements and between 2.1 and 5.6 ng m(-3) for major elements (Fe, Ti, Zn). The recovery of the analytes was tested with NIST SRM 1648 urban dust within 10% of the certified values only for 3-4 mg of material. The first results were discussed for a field campaign which was carried out simultaneously in the heaviest traffic road tunnel of the centre of Nice and near the landing-taking-off runways in the international airport of Nice Côte d'Azur. The behaviour of some combustion tracers was especially studied.

Numerous palaeo metallurgical sites (n = 70) characterized by slag presenting a homogeneous typology have been reported on the Mont-Lozère Massif (Southern France). These activities took place in the medieval period. The silicated slag matrix comprises mainly Pb (25%), Sb (0.4%), and several thousand parts per million of As, Cu, and Zn. Soil samples were collected in and around two sites, to understand the dispersion mechanism affecting the slag tailings through use of metal concentrations and lead isotopic compositions. The majority of polluted soil samples show high enrichment factors (EF) for Pb and Sb, slightly lower EFs for Cu, and much lower EFs for As and Zn. We show that this "old" metal pollution was physically dispersed, through erosion of workshop soils and slag tailings, in a restricted area (ca. 200 m down slope form the site). There is no evidence for massive leaching of slag metals by soil waters, except for Zn. Thus, the pollution is mainly due to the metal-making process, i.e., smoke-fallout, pieces of ore, the crackling of smelting ore outside the oven during reduction, and charcoal, etc. The lead isotopic compositions of the soils define a binary mixing trend between local granite or background soil and slag (which represent the workshop soil). Simple mass balance equations using either Pb isotopes or Pb concentrations suggest that between 40 and 100% of the total Pb in soils comes from the Medieval workshop pollution, leaving any later pollution negligible. The large number of sites on the Mont-Lozère means this medieval pollution is significant and poses a real environmental risk.

Novel prognostic biomarkers are imperatively needed to help direct treatment decisions by typing subgroups of node-negative breast cancer patients. The current study has used a proteomic approach of SELDI-TOF-MS screening to identify differentially cytosolic expressed proteins with a prognostic impact in 30 node-negative breast cancer patients with no relapse versus 30 patients with metastatic relapse. The data analysis took into account 73 peaks, among which 2 proved, by means of univariate Cox regression, to have a good cumulative prognostic-informative power. Repeated random sampling (n = 500) was performed to ensure the reliability of the peaks. Optimized thresholds were then computed to use both peaks as risk factors and, adding them to the St. Gallen ones, improve the prognostic classification of node-negative breast cancer patients. Identification of ubiquitin and ferritin light chain (FLC), corresponding to the two peaks of interest, was obtained using ProteinChip LDI-Qq-TOF-MS. Differential expression of the two proteins was further confirmed by Western blotting analyses and immunohistochemistry. SELDI-TOF-MS protein profiling clearly showed that a high level of cytosolic ubiquitin and/or a low level of FLC were associated with a good prognosis in breast cancer.

Background: Adjustments in intestinal absorption and losses of zinc (Zn) are thought to maintain Zn homeostasis when dietary intake levels are altered. Zn status may also influence efficiency of intestinal Zn absorption., Objectives: To determine the impact of dietary intake and status of some micronutrients on Zn absorption in late middle-aged men., Design and Participants: Dietary intake and status of Zn, Cu, Fe, vitamin A, C and fibre, and absorption of Zn were measured in 48 men, aged 58-68 y, confined to a metabolic unit and consuming a typical French diet. Dietary intake was estimated using 4-day food-intake records (including the weekend) and the GENI program. To assess Zn status, serum, erythrocyte, urine Zn levels and serum alkaline phosphatase activity were determined. Zn absorption was determined using the isotope double-labelling method. Zn stable isotopic ratios were measured in plasma samples collected before and 48 h after isotope administration using ICP/MS., Results: Zn intake within the group of men varied from 5.7 to 20.5 mg/day and averaged 12.9 mg/day. Serum Zn level varied from 10 to 18 micromol/l and averaged 12.9 micromol/l. Zn absorption varied from 12 to 46% and averaged 29.7%. Zn absorption was not significantly (P > 0.05) correlated with Zn intake or with any of the Zn status parameters. Zn absorption was only slightly negatively correlated with serum and erythrocyte Zn levels and with serum Fe and ferritin levels in this study., Conclusion: Zn dietary intake and Zn absorption were satisfactory and led to an adequate Zn status in this population.

The potential of quadrupole-based ICP-MS as a tool for B-isotopic analysis of wines and its usefulness in provenance determinations were assessed. A precision of 0.1-0.25% RSD (corresponding to a relative standard deviation of the mean of three replicate measurements of 0.06-0.12%) was sufficient to establish small differences in the B isotope ratios in wines from different geographical origins. Each sample measurement was bracketed by measurements of a standard and mass bias drift correction made by interpolation. Sample preparation was kept to a minimum to avoid possible fractionation. Dilution of the wine samples by a factor of 100 with 0.65% HNO3 was found to reduce matrix-induced mass discrimination substantially. Wines from three wine-producing regions, Stellenbosch, Robertson, and Swartland, in the Western Cape Province of South Africa, and wines from specific regions in France (Bergerac) and Italy (Valpolicella) were analyzed by ICP-QMS for their B-isotopic compositions. It was concluded that the 11B/10B ratios can be used to characterize wines from different geographical origins. Average 11B/10B ratios in red wines from South Africa (Stellenbosch), France (Bergerac), and Italy (Valpolicella) were found to differ by between 0.5 and 1.5%.

A multiresidue method using gas chromatography coupled to ion-trap tandem mass spectrometry (MS/MS) was developed for the analysis of 27 pesticides, commonly used in Alsace, in atmospheric samples (particle and gas phases). As pesticides are expected to be present at very low concentrations and in a complex matrix, the analytical method used was both highly selective and sensitive. These two properties were obtained by associating chromatography with ion-trap MS/MS. To develop this method, analysis of electron impact in single MS was first conducted to choose the parent ions of the pesticides studied. Among the 27 pesticides analysed, seven of them require a derivatisation step. This was the case of some ureas (chlorotoluron, diuron and isoproturon), phenoxy acids (2,4-dichlorophenoxyacetic acid, 4-chloro-2-methylphenoxyacetic acid and mecoprop) and of bromoxynil. The derivatisation was performed with success with pentafluorobenzylbromide. Then, a MS/MS method was optimised by parameters such as the radio frequency storage level and the collision-induced dissociation excitation voltage. Finally, a last step enabled the development of two calibrating programs based on the quantification of daughter ions for the 20 pesticides analysed directly (run 1) and for the seven pesticides which needed derivatisation (run 2). With this analytical procedure, the detection limits varied between 2.5 and 1,250 pg m(-3) depending on the compounds studied. This method was tested with success for atmospheric samples collected in Strasbourg (France) during intensive pesticide treatment in 2002.

Prenatal diagnosis is available for many lysosomal storage disorders (LSD) using chorionic villus samples or amniocytes. Such diagnoses can be problematical if sample transport and culture are required prior to analysis. The purpose of this study was to identify useful biochemical markers for the diagnosis of lysosomal storage disorders from amniotic fluid. Amniotic fluid samples from control (n=49) and LSD affected (n=36) pregnancies were analysed for the protein markers LAMP-1 and saposin C by ELISA, and for oligosaccharide and lipid metabolite markers by electrospray ionisation-tandem mass spectrometry. Lysosomal storage disorder samples include; aspartylglucosaminuria, galactosialidosis, Gaucher disease, GM1 gangliosidosis, mucopolysaccharidosis types I, II, IIIC, IVA, VI, and VII, mucolipidosis type II, multiple sulfatase deficiency, and sialidosis type II. Each disorder produced a unique signature metabolic profile of protein, oligosaccharide, and glycolipid markers. Some metabolite elevations directly related to the disorder whilst others appeared unrelated to the primary defect. Many lysosomal storage disorders were clearly distinguishable from control populations by the second trimester and in one case in the first trimester. Samples from GM1 gangliosidosis and mucopolysaccharidosis type VII displayed a correlation between gestational age and amount of stored metabolite. These preliminary results provide proof of principal for the use of biomarkers contained in amniotic fluid as clinical tests for some of the more frequent lysosomal storage disorders causal for hydrops fetalis.

Extensive studies of the radiocarbon (14C) distribution and transfer in the marine environment of the North-Cotentin peninsula and along the English Channel have been carried out. The main aims of these studies have been to estimate the spatial and temporal variation of the 14C concentration in seawater and to calculate 14C concentration factors for some biological species. Such information will be helpful in order to calculate precisely radiation doses to humans. First results obtained in the vicinity of the COGEMA La Hague nuclear plant (Goury) indicate a 14C labelling of the dissolved inorganic carbon (DIC) in seawater (8.0-26.2 Bq.m(-3)) and a tight relationship between the 14C in the liquid releases from the plant and the 14C concentrations in DIC. The particulate organic carbon (POC) is also labelled. The concentration factor calculations for the brown algae (Fucus serratus) sampled from Goury, and also along the English Channel, give 14C values around 3000 Bq.kg(-1) fresh weight / Bq.L(-1).

Static headspace (SHS), headspace solid phase microextraction (HS-SPME), headspace sorptive extraction (HSSE), and direct thermal desorption (DTD) were applied to the analysis of four French virgin olive oils from Corsica. More than 60 compounds were isolated and characterized by GC-RI and GC-MS. SHS was not suited to the characterization of olive oil volatile compounds because of low sensitivity. The SPME and HSSE techniques were successfully applied to olive oil headspace analysis. Both methods allow the characterization of volatile compounds (mainly C(6) aldehydes and alcohols), which contribute significantly to the "green" flavor note of virgin olive oils. The PDMS stir bar showed a higher concentration capacity than a DVB/CAR/PDMS SPME fiber due to the higher volume of polymeric coating. DTD was a very good tool for extracting volatile and especially semivolatile compounds, such as sesquiterpenes, but requires a significant investment like that for HSSE. Finally, SPME may be a more appropriate technique for routine quality control due to its operational simplicity, repeatability, and low cost.

A rapid procedure--dilution of urine+ICP-MS measurement--for the determination of uranium in urine was validated. Large ranges of concentration and isotopic composition were studied on urine samples excreted by occupationally exposed workers. The results were consistent with those obtained by fluorimetry and by alpha spectrometry after a purification procedure, two currently used techniques. However, the proposed procedure is limited for determination of the minor isotope 234U. Thus for worker monitoring, the conversion of 234U mass concentration into activity concentration can lead to an erroneous value of the effective dose, in particular for a contamination at very low level with highly enriched uranium. A solution to avoid this hazard is to perform a chemical purification prior to ICP-MS measurement to lower uncertainty and detection limit for 234U.

An estimation of the dietary exposure of French consumers to 21 essential and non-essential mineral elements using duplicate meals (breakfast and lunch) purchased from catering establishments was investigated after digestion by a closed vessel microwave procedure and quantification by ICP-MS. Daily dietary exposure estimates for metals and minerals were compared with the Provisional Tolerable Weekly Intakes (PTWI), the Tolerable Daily Intake (TDI) or the Acceptable Daily Intakes (ADI), as established by the FAO/WHO to estimate the risk of toxicity, and the US Recommended Daily Allowances (US RDA) or the Estimate Safe & Adequate Daily Dietary Intakes (ESADDI). Moreover, comparisons were made with those from previous French studies as well as those from other countries. The estimated mean daily intakes were 11 microgram for lithium, 3.42 g for sodium, 192 mg for magnesium, 2.03 mg for aluminium, 3.64 g for potassium, 642 mg for calcium, 154 microgram for chromium, 12.3 mg for iron, 2.15 mg for manganese, 4 microgram for cobalt, 74 microgram for nickel, 925 microgram for copper, 10.2 mg for zinc, 147 microgram for arsenic, 66 microgram for selenium, 112 microgram for molybdenum, 3.6 microgram for cadmium, 2.32 mg for tin, 3 microgram for antimony, 9 microgram for mercury and 34 microgram for lead. For the non-essential (toxic) elements, aluminium, tin, antimony, cadmium, arsenic, mercury and lead, the daily intake estimates were far below tolerable limits; and similar or somewhat lower than their respective PTWI, ADI, TDI, ESADDI and US RDA for individual minerals and essential trace elements, with good agreement with other country studies. The performance of the multi-elemental ICP-MS technique was also evaluated.

The organic composition of surface water (a canal network fed by the Rhône river, France) was studied over a period of 3 years. The spatial and temporal evolution of extractable organic compounds was determined by monitoring the water of the principal canal (72 km long) over 3 years and 139 compounds were detected at the ng/l concentration level. Using these data the organic fingerprints were constructed for every sampling point. These fingerprints depend on sampling dates and climatic conditions. Analysed compounds were classified according to two criteria: appearance frequency and average concentrations. Three classes were defined, corresponding to: organic background, occasional component and chronic component. The preponderance of organic background, corresponding to the natural organic fingerprint, indicates the high quality of this surface water. The proportion of some chemical families were calculated in order to assess their anthropogenic impact on the water. This study produced a databank which was useful as a reference for the monitoring and checking of water quality. Any anomaly disturbing organic fingerprints can thus rapidly be detected and identified by comparison with the databank, making better crisis management possible.