Éditeur(s) : HAL CCSD BioMed Central
Résumé : International audience
UNLABELLED: ABSTRACT: BACKGROUND: Genomics, transcriptomics and proteomics of glioblastoma multiforme (GBM) have recently emerged as possible tools to discover therapeutic targets and biomarkers for new therapies including immunotherapy. It is well known that macroscopically complete surgical excision, radiotherapy and chemotherapy have therapeutic limitations to improve survival in these patients. In this study, we used a differential proteomic-based technique (2D-Difference Gel Electrophoresis) coupled with matrix-assisted laser desorption/ionization-time of flight (MALDI-TOF) mass spectrometry to identify proteins that may serve as brain tumor antigens in new therapeutic assays. Five samples of patients presenting a GBM and five samples of microscopically normal brain tissues derived from brain epileptic surgery specimen were labeled and run in 2D-PAGE (Two-Dimensional Polyacrylamide Gel Electrophoresis) with an internal pool sample on each gel. Five gels were matched and compared with DIA (Difference In-gel Analysis) software. Differential spots were picked, in-gel digested and peptide mass fingerprints were obtained. RESULTS: From 51 protein-spots significantly up-regulated in GBM samples, mass spectrometry (MS) identified twenty-two proteins. The differential expression of a selected protein set was first validated by western-blotting, then tested on large cohorts of GBM specimens and non-tumor tissues, using immunohistochemistry and real-time RT-PCR. CONCLUSIONS: Our results confirmed the importance of previously described proteins in glioma pathology and their potential usefulness as biological markers but also revealed some new interesting targets for future therapies.
ISSN: 1477-5956

inserm-00585020
http://www.hal.inserm.fr/inserm-00585020
http://www.hal.inserm.fr/inserm-00585020/document
http://www.hal.inserm.fr/inserm-00585020/file/1477-5956-9-16.pdf
DOI : 10.1186/1477-5956-9-16

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
The 90-kDa heat shock protein (Hsp90) is a highly flexible dimer able to self-associate in the presence of divalent cations or under heat shock. This study investigated the relationship between Hsp90 oligomers and the Hsp90 cochaperone Aha1 (activator of Hsp90 ATPase). The interactions of Aha1 with Hsp90 dimers and oligomers were evaluated by ultracentrifugation, size-exclusion chromatography coupled to multiangle laser light scattering and high-mass matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Hsp90 dimer was able to bind up to four Aha1 molecules, and Hsp90 oligomers are also able to interact with Aha1. The binding of Aha1 did not interfere with the Hsp90 oligomerization process. Except for Hsp90 dimer, the stoichiometry of the interaction remained constant, at 2 Aha1 molecules per Hsp90 dimer, regardless of the degree of Hsp90 oligomerization. Moreover, Aha1 predominantly bound to Hsp90 oligomers. Thus, the ability of Hsp90 oligomers to bind the Aha1 ATPase activator reinforces their role within the Hsp90 chaperone machineries
ISSN: 0003-2700

hal-01175535
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01175535
DOI : 10.1021/acs.analchem.5b00051
PUBMED : 26076190

Éditeur(s) : HAL CCSD
Résumé : The spectrin-based skeleton is an essential scaffold underlying different lipid bilayers in all animal cells. Spectrins (Sp), as giant extended flexible heterotetramers (αβ)2, constitute the filaments of this network, the nodes of which are cross-linked by actin filaments. The functions of the Sp-based skeleton, which are well defined in red blood cells (required for shape, resistance to shear stress and deformability) are less well understood in non-erythroid cells.The non-erythroid Sp might participate in the establishment and/or the maintenance of specialized membrane subdomains by accumulating integral membrane proteins (such as ionic channels, ionic pumps, receptors and cell adhesion molecules) as revealed by loss of the main non-erythroid β-Sp. However the effect of non-erythroid α-Sp are less well established. In mammals, α-Sp are encoded by two genes: one for αI-Sp mainly expressed in mature erythrocyte, the second one for αII-Sp which is expressed in all nucleated cells.In the pursuit of αII-Sp functions, we have checked the effect of αII-Sp knock down by siRNA melanoma human cell line. Our data revealed that spectrin depletion is associated with i) an arrest of cell cycle at G1 state ii) a loss of cell adhesion in spite of increase in some integrins iii) some modifications of actin organisation.
Le squelette dépendant de la spectrine, localisé sous la bicouche lipidique, est un échafaudage essentiel de toutes les cellules animales. La Spectrine (Sp), structure géante, robuste mais flexible d'hétéro tétramères (αβ)2, constitue les filaments de ce réseau, dont chaque nœud interagit avec des filaments d'actine. Les fonctions du squelette de Sp, qui sont bien définies dans le globule rouge (rôle dans sa forme, dans sa résistance aux forces de cisaillement et dans sa déformabilité) sont moins bien connues dans les cellules non-érythroïdes. La Sp non-érythroïde pourrait participer à l'établissement et/ou au maintien de sous-domaines membranaires spécialisés dans l'accumulation de protéines de membrane (telles que les canaux ioniques, les pompes ioniques, les récepteurs et les molécules d'adhérence) comme nous le font penser les invalidations de la Sp-β non-érythroïde. Cependant le rôle de la Sp-α non-érythroïde est moins bien établi. Chez les mammifères, la Sp-α est codée par deux gènes: un pour Sp-αI, principalement exprimée dans l'érythrocyte mature, le second pour Sp-αII qui est exprimée dans toutes les cellules nucléées. Pour étudier les fonctions de la Sp-αII, nous avons utilisé une approche de SiRNA sur des cellules de mélanome humain. Nos données montrent que la diminution de Sp-αII est associée à I) un arrêt en G1 du cycle cellulaire II) une perte d'adhérence des cellules malgré l'augmentation de quelques intégrines III) des modifications dans l'organisation du réseau d'actine.
https://tel.archives-ouvertes.fr/tel-00377569

Droits : info:eu-repo/semantics/OpenAccess
tel-00377569
https://tel.archives-ouvertes.fr/tel-00377569
https://tel.archives-ouvertes.fr/tel-00377569/document
https://tel.archives-ouvertes.fr/tel-00377569/file/these_210409_entiere.pdf
https://tel.archives-ouvertes.fr/tel-00377569/file/II-Spectrin_Is_Critical_for_Cell_Adhesion_and_Cell_Cycle.PDF

Éditeur(s) : HAL CCSD Society for the Study of Reproduction
Résumé : International audience
Matrix-assisted laser desorption/ionization (MALDI) tissue imaging mass spectrometry is particularly promising among the numerous applications of mass spectrometry. It is used for probing and analyzing the spatial arrangement of a wide range of molecules, including proteins, peptides, lipids, drugs, and metabolites, directly in thin slices of tissue. In the field of proteomics, the technology avoids tedious and time-consuming extraction and fractionation steps classically required for sample analysis. MALDI imaging mass spectrometry is increasingly recognized as a powerful method for clinical proteomics, particularly in cancer research. The technology has particular potential for the discovery of new tissue biomarker candidates, classification of tumors, early diagnosis or prognosis, elucidating pathogenesis pathways, and therapy monitoring. Over recent years, MALDI imaging mass spectrometry has been used for molecular profiling and imaging directly in male and female reproductive tissues. This review will consider some of the recent publications in the field, addressing a range of issues covering embryo development, gene expression product profiling during gametogenesis, and seeking and identifying biomarkers of reproductive cancers. The wealth of advances in mass spectrometry imaging will inevitably attract biologists and clinicians as the advantages and power of this technology become more widely known. This review will also discuss bottlenecks and the many technical issues that remain to be resolved before laboratories in the field can adopt the technology. We foresee that MALDI imaging mass spectrometry will have a major impact in reproductive research by opening new avenues to the understanding of various molecular mechanisms and the diagnosis of reproductive pathologies.
ISSN: 0006-3363

hal-00877851
https://hal.archives-ouvertes.fr/hal-00877851
DOI : 10.1095/biolreprod.111.094896
PUBMED : 22156474

Éditeur(s) : HAL CCSD
Résumé : International audience
Abstract View references (38)This work presents a facile, scalable method for the fabrication of graphene oxide-iron oxide (GO-Fe3O4) nanocomposites produced by co-precipitation of iron ions onto the GO surfaces in basic aqueous media. FTIR and XRD characterisation suggests that Fe3O4 was chemically anchored to the GO sheets, possibly via the carboxyl and hydroxyl groups. Small GO loadings of 0.5 and 1 wt% were not sufficient to alter the Fe3O4 structures. However, increasing the GO loading to 5 and 10 wt% resulted in significant loss in pore volume, thus suggesting the lamellar GO sheets decorated with Fe3O4 were assembling into GO-Fe3O4 nanocomposite stacks. It was found that the GO-Fe3O4 nanocomposites had an enhanced catalytic activity in the heterogeneous Fenton-like oxidation of Acid Orange 7 (AO7) compared to pure GO flat sheets and Fe3O4 nanoparticles. Interestingly, the GO-Fe3O4 nanocomposite with 5 wt% loading ratio exhibited the best catalytic activity with 76% degradation of AO7 dye observed within 90 min of reaction. This was attributed to the synergistic effect of GO by enriching the adsorbed AO7 molecules onto the nanocomposite to be further oxidised in the vicinities of active sites. This finding suggests the promising employment of GO-Fe3O4 nanocomposites in removing organic dyes from polluted water by heterogeneous Fenton-like reaction. © 2014 by American Scientific Publishers.
SCIENCE OF ADVANCED MATERIALS

hal-01683207
https://hal.univ-antilles.fr/hal-01683207
DOI : 10.1166/sam.2014.1812

Éditeur(s) : HAL CCSD Institute of Electrical and Electronics Engineers (IEEE) Institute of Electrical and Electronics Engineers
Résumé : International audience
Conventional quantitative electron probe microanalysis of actinides requires the use of reference standard samples. However, for such elements, standards are generally not available. To overcome this difficulty, standardless methods of analysis are used, in which the x-ray intensity emitted by the standard is calculated. To be reliable, such calculations require accurate knowledge of physical data such as the x-ray production cross section. However, experimental data of this quantity are not always available for actinide elements. In the present work, experimental L and M x-ray production cross sections were measured for elements uranium and lead. Measurements were performed with two electron microprobes using wavelength-dispersive spectrometers using thin self-supporting targets. Experimental results are compared with calculated cross sections obtained from different analytical formulae, and, whenever possible, with experimental data obtained from the literature.
ISSN: 0018-9499

hal-01122820
https://hal.archives-ouvertes.fr/hal-01122820
DOI : 10.1109/TNS.2014.2321016

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
2-Amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (PhIP), a carcinogenic heterocyclic aromatic amine formed in cooked meats, is metabolically activated to electrophilic intermediates that form covalent adducts with DNA and protein. We previously identified an adduct of PhIP formed at the Cys34 residue of human serum albumin following reaction of albumin with the genotoxic metabolite 2-hydroxyamino-1-methyl-6-phenylimidazo[4,5-b]pyridine (HONH-PhIP). The major adducted peptide recovered from a tryptic/chymotryptic digest was identified as the missed-cleavage peptide LQQC*[SO2PhIP]PFEDHVK, a [cysteine-S-yl-PhIP]-S-dioxide linked adduct. In this investigation, we have characterized the albumin adduction products of N-sulfooxy-2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (N-sulfooxy-PhIP), which is thought to be a major genotoxic metabolite of PhIP formed in vivo. Targeted and data-dependent scanning methods showed that N-sulfooxy-PhIP adducted to the Cys34 of albumin in human plasma to form LQQC*[SO2PhIP]PFEDHVK at levels that were 8-10-fold greater than the adduct levels formed with N-(acetyloxy)-2-amino-1-methyl-6-phenylimidazo[4,5-b]pyridine (N-acetoxy-PhIP) or HONH-PhIP. We also discovered that N-sulfooxy-PhIP forms an adduct at the sole tryptophan (Trp214) residue of albumin in the sequence AW*[PhIP]AVAR. However, stable adducts of PhIP with albumin were not detected in human hepatocytes. Instead, PhIP and 2-amino-1-methyl-6-(5-hydroxy)phenylimidazo[4,5-b]pyridine (5-HO-PhIP), a solvolysis product of the proposed nitrenium ion of PhIP, were recovered during the proteolysis, suggesting a labile sulfenamide linkage had formed between an N-oxidized intermediate of PhIP and Cys34 of albumin. A stable adduct was formed at the Tyr411 residue of albumin in hepatocytes and identified as a deaminated product of PhIP, Y*[desaminoPhIP]TK, where the 4-HO-tyrosine group bound to the C-2 imidazole atom of PhIP.
ISSN: 0893-228X

hal-01146777
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01146777
DOI : 10.1021/acs.chemrestox.5b00075
PUBMED : 25815793

Éditeur(s) : HAL CCSD
Résumé : International audience
This study assessed the inhaled dose of alcohol during hand disinfection. Experiments were conducted with two types of hand rub using two hand disinfection procedures. Air samples were collected every 10 s from the breathing zone, by bubbling through a mixture of K2Cr2O7 and H2SO4. The reduction of dichromate ions in the presence of alcohols was followed by UV-vis spectrophotometry. The difference in intensity of the dichromate absorption peak was used to quantify the alcohol concentration expressed in ethanol equivalent. During hygienic hand disinfection, the mean ethanol equivalent concentrations peaked at around 20-30 s for both hand rubs (14.3 ± 1.4 mg/L for hand rub 1 and 13.2 ± 0.7 mg/L for hand rub 2). During surgical hand disinfection, two peaks were found at the same time (40 and 80 s) for both hand rubs. The highest mean concentrations were 20.2 ± 0.9 mg/L for hand rub 1 and 18.1 ± 0.9 mg/L for hand rub 2. For hand rub 1, the total absorbed doses, calculated from ethanol with an inhalation flow of 24 L/min and an absorption rate of 62%, were 46.5 mg after one hygienic hand disinfection and 203.9 mg after one surgical hand disinfection. Although the use of ABHRs leads to the absorption of very low doses, sudden, repeated inhalation of high alcohol concentrations raises the question of possible adverse health effects.
International Journal of Environmental Research and Public Health

hal-00878450
https://hal.archives-ouvertes.fr/hal-00878450
https://hal.archives-ouvertes.fr/hal-00878450/document
DOI : 10.3390/ijerph9030868

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
Chlordecone is an organochlorine pesticide that was extensively used in the French West Indies to fight weevils in banana plantations from 1973 to 1993. This has led to a persistent pollution of the environment and to the contamination of the local population for several decades with effects demonstrated on human health. Chlordecone accumulates mainly in the liver where it is known to potentiate the action of hepatotoxic agents. However, there is currently no information on its in situ localization in the liver. We have thus evaluated a matrix-assisted laser desorption ionization (MALDI) imaging quantification method based on labeled normalization for the in situ localization and quantification of chlordecone. After validating the linearity and the reproducibility of this method, quantitative MALDI imaging was used to study the accumulation of chlordecone in the mouse liver. Our results revealed that normalized intensities measured by MALDI imaging could be first converted in quantitative units. These quantities appeared to be different from absolute quantities of chlordecone determined by gas chromatography (GC), but they were perfectly correlated (R(2) = 0.995). The equation of the corresponding correlation curve was thus efficiently used to convert quantities measured by MALDI imaging into absolute quantities. Our method combining labeled normalization and calibration with an orthogonal technique allowed the in situ absolute quantification of chlordecone by MALDI imaging. Finally, our results obtained on the pathological mouse liver illustrate the advantages of quantitative MALDI imaging which preserves information on in situ localization without radioactive labeling and with a simple sample preparation.
ISSN: 0003-2700

hal-01118103
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01118103
PUBMED : 24837422
DOI : 10.1021/ac500313s

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
Abstract The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.
ISSN: 2045-2322

hal-01683204
https://hal.univ-antilles.fr/hal-01683204
DOI : 10.1038/srep02449

Éditeur(s) : HAL CCSD
Résumé : International audience
MOTIVATION: Imaging mass spectrometry (IMS) is a maturating technique of molecular imaging. Confidence in the reproducible quality of IMS data is essential for its integration into routine use. However, the predominant method for assessing quality is visual examination, a time consuming, unstandardized and non-scalable approach. So far, the problem of assessing the quality has only been marginally addressed and existing measures do not account for the spatial information of IMS data. Importantly, no approach exists for unbiased evaluation of potential quality measures. RESULTS: We propose a novel approach for evaluating potential measures by creating a gold-standard set using collective expert judgements upon which we evaluated image-based measures. To produce a gold standard, we engaged 80 IMS experts, each to rate the relative quality between 52 pairs of ion images from MALDI-TOF IMS datasets of rat brain coronal sections. Experts' optional feedback on their expertise, the task and the survey showed that (i) they had diverse backgrounds and sufficient expertise, (ii) the task was properly understood, and (iii) the survey was comprehensible. A moderate inter-rater agreement was achieved with Krippendorff's alpha of 0.5. A gold-standard set of 634 pairs of images with accompanying ratings was constructed and showed a high agreement of 0.85. Eight families of potential measures with a range of parameters and statistical descriptors, giving 143 in total, were evaluated. Both signal-to-noise and spatial chaos-based measures performed highly with a correlation of 0.7 to 0.9 with the gold standard ratings. Moreover, we showed that a composite measure with the linear coefficients (trained on the gold standard with regularized least squares optimization and lasso) showed a strong linear correlation of 0.94 and an accuracy of 0.98 in predicting which image in a pair was of higher quality. AVAILABILITY AND IMPLEMENTATION: The anonymized data collected from the survey and the Matlab source code for data processing can be found at: https://github.com/alexandrovteam/IMS_quality. CONTACT: theodore.alexandrov@embl.de
Bioinformatics (Oxford, England)

hal-01163754
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01163754
DOI : 10.1093/bioinformatics/btv266
PUBMED : 26072506

Éditeur(s) : HAL CCSD
Résumé : International audience
Millimeter waves (MMW) will be increasingly used for future wireless telecommunications. Previous studies on skin keratinocytes showed that MMW could impact the mRNA expression of Transient Receptor Potential cation channel subfamily Vanilloid, member 2 (TRPV2). Here, we investigated the effect of MMW exposure on this marker, as well as on other membrane receptors such as Transient Receptor Potential cation channel subfamily Vanilloid, member 1 (TRPV1) and purinergic receptor P2X, ligand-gated ion channel, 3 (P2 × 3). We exposed the Neuroscreen-1 cell line (a PC12 subclone), in order to evaluate if acute MMW exposures could impact expression of these membrane receptors at the protein level. Proteotoxic stress-related chaperone protein Heat Shock Protein 70 (HSP70) expression level was also assessed. We used an original high-content screening approach, based on fluorescence microscopy, to allow cell-by-cell analysis and to detect any cell sub-population responding to exposure. Immunocytochemistry was done after 24 h MMW exposure of cells at 60.4 GHz, with an incident power density of 10 mW/cm2. Our results showed no impact of MMW exposure on protein expressions of HSP70, TRPV1, TRPV2, and P2 × 3. Moreover, no specific cell sub-populations were found to express one of the studied markers at a different level, compared to the rest of the cell populations. However, a slight insignificant increase in HSP70 expression and an increase in protein expression variability within cell population were observed in exposed cells, but controls showed that this was related to thermal effect. Bioelectromagnetics. 37:444–454, 2016. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.
Bioelectromagnetics

hal-01371963
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01371963
DOI : 10.1002/bem.21995
PUBMED : 27483046

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Thermal acclimation drastically alters thermotolerance of ectotherms, but the mechanisms determining this plastic response are not fully understood. The present study investigates the proteomic response (2D-DIGE) of adult Drosophila melanogaster acclimated at 11, 25 or 31 C. As expected 11 C-acclimation improved cold tolerance and 31 C-acclimation improved heat tolerance. We hypothesized that the marked organismal responses to acclimation could be detected at the proteomic level assuming that changes in the abundance of specific proteins are linked to the physiological changes underlying the phenotypic response. The 31 C-acclimated flies displayed a particular divergent proteomic profile where molecular chaperones made up a large number of the proteins that were modulated during heat acclimation. Many other proteins showed significant modulation during acclimation including proteins involved in iron ion and cell redox homeostasis, carbohydrate and energy metabolism, chromatin remodeling and translation, and contractile machinery. Interestingly the changes in protein abundance were often unrelated to transcriptional activity of the genes coding for the proteins, except for the most strongly expressed proteins (e.g. Hsp70). The 11 C-acclimation evoked weak proteomic response despite the marked effect on the organismal phenotype. Thus the acquired cold tolerance observed here may involve regulatory process such as posttranslational regulation rather than de novo protein synthesis.
ISSN: 0965-1748

hal-00826939
https://hal.archives-ouvertes.fr/hal-00826939
DOI : 10.1016/j.ibmb.2013.01.006
PUBMED : 23416132

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : International audience
Despite a relatively 'uniform' fertile composition (Al2O3 = 2 center dot 19-4 center dot 47 wt %; Fo% = 89 center dot 2 +/- 0 center dot 3%; Cr#(Spl) = 8 center dot 9 +/- 1 center dot 5%), the Montferrier peridotite xenoliths show a wide range of S contents (22-590 ppm). Most sulphides are interstitial and show peculiar pyrrhotite-pentlandite intergrowths and low abundances of Cu-rich phases. Sulphide-rich samples are characterized by strong enrichment in the light rare earth elements and large ion lithophile elements without concomitant enrichment of the high field strength elements. Such trace-element fractionation is commonly ascribed to metasomatism by volatile-rich melts and/or carbonatitic melts. S and Se (11-67 ppb), as well as S/Se (up to approximate to 12 000), are correlated with La/Sm. Cu, however, remains broadly constant (30 +/- 5 ppm). These features strongly suggest that the percolation-reaction of such volatile-rich fluids has led to sulphide enrichment with an atypical signature marked by strong fractionation of the chalcophile elements (i.e. S vs Se and Cu). S-rich xenoliths are also characterized by high (Pd/Ir)(N) (1 center dot 2-1 center dot 9; where subscript N indicates normalized to chondrite), (Pd/Pt)(N) between 1 center dot 5 and 2 center dot 2, and (Os/Ir)(N) up to 1 center dot 85. Despite the relative uniform fertile composition of the xenoliths, Re/Os ranges between 0 center dot 02 and 0 center dot 18. Os-187/Os-188 is extremely variable even within a single sample and can be as high as 0 center dot 1756 for the most S-rich samples. Sulphides show highly fractionated and variable abundances of the highly siderophile elements (HSE) [0 center dot 03 (Pd/Ir)(N) < 1283] and Re-Os isotopic composition (0 center dot 115 < Os-187/Os-188 < 0 center dot 172). Such variation can be observed at the thin-section scale. Whole-rock and in situ sulphide data demonstrate that chalcophile and HSE systematics and the Os isotopic composition of the upper mantle could be significantly modified through metasomatism, even with volatile-rich fluids. These features highlight the complex behaviour of the HSE in fluid-rock percolation-reaction models and suggest a complex interplay between sulphide addition (crystallization or sulphidation) and partial equilibration of pre-existing sulphide. The specific fractionations observed in chemical proxies such as S and Se, Os and Ir, and Pd and Pt, as well as the low abundance of Cu-rich sulphides, suggest that sulphide addition may not have occurred via sulphide melts. Rather, we infer that S was present as a dissolved species in a (supercritical) oxidizing, volatile-rich fluid (C-O-H-S +/- Cl) along with other chalcophile and siderophile elements such as Os, Pd, Re and Au. The highly radiogenic Os composition of this fluid ( Os-187/ Os-188 > 0 center dot 17) would imply that such fluids are derived from an uncommon type of mantle source possibly related to carbonatite melts.
ISSN: 0022-3530

hal-00644524
https://hal.archives-ouvertes.fr/hal-00644524
DOI : 10.1093/petrology/egr038

Résumé : Les forêts côtières inondables (FCI) des régions tropicales et subtropicales remplissent des fonctions écologiques nécessaires aux écosystèmes marins côtiers situés en aval et aux populations humaines vivant à proximité Aux Antilles, les mangroves et les forêts marécageuses à Pterocarpus officinalis sont structurés par des espèces ligneuses qui ont développé des adaptations particulières à la salinité, à l’inondation et aux substrats meubles sur lesquels elles reposent. Dans des contextes climatiques à forte saisonnalité, les saisons sèches prolongées entraînent de fortes variations de la salinité et du niveau de la nappe, que le changement climatique devrait amplifier. Les modèles climatiques de la région Caraïbe prévoient des saisons sèches plus sèches liées à une baisse des précipitations de 20 à 50 %. Or, la question des capacités de résistance et d’acclimatation des espèces ligneuses des FCI à des variations saisonnières marquées de leur environnement édaphique a été peu traitée dans la littérature scientifique.L’objectif de ce travail de thèse a été double. Il s’est agi, d'une part, de caractériser la structure et la croissance de faciès de végétation représentatifs des FCI antillaises et de mettre en évidence leurs déterminants. A cet effet, des individus adultes, des espèces ligneuses dominantes des FCI, (Avicennia germinans, Laguncularia racemosa, Pterocarpus officinalis, Rhizophora mangle), dans cinq faciès de végétation sur le gradient terre-mer, ont été suivis sur l'île de Grande-Terre (Guadeloupe). D’autre part, les effets de variations salines extrêmes sur la croissance et l’écophysiologie de ces quatre espèces ont été évalués au stade plantule par une expérience en conditions contrôlées.A travers cette étude, il a été montré que les différences de salinité et de fertilité entre les stationspermettent d’expliquer la composition et la structure des peuplements de FCI. Cette étude a égalementmontré que P. officinalis peut se maintenir dans une gamme de salinité plus large que ne l'indiquait lalittérature.Dans le contexte des Antilles où les marnages sont faibles, la saisonnalité du climat entraine des variations saisonnières importantes d’un ensemble de descripteurs édaphiques tels que le niveau de la nappe, la salinité du sol, le pH et le potentiel RedOx. L’inondation et la salinité des sols sont fortement corrélées aux variations mensuelles des précipitations. Les périodes sèches sont accompagnées de salinités élevées et d’une baisse du niveau de la nappe allant jusqu’à l’exondation des sols dans toutes les stations suivies. Les stress environnementaux liés à la saisonnalité entrainent une baisse de la production primaire. L’accroissement cambial mensuel des individus est fortement corrélé avec les précipitations et l’intensité du vent. Dans les stations de mangrove, la sècheresse édaphique régule la production primaire des palétuviers. En forêt marécageuse, la part de la sècheresse atmosphérique semble plus importante pour expliquer la production de P. officinalis. Aussi, les sècheresses édaphique et atmosphérique doivent être prises en compte toutes deux pour modéliser efficacement la croissance des peuplements des FCI.Lors de la saison sèche, le stress le plus important est le stress hydrique, lié à la diminution de la teneur en eau du sol et à l’augmentation de la salinité, qui entraine des contraintes physiologiques sur les palétuviers (ajustements stomatiques, pertes de surface foliaire et de conductivité hydraulique). Le stress ionique, lié à la toxicité des ions Na+ et Cl-, permet aussi d’expliquer une partie de la contrainte sur l’assimilation en carbone. En saison sèche, l’aération des sols ne se traduit pas par une amélioration des performances de croissance chez toutes les espèces. Aussi, la croissance cambiale maximale de toutes les espèces de FCI est réalisée en saison des pluies lorsque la salinité est faible et les niveaux d’inondation élevés.
In tropical and subtropical regions, flooded coastal forests provide essentials goods and services to local communities. In the Antilles, mangrove forests and the Pterocarpus officinalis swamp forest host tree species that are adapted to salinity, flooding and loose substrates. In areas were climatic seasonality is strong, dry seasons lead to strong fluctuations of soil salinity and water table level ; that climate change is likely to make stronger again. Climate model for the Caribbean project drier dry seasons with a decease of 20 to 50 % in annual rainfall amounts. However, resistance and acclimation ability of flooded coastal forest’s species to strong environmental fluctuations still remain poorly studied.This thesis aims two objectives. On the one hand, it aims to characterize the forest structure and monthly growth of vegetation structures representative of the Antillean flooded coastal forests and to highlight their determinants. In this respect, adult trees of the four dominant species of local flooded coastal forest (Avicennia germinans, Laguncularia racemosa, Pterocarpus officinalis, Rhizophora mangle), in five stations along a sea – land gradient were monitored on the Grande-Terre island (Guadeloupe). On the other hand, the effects of salinity variation patterns and salinity levels on growth performances and physiology of seedlings from the four same species were investigated through a greenhouse experiment.This study shows that differences among average salinity and soil fertility explain the vegetation structure of flooded coastal forest. It also extents, in the literature, the range of salinity in which P. officinalis can stand at the tree stage.In the Antilles were tidal range is small, climate seasonality lead to strong edaphic seasonal variations in water table level, soil salinity, pH and RedOx potential. Flooding and soil salinity are strongly correlated to monthly rainfall amounts: dry periods lead to high salinity and to a decrease in water table level under the soil surface. Seasonal environmental stresses lead to a decrease of primary production. Cambial growth was strongly correlated to monthly precipitation and average wind speed. In mangrove stations, edaphic drought determines primary production of mangrove trees, when, in swamp forest stations, atmospheric drought determines an important part of P. officinalis’ primary production.During the dry season, water stress is the more important environmental stress, both by the decrease in soil humidity and the increase in soil salinity, and leads to physiological strains (stomatal adjustment, loss of leaf area and hydraulic conductivity) for mangrove trees. Ionic toxicity of ions Na+ and Cl- also explains a part of the strain on carbon assimilation. During the dry season, re oxygenation of soils via low water table level does not lead to an increase of physiological traits. Thus, maximum cambial growth of all species is observed during the rainy season, when salinity is low and water table level is high.Flooded coastal forest’s species do not have the same ability to recover after a dry episode. In all the studied stations, A. germinans’ cambial growth rises back as soon as the rainy season starts, when, for one station, cambial growth of L. racemosa and R. mangle stay null during the three first month of the rainy season. This low ability to recover after a dry episode is correlated to a stronger impact of the dry season on the physiological traits of these two species.The greenhouse experiment shows that salinity variation patterns are to be taken into consideration for explaining seedlings’ growth and salinity tolerance. A stronger salinity increase impacts the growth of all the studied species; a punctual drop of salinity highlights that flooded coastal forest’s species differ in ability to take advantage of a low salinity episode. These results are coherent with field observations as cambial growth was fairly explained by monthly precipitation.

http://www.theses.fr/2013AGUY0674/document

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The behaviour of the four Ra isotopes (measured by gamma spectrometry) and 222Rn (measured with an AlphaGUARD ionisation chamber) has been investigated in NaCl-rich thermal waters of Balaruc-les-Bains on the Mediterranean coast (South of France). This study allows identification of the deep thermal water signature and reveals the influence of seawater or karst water inflows on Ra isotopes and 222Rn. The deep thermal water has 226Ra and 222Rn activities of 840 and 1900 mBq/l, respectively, a (228Ra/226Ra) activity ratio of 0.59, and low (224Ra/228Ra) and (223Ra/226Ra) ratios of 0.67 and 0.025, respectively. Several arguments suggest a dominant role of radioactive decay for short-lived Ra isotopes and Rn during the relatively rapid ascent of thermal water through wide open fractures and drains. The low (223Ra/226Ra) ratio constrains the maximum ascent velocity of thermal water to 8-10 m/h. Seawater inflow into the hydrothermal system results in an enrichment in short-lived Ra isotopes and 222Rn. The high (223Ra/226Ra) ratio (0.23) suggests that 223Ra, 224Ra and 222Rn produced by alpha-recoil in the upper-Jurassic limestone are entrained by seawater percolation through the coastal basement, due to active pumping in one of the near shore production well. This process would be enhanced by a low water/rock ratio (i.e. in a low-porosity, micro-fractured limestone). Mixing of this enriched seawater with thermal water induces barite precipitation with co-precipitation of a large fraction of Ra. Short-lived Ra isotopes may thus be useful tracers of seawater flux towards the continent. Conversely, the inflow and mixing of karst groundwater result in a general dilution of all dissolved elements, only a small enrichment in 224Ra and 223Ra, but a large enrichment in 222Rn (up to 26 Bq/l). The combination of Ra isotopes and 222Rn data provides a good way to trace the dynamics of different water masses along coastal areas.
ISSN: 0016-7037

hal-00795512
https://hal.archives-ouvertes.fr/hal-00795512
DOI : 10.1016/j.gca.2012.09.010

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Melting experiments were performed on a silica-rich peridotite composition at 10-17 GPa to determine majoritic garnet-melt partition coefficients (D) for major and trace elements. Our results show that D for many elements, including Na, Sc, Y and rare earth elements (REE), varies significantly with increasing pressure or proportion of majorite component. Lu and Sc become incompatible at 17 GPa, with D decreasing from 1.5 at 10 GPa to 0.9 at 17 GPa. As predicted from lattice strain, log D for isovalent cations entering the large site of majoritic garnet exhibits a near-parabolic dependence on ionic radius. Our data are used to refine a previously published predictive model for garnet-melt partitioning of trivalent cations, which suffered from a lack of calibration in the 10-20 GPa range. Our results suggest that Archean Al-depleted komatiites from Barberton (South Africa) may have been generated by partial melting of dry peridotite at depths between 200 and 400 km. We also speculate that transition zone diamonds from Kankan (Guinea), which contain inclusions of majoritic garnet, may have formed from the partial reduction of CO2-rich magmas that subsequently transported them to the surface. This hypothesis would provide an explanation for the REE patterns of majoritic garnet trapped within these diamonds, including Eu anomalies. Finally, we show that segregation of majoritic garnet-bearing cumulates during crystallisation of a deep Martian magma ocean could lead to a variety of Lu/Hf and Sm/Nd ratios depending on pressure, leading to a range of ε143Nd and ε176Hf isotope signatures for potential mantle sources of Martian rocks.
ISSN: 0024-4937

hal-00767567
https://hal.archives-ouvertes.fr/hal-00767567
DOI : 10.1016/j.lithos.2012.06.013

Éditeur(s) : HAL CCSD American Society for Biochemistry and Molecular Biology
Résumé : International audience
2-Amino-9H-pyrido[2,3-b]indole (AαC) is a carcinogenic heterocyclic aromatic amine formed during the combustion of tobacco. AαC undergoes bioactivation to form electrophilic N-oxidized metabolites that react with DNA to form adducts, which can lead to mutations. Many genotoxicants and toxic electrophiles react with human serum albumin (albumin); however, the chemistry of reactivity of AαC with proteins has not been studied. The genotoxic metabolites, 2-hydroxyamino-9H-pyrido[2,3-b]indole (HONH-AαC), 2-nitroso-9H-pyrido[2,3-b]indole (NO-AαC), N-acetyloxy-2-amino-9H-pyrido[2,3-b]indole (N-acetoxy-AαC), and their [(13)C6]AαC-labeled homologues were reacted with albumin. Sites of adduction of AαC to albumin were identified by data-dependent scanning and targeted bottom-up proteomics approaches employing ion trap and Orbitrap MS. AαC-albumin adducts were formed at Cys(34), Tyr(140), and Tyr(150) residues when albumin was reacted with HONH-AαC or NO-AαC. Sulfenamide, sulfinamide, and sulfonamide adduct formation occurred at Cys(34) (AαC-Cys(34)). N-Acetoxy-AαC also formed an adduct at Tyr(332). Albumin-AαC adducts were characterized in human plasma treated with N-oxidized metabolites of AαC and human hepatocytes exposed to AαC. High levels of N-(deoxyguanosin-8-yl)-AαC (dG-C8-AαC) DNA adducts were formed in hepatocytes. The Cys(34) was the sole amino acid of albumin to form adducts with AαC. Albumin also served as an antioxidant and scavenged reactive oxygen species generated by metabolites of AαC in hepatocytes; there was a strong decrease in reduced Cys(34), whereas the levels of Cys(34) sulfinic acid (Cys-SO2H), Cys(34)-sulfonic acid (Cys-SO3H), and Met(329) sulfoxide were greatly increased. Cys(34) adduction products and Cys-SO2H, Cys-SO3H, and Met(329) sulfoxide may be potential biomarkers to assess exposure and oxidative stress associated with AαC and other arylamine toxicants present in tobacco smoke
ISSN: 0021-9258

hal-01169796
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01169796
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01169796/file/Manuscript_KP_JBC_REV_050515_final_TC.pdf
DOI : 10.1074/jbc.M115.646539
PUBMED : 25953894

Éditeur(s) : HAL CCSD Elsevier
Résumé : Nominally anhydrous minerals (NAMs) of Earth's mantle can contain hydrogen as atomic impurity in their crystal structures. This hydrogen substantially modifies many physical properties of Earth's mantle rocks. Also, the Earth's deep interior is made of rocks where minerals are separated by nanometer-scale interfaces call grain boundaries and interphase boundaries. These grain boundaries should carefully be considered as a potential hydrogen reservoir as well. I report here an experimental investigation of hydrogen diffusion through grain boundaries in olivine polycrystalline aggregates. Hot-press and diffusion experiments were performed using a gas-medium high-pressure vessel at a confining pressure of 300 MPa, over a temperature range of 1000-1200 degrees C. The diffusion assembly consisted of a dense polycrystalline cylinder of natural olivine from San Carlos (Arizona) mixed with olivine singles crystals of millimeter size. This mixture was couple with a talc cylinder. Ni capsule were used to buffer the oxygen fugacity at Ni-NiO level. Experiment durations varied from 3 min to 4 h. The presence of hydrogen in the sample was quantified using Fourier transform infrared spectroscopy. The calculation of the diffusion coefficients was based on the estimation of the length of polycrystalline solid affected by the diffusion of hydrogen. The absence or presence of hydrogen was recorded by the large olivines behaving here as "hydrogen sensor", which are implanted in the aggregate. The results indicate that effective hydrogen diffusivity which includes grain boundaries effect in olivine aggregate is barely one order of magnitude faster than hydrogen diffusion in an olivine single crystal with a diffusivity similar to 8.5x 10(-10) m(2) s(-1) 1000 degrees C and only twice faster similar to 2.1 x10(-9) m(2) s(-1) 1200 degrees C. Calculations of the diffusion data in relation to the Arrhenius Law, yield an activation energy of similar to 70 +/- 10 kJ mol(-l) . From these effective diffusivities and combined with published diffusion data for olivine single crystals, hydrogen diffusion in grain boundaries is extracted and yield diffusivities almost three order of magnitude faster (similar to 5 x 10(-6) m(2) s(-1) at 1200 degrees C) than in an olivine single crystal at the equivalent high temperature. On geological scales and for coarse-grain rocks, hydrogen diffusivity in grain boundaries is not fast enough to compete with lattice diffusion. The relative large grain size of mantle rocks will ensure a very limited hydrogen transport by effective diffusion, and a good conservation of water-rich zones in the Earth's mantle.
ISSN: 0012-821X

hal-00512821
https://hal.archives-ouvertes.fr/hal-00512821
DOI : 10.1016/j.epsl.2010.04.019

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
We report concentrations of hydrogen (H) in upper mantle minerals of peridotites (olivine and pyroxenes) transported by alnöitic lavas, which erupted on the southwestern border of the Ontong Java Plateau (Malaita, Solomon Islands, West Pacific). Unpolarized FTIR analyses show that olivine, orthopyroxene, and diopside contain 2–32 ppm, 162–362 ppm and 159–459 ppm wt H2O, respectively. In the studied lherzolites, garnets are anhydrous. The concentration of hydrogen within individual olivine and pyroxene grains is almost homogeneous, indicating no evidence of dehydration or hydration by ionic diffusion. In the lherzolite, the concentration of hydrogen in olivine tends to increase weakly with depth (based on geothermobarometry), consistent with the increase of water solubility with increasing water fugacity as a function of pressure, but concentrations remain well below water-saturation values determined experimentally. The highest concentration of H in olivine (32 ppm wt H2O) is, however, found in refractory spinel harzburgites, which equilibrated at depths of 85 km., while deeper specimens as the high-temperature spinel harzburgites, and some of the garnet lherzolites, contain less hydrogen in olivine. Olivines from pyroxene- or pargasite-rich peridotites have also lower hydrogen concentrations. We interpret the high hydrogen concentrations in olivine from the refractory spinel harzburgites as due to (1) simultaneous hydration and metasomatism of the lithospheric mantle by a water-rich silicate melt/fluid, during which hydrogen follows MREE and where spinel harzburgite have experienced ‘stealth’ metasomatism, and/or (2) to a late ‘fleeting’ hydrogen metasomatism, which would hydrate the rock after this first ‘stealth’ metasomatism event. In the second case, the composition of the ‘fleeting’ percolating fluid (small volume fraction of very evolved fluids, with high volatiles concentration and transient properties) is likely to be linked to the decrease of the plume activity and resulting in the downwelling of the lithosphere asthenosphere boundary. The difference in hydrogen concentration between harzburgites and lherzolites could be linked to variation in trace elements in olivine induced by the first ‘stealth’ metasomatism alone or associated to the late ‘fleeting’ hydrogen metasomatism, triggered by the lack of secondary crystallization of clinopyroxenes in the harzburgite. To conclude, H concentrations in upper mantle minerals may thus be correlated to metasomatic events, with the later yielding variation of the mineral assemblage and trace element composition that constitute the peridotites.
ISSN: 0024-4937

hal-01143385
https://hal.archives-ouvertes.fr/hal-01143385
DOI : 10.1016/j.lithos.2014.11.005