Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
A suite of eclogite xenoliths from the Roberts Victor kimberlite (South Africa) is remarkable for its high abundances of base metal sulfides (BMS; up to 2 modal %). However, while sulfides are nearly ubiquitous in Type I eclogites (garnet > 0.07% Na2O), Type II eclogites (garnet < 0.07% Na2O) systematically lack sulfides. Two different sulfide assemblages are recognised within the Type I xenolith suite. Both populations are polyphase Cu-Ni-Fe sulfides, one characterised by the pyrrhotite (Po) + pentlandite (Pn) + chalcopyrite (Cp) assemblage and the other by the smythite/violarite (Smy/Vi) + (Ni)pyrite (Py) + Cp assemblage. The latter is the most abundant assemblage and reflects the supergene alteration of the "primary" Po + Pn + Cp assemblage. This process overprints the original composition of the sulfides by remobilising elements such as S, Fe, Ni, Se and Te. In the Type I eclogites, BMS occur as inclusions within silicates (garnet and clinopyroxene) and as interstitial grains. No chemical differences were observed between enclosed and interstitial sulfides. However, their relative abundances are correlated, indicating a similar origin. The Po + Pn + Cp assemblage is identical to eclogitic sulfides previously described in some Roberts Victor diamonds. Silicate-enclosed sulfides could appear to be early phases, but they are restricted to the outer parts of the silicate grains, suggesting a late incorporation during partial recrystallisation of silicate phases, induced by fluid-rock percolation-reaction during a metasomatic event. Positive whole-rock correlations between Se and (La/Sm)N⁎ and between Cu and ΣLREEN⁎ indicate a direct link between sulfide content and the enrichment of Mg + incompatible elements in the Type I eclogites, further supporting a metasomatic origin of the sulfide component. Similarly, a negative correlation between ΣLREEN⁎ and Cucpx implies that the metasomatic agent was at least partially composed of S-rich fluid (e.g. H2S, SO2) that reacted with the rock and leached Cu out of the silicates. The coupling between sulfides and LREE in the Type I eclogites, as well as the absence of sulfides and metasomatic features (e.g. unequilibrated grain boundaries, melt pockets, fluid inclusions, phlogopite) in the Type II eclogites, demonstrate that Type II eclogites did not undergo such a metasomatic event and therefore may represent the less-modified protoliths of Type I eclogites.
ISSN: 0009-2541

hal-00903856
https://hal.archives-ouvertes.fr/hal-00903856
DOI : 10.1016/j.chemgeo.2013.06.015

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Kimberlites of the Udachnaya-East pipe (Siberia) include a uniquely dry and serpentine-free rock type with anomalously high contents of chlorine (Cl ≤ 6.1 wt%), alkalies (Na2O + K2O ≤ 10 wt%) and sulfur (S ≤ 0.50 wt%), referred to as a “salty” kimberlite. The straightforward interpretation is that the Na-, K-, Cl- and S-rich components originate directly from a carbonate-chloride kimberlitic magma that is anhydrous and alkali-rich. However, because brines and evaporites are present on the Siberian craton, previous studies proposed that the kimberlitic magma was contaminated by the assimilation of salt-rich crustal rocks. To clarify the origin of high Cl, alkalies and S in this unusual kimberlite, here we determine its sulfur speciation and isotopic composition and compare it to that of non-salty kimberlites and kimberlitic breccia from the same pipe, as well as potential contamination sources (hydrothermal sulfides and sulfates, country-rock sediment and brine collected in the area). The average δ34S of sulfides is − 1.4 ± 2.2‰ in the salty kimberlite, 2.1 ± 2.7‰ in the non-salty kimberlites and 14.2 ± 5.8‰ in the breccia. The average δ34S of sulfates in the salty kimberlites is 11.1 ± 1.8‰ and 27.3 ± 1.6‰ in the breccia. In contrast, the δ34S of potential contaminants range from 20 to 42‰ for hydrothermal sulfides, from 16 to 34‰ for hydrothermal sulfates, 34‰ for a country-rock sediment (Chukuck suite) and the regional brine aquifer. Our isotope analyses show that (1) in the salty kimberlites, neither sulfates nor sulfides can be simply explained by brine infiltration, hydrothermal alteration or the assimilation of known salt-rich country rocks and instead, we propose that they are late magmatic phases; (2) in the non-salty kimberlite and breccia, brine infiltration lead to sulfate reduction and the formation of secondary sulfides – this explains the removal of salts, alkali-carbonates and sulfates, as well as the minor olivine serpentinization; (3) hydrothermal sulfur was added to the kimberlitic breccia, but not to the massive kimberlites. In situ measurements of sulfides confirm this scenario, clearly showing the addition of two sulfide populations in the breccia (pyrite-pyrrhotites with average δ34S of 7.9 ± 3.4‰ and chalcopyrites with average δ34S of 38.0 ± 0.4‰) whereas the salty and non-salty kimberlites preserve a unique population of djerfisherites (Cl- and K-rich sulfides) with δ34S values within the mantle range. This study provides the first direct evidence of alkaline igneous rocks in which magmatic sulfate is more abundant than sulfide. Although sulfates have been rarely reported in mantle materials, sulfate-rich melts may be more common in the mantle than previously thought and could balance the sulfur isotope budget of Earth's mantle.
ISSN: 0009-2541

hal-01571982
https://hal.archives-ouvertes.fr/hal-01571982
DOI : 10.1016/j.chemgeo.2016.10.037

Éditeur(s) : HAL CCSD American Chemical Society
Résumé : International audience
2-Amino-9H-pyrido[2,3-b]indole (AalphaC) is the most abundant carcinogenic heterocyclic aromatic amine (HAA) formed in mainstream tobacco smoke. AalphaC is a liver carcinogen in rodents, but its carcinogenic potential in humans is not known. To obtain a better understanding of the genotoxicity of AalphaC in humans, we have investigated its metabolism and its ability to form DNA adducts in human hepatocytes. Primary human hepatocytes were treated with AalphaC at doses ranging from 0.1-50 muM, and the metabolites were characterized by ultra-performance LC/ion trap multistage mass spectrometry (UPLC/MSn). Six major metabolites were identified: a ring-oxidized doubly conjugated metabolite, N2-acetyl-2-amino-9H-pyrido[2,3-b]indole-6-yl-oxo-(beta-d-glucuronic acid) (N2-acetyl-AalphaC-6-O-Gluc); two ring-oxidized glucuronide (Gluc) conjugates: 2-amino-9H-pyrido[2,3-b]indol-3-yl-oxo-(beta-d-glucuronic acid) (AalphaC-3-O-Gluc) and 2-amino-9H-pyrido[2,3-b]indol-6-yl-oxo-(beta-d-glucuronic acid) (AalphaC-6-O-Gluc); two sulfate conjugates, 2-amino-9H-pyrido[2,3-b]indol-3-yl sulfate (AalphaC-3-O-SO3H) and 2-amino-9H-pyrido[2,3-b]indol-6-yl sulfate (AalphaC-6-O-SO3H); and the Gluc conjugate, N2-(beta-d-glucosidurony1)-2-amino-9H-pyrido[2,3-b]indole (AalphaC-N2-Gluc). In addition, four minor metabolites were identified: N2-acetyl-9H-pyrido[2,3-b]indol-3-yl sulfate (N2-acetyl-AalphaC-3-O-SO3H), N2-acetyl-9H-pyrido[2,3-b]indol-6-yl sulfate (N2-acetyl-AalphaC-6-O-SO3H), N2-acetyl-2-amino-9H-pyrido[2,3-b]indol-3-yl-oxo-(beta-d-glucuronic acid) (N2-acetyl-AalphaC-3-O-Gluc), and O-(beta-d-glucosidurony1)-2-hydroxyamino-9H-pyrido[2,3-b]indole (AalphaC-HN2-O-Gluc). The latter metabolite, AalphaC-HN2-O-Gluc is a reactive intermediate that binds to DNA to form the covalent adduct N-(2'-deoxyguanosin-8-yl)-2-amino-9H-pyrido[2,3-b]indole (dG-C8-AalphaC). Preincubation of hepatocytes with furafylline, a selective mechanism-based inhibitor of P450 1A2, resulted in a strong decrease in the formation of AalphaC-HN2-O-Gluc and a concomitant decrease in DNA adduct formation. Our findings describe the major pathways of metabolism of AalphaC in primary human hepatocytes and reveal the importance of N-acetylation and glucuronidation in metabolism of AalphaC. P450 1A2 is a major isoform involved in the bioactivation of AalphaC to form the reactive AalphaC-HN2-O-Gluc conjugate and AalphaC-DNA adducts.
ISSN: 0893-228X

anses-01419468
https://hal-anses.archives-ouvertes.fr/anses-01419468
https://hal-anses.archives-ouvertes.fr/anses-01419468/document
https://hal-anses.archives-ouvertes.fr/anses-01419468/file/Bellamri%20et%20al.%20-%202016%20-%20Metabolism%20of%20the%20Tobacco%20Carcinogen%202-Amino-9H-py.pdf
DOI : 10.1021/acs.chemrestox.6b00394

Éditeur(s) : HAL CCSD Société Géologique de France
Résumé : The Udachnaya-East pipe in Yakutia in Siberia hosts a unique dry (serpentine-free) body of hypabyssal kimberlite (<0.64wt% H2O), associated with a less dry type of kimberlite and a serpentinized kimberlitic breccia. The dry kimberlite is anomalously rich in salts (Na2O and Cl both up to 6wt%) whereas the slightly less dry and the breccia kimberlite are salt free. Yet the Udachnaya kimberlite is a group-I kimberlite, as is the archetypical kimberlite from Kimberley, South Africa. Samples were studied from the three different types of kimberlite (dry-salty, n=8, non-salty, n=5 and breccia, n=3) regarding their mineralogy, geochemistry, and more specifically their sulfur content. Our results show the salty kimberlite is unprecedentedly rich in sulfur (0.13-0.57wt%) compared to the non-salty kimberlite (0.04-0.12wt%) and the breccia (0.29-0.33wt%). In the salty kimberlite, most of the sulfur is present as sulfates (up to 97% of Stotal) and is disseminated throughout the groundmass in close association with Na-K-bearing carbonates. Sulfates occur within the crystal structure of these Na-K-bearing carbonates as the replacement of (CO3) by (SO3) groups, or as Na- and K-rich sulfates (e.g. aphtitalite, (K,Na)3Na(SO4)2). The associated sulfides are djerfisherite; also Na- and K-rich species. The close association of sulfates and carbonates in these S-rich alkaline rocks suggests that the sulfates crystallized from a mantle-derived magma, a case that has strong implication for the oxygen fugacity of kimberlite magmatism and more generally for the global S budget of the mantle.
ISSN: 0037-9409

hal-01622633
https://hal.archives-ouvertes.fr/hal-01622633
DOI : 10.1051/bsgf/2017007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Wood debris are an important component of mangrove marine environments. Current knowledge of the ecological role of wood falls is limited by the absence of information on metazoan colonization processes over time. The aim of this study was to provide insights to their temporal dynamics of wood eukaryotic colonization from a shallow water experiment in a mangrove swamp. Combined in situ chemical monitoring and biological surveys revealed that the succession of colonizers in the mangrove swamp relates with the rapid evolution of sulfide concentration on the wood surface. Sulfide-tolerant species are among the first colonizers and dominate over several weeks when the sulfide content is at its maximum, followed by less tolerant opportunistic species when sulfide decreases. This study supports the idea that woody debris can sustain chemosynthetic symbioses over short time-scale in tropical shallow waters.
ISSN: 0141-1136

hal-01545913
https://hal.archives-ouvertes.fr/hal-01545913
DOI : 10.1016/j.marenvres.2013.03.007

Éditeur(s) : HAL CCSD Mineralogical Society
Résumé : International audience
Almost all magmas contain sulfide- or sulfate-bearing phases. In most natural samples the sulfur-bearing phase is a sulfide, which typically is pyrrhotite (Fe1−xS) or pyrite (FeS2) although chalcopyrite (CuFeS2), pentlandite ((Fe,Ni)9S8), sphalerite (ZnS) or molybdenite (MoS2) may be present as well. Sulfate minerals are rare at magmatic conditions, and anhydrite (CaSO4) is the most common. Other magmatic SO4-bearing minerals include the sodalite group minerals (haüyne simplified formula: (Na,Ca)4-8(Al6Si6(O,S)24)(SO4,Cl)1-2), scapolite minerals (silvialite: (Ca,Na)4Al6Si6O24(SO4,CO3)), and S-bearing apatite (Ca5(PO4)3(F, Cl, OH)). Barite (BaSO4) has been mentioned in rare cases (Marchev 1991). Sulfur-bearing minerals usually constitute a negligible fraction of the mineral assemblage in magmatic rocks and thus can be classified as accessory minerals. The crystallization of sulfide, sulfate, and S-bearing minerals strongly depends on melt composition, temperature and pressure, and the S speciation in melt which, in turn, is strongly dependent on the prevailing oxygen fugacity (Baker and Moretti 2011, this volume; Wilke et al. 2011, this volume). Irrespectively of the low abundance of S-bearing minerals, the evolution of sulfur in magmas may be evaluated from the occurrence of sulfides and sulfates. These minerals are critical for estimating the activity of various sulfur-bearing species in magmas and can be used to constrain the oxygen fugacity and the S concentration in the melt (e.g., pre-eruptive sulfur concentration in melts). The presence of either sulfide or sulfate in silicate melt indicates that the predominant dissolved sulfur species in the melt are S2− or S6+, respectively. Typically one of these species is dominant, but there are conditions where S2− ...
ISSN: 1529-6466

hal-00644580
https://hal.archives-ouvertes.fr/hal-00644580
DOI : 10.2138/rmg.2011.73.10

Éditeur(s) : HAL CCSD
Résumé : This work focus on the characterization of the source and dynamic of compactional fluids during sedimentary burial, through two complementary examples of late orogenic oil‐field half‐grabens: The exhumed Lodève Permian Basin and a deep buried Jurassic basin in the North Viking Graben (North Sea).Constituting the main part of the thesis, a multi‐disciplinary approach was conducted in the Lodève Basin where Ba‐F‐Cu‐Pb polymetallic mineralized systems are trapped into synrift faults and paleokarsts in the carbonate basement at the hinge point of the rollover. The source, timing and P/T conditions of fluid migration were deduced from the analysis of the microfabric, the fluid inclusions microthermometry, and the isotopic (Sr, S, O, H) and Rare Earth Element (REE) signature. Results are then crossed with a structural and thermal modeling that consolidates the sequence and dynamics of fluid during burial.A similar approach was conducted in the North Viking Graben where fluid markers are restricted to 3D seismic and well core data. Comparable Ba‐Pb‐Zn veins are reported in basin margin, plugging one of the most important siliciclastic hydrocarbon reservoir in the substratum. This analysis provides additional constraints on basinal fluid behavior and allows us to propose a global dynamic model for various compositions of fluids and reservoirs.We conclude to a polyphase fluid sequence history including:(a) In the carbonate basement of the Lodève Basin, karstic paleocanyon incisions and associated cavities coupled to synrift fault, act as major drain for fluids. These structures are early affected by hypogen‐sulfuric karstification in response to the interaction between bacterial oxidation of sulfides entrapped within Lower Permian blackshales and the basement oxidizing aquifer.(b) Disequilibrium compaction initiates overpressure‐driven basinal fluid migration towards basin margins, characterized by temperatures around 150‐180°C and salinities between 9 et 18wt%eq.NaCl. Isotopic (Sr, S, O) and REE analyses reveal that Ba‐M+‐rich mineralizing fluids derived mainly from buried blackshales diagenesis. External fluids coming from the lower crust are also identified that play a key role in fluorite precipitation by the leaching of late hercynian granites (mean temperature of 250°C and salinity > 20wt%eq.NaCl).(c) During the synrift period, fluid overpressure is responsible for the periodic reactivation of fault plane according to seismic‐valve process, bedded‐control shearing and hydraulic brecciation at the basement‐seal interface. These mechanisms induce cyclic polymetallic mineralization by the mixing between in‐situ formation water and deep ascending basinal fluids.(d) Thermogenic fluids expulsion starts with last basinal fluids during late burial stage. Hydrocarbons thus migrate along the same regional pathways up to the rollover crest, where they are partly rerouted by the previous mineralized baffle.(e) In the Lodève basin, post‐rift exhumation of the margins led to the remobilization of synrift deposits by subaerial biochemical processes at the sulfate‐methane transition. The latter results from the interaction between the still active hydrocarbon dysmigration with a playa lake sulfate‐rich aquifer. Secondary low‐temperature barite fronts precipitate then within basement meteoric karsts.In addition to the « source to sink » model of basinal fluids, this work provides new insights on the early plugging of hydrocarbon reservoirs and for the metallogenesis of Mississippi Valley‐Type deposits.
Ce travail porte sur la caractérisation de la source et de la dynamique des fluides de bassin au cours de leur chargement à travers deux exemples complémentaires de demi‐grabens tardi‐orogéniques pétroliers : Le Bassin Permien de Lodève, aujourd’hui à l’affleurement et un bassin jurassique enfouis dans le North Viking Graben (Mer du Nord).Le coeur de la thèse concerne le Bassin de Lodève où, à partir d’une approche pluridisciplinaire intégrée, nous avons caractérisé l’architecture des minéralisations (Ba, F, Cu, Pb) piégées dans un réseau paléokarstique alimenté par les failles syn‐rift, dans le substratum carbonaté à l’apex du roll‐over. La source, le calendrier et les conditions de migration des fluides ont été approchés à partir de l’analyse de la micro‐fabrique, la microthermométrie sur inclusions fluides, les analyses isotopiques (Sr, S, O, H) et de Terres Rares. Les résultats analytiques ont été enfin croisés avec un modèle thermique et structural du bassin qui conforte la séquence et la dynamique du système fluide en cours d’enfouissement.Une démarche similaire, mais plus limitée, a été conduite dans le bassin du North Viking Graben où l’accès aux marqueurs fluides est restreint aux données de sismique 3D et de carottes. Comme à Lodève, les minéralisations Ba‐Pb‐Zn colmatent un réservoir dans le substratum à l’apex du roll‐over. Elles se présentent sous forme de ciments dans des grès ou des fractures. Cette analyse apporte des contraintes complémentaires et permet de proposer un modèle dynamique général avec des variantes en fonction de la nature des fluides et des réservoirs.On retiendra donc la séquence fluide suivante :(a) Dans le cas du bassin de Lodève sur substratum carbonaté, les chemins préférentiels de drainage se développent dans des paléocanyons N‐S couplés à un réseau de fractures et d’endokarsts météoriques. Ces derniers sont élargis en début de rifting par la dissolution hypogène sulfurique produite par l’oxydation bactérienne des sulfates et des pyrites des blackshales, au contact de l’aquifère oxydant du Cambrien.(b) Le déséquilibre de compaction initie la migration des fluides interstitiels en surpression vers les marges avec des températures autour de 150‐180°C et des salinités entre 9 et 18wt%eq.NaCl. Les analyses isotopiques (Sr, S, O) révèlent que la majorité des fluides provient de l’altération diagénétique des blackshales riches en métaux. Des interactions sont également mises en évidence avec des fluides profonds (entre 240°C et 260°C ; salinités > à 20wt%eq.NaCl), qui lessivent les granites tardi‐hercyniens.(c) Pendant le syn‐rift, les conditions de surpression de fluide permettent la réactivation cyclique des failles, les décollements stratigraphiques et la formation de brèches hydrauliques, favorisant la mise en connexion avec les réservoirs superficiels à l’apex du rollover. Le modèle de Sibson ajusté aux fluides de bassins est alors le moteur de la migration verticale.(d) Les fluides thermogéniques commencent à être expulsés avec les derniers fluides de compaction au cours d’un stade plus évolué de l’enfouissement en empruntant les mêmes chemins jusqu’à l’apex du roll over. Ils sont alors partiellement freinés et déviés par les colmatages minéralisés antérieurs.(e) A Lodève, la continentalisation des minéralisations antérieures au cours de l’exhumation post‐rift conduit à leur remaniement partiel au niveau de la transition sulfate‐méthane induite par l’interaction entre une playa évaporitique et la dysmigration des hydrocarbures. Des barytines secondaires de basse température, déprimées en Sr sont alors précipitées de manière synsédimentaire dans des karsts météoriques du socle.Outre l’illustration d’un modèle complet (source to sink) de dynamique des fluides dans un bassin, ce travail apporte de nouvelles contraintes dans l’approche du colmatage des réservoirs à hydrocarbures sur les têtes de blocs basculés et sur la genèse des gîtes miniers de type Mississippi Valley‐Type.
https://hal.archives-ouvertes.fr/tel-01457583

tel-01457583
https://hal.archives-ouvertes.fr/tel-01457583
https://hal.archives-ouvertes.fr/tel-01457583/document
https://hal.archives-ouvertes.fr/tel-01457583/file/th%C3%A8seLaurent2015V2.pdf

Éditeur(s) : Université Bordeaux 1
Résumé : The mercury cycle was explored in the Petit-Saut reservoir / Sinnamary Estuary continuum in French Guiana. Main processes involve (i) photo-induced reduction, (ii) adsorption and desorption at the particle surfaces, (iii) methylating bacterial activity, (iv) precipitation and dissolution of iron oxyhydroxides and sulfides. Sources of mercury to the Petit-Saut reservoir consist of the partly impacted river-tributaries, the atmospheric deposition and the flooded soils or vegetation. Once into the reservoir, divalent mercury undergoes a large spectrum of transformations including speciation and phase changes. We, here, probe these processes and demonstrate that the Petit-Saut reservoir behaves as a privileged site for atmospheric recycling and in situ methylation. At the air / water interface, the mercury evasion exceeds by 50 % the direct atmospheric deposition. The in situ monomethylmercury (MMHg) production mostly occurs at the water-column chemocline and near the benthic interface. It reaches, for the whole reservoir, 8.1 moles yr-1 which corresponds to a 0.06 % d-1 methylation rate. We calculated that the 2003/04 period MMHg outputs from the reservoir to the Sinnamary Estuary averaged 13.5 moles yr-1 while the inputs were 5.4 moles yr-1. The dynamic Sinnamary Estuary is the genuine geochemical reactor of the continuum. There, the divalent mercury undergoes rapid yet profound partitioning among phases, recycling to the atmosphere and methylation processes. Those mostly originate from the long-scale oxygen paucity of the dam discharged waters. The expression of marked redox gradients and the intense organic matter turnover enhance the production of methylable inorganic mercurial species and tend to favor the sulfate reducing bacteria (methylating agents) activity. As a result, the dynamic Sinnamary Estuary exports 60 % more MMHg than it does import: 27 versus 17 moles yr-1. Further at large, in the saline estuary, we determined: (i) a non conservative behavior of dissolved (< 0.2 µm) mercury, (ii) a lowering of the mercury level of particles during mixing with the Amazon plume and (iii) a gradual dilution of the estuarine mercury concentrations by oceanic waters.
La retenue de Petit-Saut et, à l'aval, l'estuaire du Sinnamary sont deux centres d'altération du cycle naturel du mercure. Les processus sont, entre autres, (i) la photoréduction, (ii) la sorption / désorption en surface des particules, (iii) l'activité méthylante des bactéries, (iv) la dissolution / précipitation des oxyhydroxydes et des sulfures de fer. Les sources de mercure vers la retenue sont variées. Elles regroupent, en premier lieu, les affluents (partiellement orpaillés), l'atmosphère, les sols et la végétation ennoyés. Dans la colonne d'eau, les formes divalentes du mercure subissent un train complet de transformations couplant changements de phase et de spéciation. Nos résultats illustrent ces processus et démontrent que la retenue constitue un site privilégié de recyclage vers l'atmosphère et de méthylation. A l'interface air / eau, les exports en mercure de la retenue excèdent de 50 % le dépôt atmosphérique. La production endogène de monométhylmercure (MMHg) a lieu dans des sites particuliers : la chemocline et l'interface benthique. Elle atteint pour l'ensemble de la retenue 8,1 moles a-1 soit un taux de méthylation de 0,06 % j-1. On estime que la retenue exporte vers l'estuaire du Sinnamary 13,5 moles a-1 de MMHg alors qu'elle n'importe que 5,4 moles a-1. L'estuaire dynamique du Sinnamary constitue le véritable réacteur chimique du système fonctionnant en liaison avec celui de la retenue. Le mercure y décrit un cycle rapide aux processus de partition, de recyclage et de méthylation marqués. Ces processus résultent de l'oxygénation incomplète et durable des masses d'eau anoxiques exportées par la retenue de Petit-Saut. L'expression de gradients rédox prononcés conjuguée à un intense recyclage de la matière organique y favorise la production de formes méthylables de mercure ainsi que l'activité des bactéries sulfatoréductrices (agents de la méthylation). C'est pourquoi, l'estuaire dynamique du Sinnamary exporte 60 % plus de MMHg qu'il n'importe : 27 contre 17 moles a-1. Plus en aval, dans l'estuaire salin, nous avons mis en évidence : (i) un comportement non conservatif du mercure dissous, (ii) un appauvrissement du mercure des particules suite au mélange avec le panache de l'Amazone et (iii) une dilution des concentrations par les masses d'eau océaniques.

Droits : info:eu-repo/semantics/openAccess
http://archimer.ifremer.fr/doc/2006/these-1508.pdf
http://archimer.ifremer.fr/doc/00000/1508/

Éditeur(s) : Université des Antilles Études caribéennes
Résumé : The tropical coast of Queensland, Australia is experiencing rapid population and tourism growth. Heavy development pressure is being placed on the biophysical environment, which includes the largest sand island in the world (World Heritage listed), Fraser Island. Despite the existence of State planning legislation oriented towards environmental sustainability, it is apparent that little, if any, regard is being paid to the long-term effects of resort and canal-estate development on the underlying biophysical environment of the coast and islands. While the remarkable surface features of the tropical coastal environment such as the surf beaches, the unique dune lakes, and the coastal vegetation, as well as the prolific wildlife, are used as selling points for new settlement and above all tourism, little is known or apparently of major concern with respect to the long term environmental impact of coastal development. While the crowding effect of large numbers of visitors and their impact on the natural environment - through significant degradation, site hardening or lack of proper on-site management – has been identified as a particular problem in certain areas, there is little knowledge of impacts on the underlying coastal geomorphology. In particular, developmental choices are often made in ignorance of, or disregard of, the widespread existence of tropical acid sulfate soils in that coastal environment. Reactive soils such as these can, and do, greatly affect the biophysical outcomes of a development if they are exposed. This paper documents such impacts in the form of a case study of the acid sulfate soil problem in relation to the development of tourist resorts, and suggests that part of the solution is for the State Government to insist on enforceable standards relating to their development for tourism in the coastal zone. These would reduce the use by many resort owners of fancy golf course developments as an environmental cover up to make it look as if they put a lot of effort into protecting the environment….
La côte tropicale du Queensland est confrontée à un accroissement rapide de la population. Les fortes pressions anthropiques pèsent sur le milieu biophysique, qui comprend notamment a plus grande île de sable du monde, un site classé Patrimoine de l’Humanité, Port Hinchinbrook et Fraser Island. Malgré l’existence d’une législation nationale orientée vers la préservation de l’environnement, il est manifeste que peu d’attention est accordée aux effets à long terme des sites touristiques et du développement de l’urbanisation sur ces franges côtières sensibles. L’aspect massif des flux de visiteurs et leurs impacts sur le milieu naturel a été identifié comme un sujet d’inquiétude particulier dans certaines régions. La connaissance des impacts sur la géomorphologie côtière souterraine est très réduite et les choix de développement sont souvent faits dans l’ignorance ou au mépris de la présence répandue de terrains de sulfate d’acide dans ce milieu côtier. Des sols réactifs comme ceux-là peuvent affecter, et affectent, grandement les résultats géophysiques d’un développement lorsqu’ils sont connus. Des études de cas sur le problème des sols de sulfate d’acide suggèrent qu’une partie de la solution pour le gouvernement de l’Etat du Queensland est d’imposer des normes obligatoires pour le développement du tourisme dans la zone côtière.
Australie
Queensland

Droits : info:eu-repo/semantics/openAccess
urn:doi:10.4000/etudescaribeennes.1272
http://journals.openedition.org/etudescaribeennes/1272

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
The western part of the Ronda peridotite massif (Southern Spain) consists mainly of highly foliated spinel-peridotite tectonites and undeformed granular peridotites that are separated by a recrystallization front. The spinel tectonites are interpreted as volumes of ancient subcontinental lithospheric mantle and the granular peridotites as a portion of subcontinental lithospheric mantle that underwent partial melting and pervasive percolation of basaltic melts induced by Cenozoic asthenospheric upwelling. The Re-Os isotopic signature of sulfides from the granular domain and the recrystallization front mostly coincides with that of grains in the spinel tectonites. This indicates that the Re-Os radiometric system in sulfides was highly resistant to partial melting and percolation of melts induced by Cenozoic lithospheric thermal erosion. The Re-Os isotopic systematics of sulfides in the Ronda peridotites thus mostly conserve the geochemical memory of ancient magmatic events in the subcontinental lithospheric mantle. Os model ages record two Proterozoic melting episodes at similar to 1.6 to 1.8 and 1.2-1.4 Ga, respectively. The emplacement of the massif into the subcontinental lithospheric mantle probably coincided with one of these depletion events. A later metasomatic episode caused the precipitation of a new generation of sulfides at similar to 0.7 to 0.9 Ga. These Proterozoic Os model ages are consistent with results obtained for several mantle suites in Central/Western Europe and Northern Africa as well as with the Nd model ages of the continental crust of these regions. This suggests that the events recorded in mantle sulfides of the Ronda peridotites reflect different stages of generation of the continental crust in the ancient Gondwana supercontinent.
ISSN: 0010-7999

hal-00564508
https://hal.archives-ouvertes.fr/hal-00564508
DOI : 10.1007/s00410-009-0429-y

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Large organic falls to the benthic environment, such as dead wood or whale bones, harbour organisms relying on sulfide-oxidizing symbionts. Nothing is known however, concerning sulfide enrichment at the wood surface and its relation to wood colonization by sulfide-oxidizing symbiotic organisms. In this study we combined in situ hydrogen sulfide and pH measurements on sunken wood, with associated fauna microscopy analyses in a tropical mangrove swamp. This shallow environment is known to harbour thiotrophic symbioses and is also abundantly supplied with sunken wood. A significant sulfide enrichment at the wood surface was revealed. A 72 h sequence of measurements emphasized the wide fluctuation of sulfide levels (0.1->100 lM) over time with both a tidal influence and rapid fluctuations. Protozoans observed on the wood surface were similar to Zoothamnium niveum and to vorticellids. Our SEM observations revealed their association with ectosymbiotic bacteria, which are likely to be sulfide- oxidizers. These results support the idea that sunken wood surfaces constitute an environment suitable for sulfide-oxidizing symbioses.
ISSN: 0141-1136

hal-00751649
https://hal.univ-antilles.fr/hal-00751649

Éditeur(s) : HAL CCSD Elsevier
Résumé : High-precision Ni isotopic variations are reported for the metal phase of equilibrated and unequilibrated ordinary chondrites, carbonaceous chondrites, iron meteorites, mesosiderites, and pallasites. We also report new Zn and Cu isotopic data for some of these samples and combine them with literature Fe, Cu, and Zn isotope data to constrain the fractionation history of metals during nebular (vapor/solid) and planetary (metal/sulfide/silicate) phase changes. The observed variations of the Ni-62/Ni-58, Ni-61/Ni-58, and Ni-60/Ni-58 ratios vary linearly with mass difference and define isotope fractionation lines in common with terrestrial samples. This implies that Ni was derived from a single homogeneous reservoir. While no Ni-60 anomaly is detected within the analytical uncertainties, Ni isotopic fractionation up to 0.45 parts per thousand per mass-difference unit is observed. The isotope compositions of Ni and Zn in chondrites are positively correlated. We suggest that, in ordinary chondrites, exchange between solid phases, in particular metal and silicates, and vapor followed by mineral sorting during accretion are the main processes controlling these isotopic variations. The positive correlation between Ni and Zn isotope compositions contrasts with a negative correlation between Ni (and Zn) and Cu isotope compositions, which, when taken together, do not favor a simple kinetic interpretation. The observed transition element similarities between different groups of chondrites and iron meteorites are consistent with the genetic relationships inferred from oxygen isotopes (IIIA/pallasites and IVA/L chondrites). Copper is an exception, which we suggest may be related to separate processing of sulfides either in the vapor or during core formation. (C) 2007 Elsevier Ltd. All rights reserved.
ISSN: 0016-7037

hal-00408304
https://hal.archives-ouvertes.fr/hal-00408304
DOI : 10.1016/j.gca.2007.06.049

Éditeur(s) : Elsevier
Résumé : The distribution, partition and speciation of mercury (Hg) were studied along the redox gradient of an anthropogenically perturbed tropical estuary, the Sinnamary Estuary in French Guiana. This system is a partially mixed estuary characterized by an anoxic freshwater end-member, while the marine end member consists of the Amazon Plume. The set up of an artificial oxygenation system in the anoxic freshwater end-member generates sharp gradients of major chemical species (iron, sulfides, etc.) coupled with intense organic matter (OM) turnover. The coexistence of oxygenated waters and dissolved sulfides in an organic rich environment depicts the Upper Sinnamary Estuary (USE: part of Sinnamary Estuary under the tidal influence but upstream of the salt intrusion) as a potential site for Hg methylation. The concentrations of all mercurial species (HgT) in the unfiltered samples (HgTUNF), in the dissolved (HgTD) and particulate (HgTP) phases of the USE average 11 ± 3, 6 ± 2 and 5 ± 3 (i.e. 600 ± 200 pmol g-1) pmol L-1 respectively. Average concentrations of monomethylmercury (MMHg) in the unfiltered (MMHgUNF), dissolved (MMHgD) and particulate (MMHgP) phases were 3.7 ± 1.0, 2.0 ± 0.9 and 1.8 ± 1.2 (i.e. 220 ± 130 pmol g-1) pmol L-1 respectively. Water oxygenation and sulfides concentrations emerged to play a critical role in controlling MMHg levels. Additionally, iron cycling, acid-base mechanisms, and edoxdependent processes were involved in the MMHg partitioning between phases. Overall, the USE constitutes a biogeochemical reactor that gathers partitioning and methylation processes. Thepermanent MMHg inputs from the anoxic freshwater end-member combined with the intense endogenous Hg methylation ensures high MMHg levels in both dissolved and particulate phases. To illustrate, the USE exports 60 ± 20 % more MMHgUNF than it imports: 5.5 ± 0.7 vs. 3.5 ± 1.2 kg y-1.
Geochimica et Cosmochimica Acta (0016-7037) (Elsevier), 2008-07 , Vol. 72 , N. 22 , P. 5416-5430

Droits : 2008 Elsevier Ltd. All rights reserved
http://archimer.ifremer.fr/doc/2008/publication-4223.pdf
DOI:10.1016/j.gca.2008.08.021
http://archimer.ifremer.fr/doc/00000/4223/

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : ODP Leg 209 Site 1274 mantle peridotites are highly refractory in terms of lack of residual clinopyroxene, olivine Mg# (up to 0.92) and spinel Cr# (∼0.5), suggesting high degree of partial melting (>20%). Detailed studies of their microstructures show that they have extensively reacted with a pervading intergranular melt prior to cooling in the lithosphere, leading to crystallization of olivine, clinopyroxene and spinel at the expense of orthopyroxene. The least reacted harzburgites are too rich in orthopyroxene to be simple residues of low-pressure (spinel field) partial melting. Cu-rich sulfides that precipitated with the clinopyroxenes indicate that the intergranular melt was generated by no more than 12% melting of a MORB mantle or by more extensive melting of a clinopyroxene-rich lithology. Rare olivine-rich lherzolitic domains, characterized by relics of coarse clinopyroxenes intergrown with magmatic sulfides, support the second interpretation. Further, coarse and intergranular clinopyroxenes are highly depleted in REE, Zr and Ti. A two-stage partial melting/melt–rock reaction history is proposed, in which initial mantle underwent depletion and refertilization after an earlier high pressure (garnet field) melting event before upwelling and remelting beneath the present-day ridge. The ultra-depleted compositions were acquired through melt re-equilibration with residual harzburgites. Electronic supplementary material Supplementary material is available in the online version of this article at ;; and is accessible for authorized users
ISSN: 0010-7999

hal-00404655
https://hal.archives-ouvertes.fr/hal-00404655
DOI : 10.1007/s00410-006-0148-6

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Whole-rock concentrations of Se and Te were determined in 53 peridotite samples collected in orogenic bodies from the Eastern Pyrenees, including the Lherz massif (33 samples), the type-locality of Iherzolite. Orogenic Iherzolites tectonically emplaced into the continental crust escaped devolatilisation that may strongly alter concentrations of those volatile trace elements in basalt-hosted peridotite xenoliths. The Se and Te concentration ranges (<3.5-100.7 ppb; <1-11 ppb) are consistent with the few analyses of mantle samples yet available, yet extending to higher Se concentrations. In-situ analyses performed by LAM-ICPMS on base metal sulfides indicate that the Se budget is controlled by sulfides whereas a large fraction of Te (50 +/- 30%) does not reside in sulfides. The missing fraction is accounted for by fractional crystallization of Pt-Pd tellurides from Cu-Ni sulfide melts. A maximum of one third of the S budget of Eastern Pyrenean peridotites was added by assimilation of crustal sulfides, which crystallized as pyrite. Disregarding those contaminated samples, some features of the Se and Te systematics (e.g. bivariate plots vs. fertility index) cannot be explained by partial melting processes. The best fit for 33 peridotites (mostly from Lherz) yields higher than chondritic S/Se (3.1213 +/- 500; r(2) = 0.96) for near chondritic Se/Te (8.6 +/- 2; r(2) = 0.9). Our study suggest that such superchondritic S/Se ratios are better explained by petrogenetic processes involving refertilization of harzburgitic lithosphere by metal (Cu,Ni)-rich sulfide melts precipitated along with clinopyroxene and Al-spinel from silicate melts en-route to the surface.
ISSN: 0009-2541

hal-00544577
https://hal.archives-ouvertes.fr/hal-00544577
DOI : 10.1016/j.chemgeo.2010.09.007

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Orogenic lherzolites exhibit a specific (although reproducible) platinum-group element signature characterized by slight positive deviations of Pd/Ir, Rh/Ir and Ru/Ir ratios from the canonical chondritic model. Such a signature was alternatively considered to be a compositional feature of the primitive upper mantle or resulting from sulfide melt addition by refertilisation reactions in the continental lithosphere. To shed additional light on this conundrum, the distribution of PGE in FON B 93, an unserpentinized, fertile (3.24% Al2O3) orogenic lherzolite (French Pyrenees) used as in-house standard by our group, has been studied to different scales, from the bulk rock to trace minerals. In addition to new ICPMS analyses after separation into Nis and Te coprecipitation, its whole-rock PGE concentrations were redetermined by three different laboratories using very precise ID-ICP-MS methods after digestion of the sample in Carius tube at T=250 degrees C and 320 degrees C or in high-pressure asher (HPA-S). The four methods produce reproducible Ru, Rh and Pd contents (7.1 +/- 0.18 ppb; 1.43 +/- 0.05 ppb; 7.1 +/- 0.30 ppb) whereas the non-ID NiS-fire assay method underestimates the Os and Ir concentrations by c.a. 10 and 15% compared to ID-ICP-MS analyses (4.40 +/- 0.07 and 4.00 +/- 0.17 ppb, respectively). Platinum was the most difficult to analyse. If performed on powder aliquots smaller than 3 g, the ID-ICP-MS analyses generate strong nugget effects while the non-ID NiS-fire assay method yields statistically lower (but highly reproducible) Pt concentrations (6.92 +/- 0.26 ppb). These features reflect the strong partitioning of Pt into trace phases that SEM and laser ablation-ICP-MS analyses on thin sections identify as both high-temperature Pt-Ir-Os alloys and Pt-(Pd) tellurides of likely subsolidus origin; ten to fifteen grains ranging in maximum dimension from a few micrometres to a few hundreds of nanometers, were identified by standard polished thin section. LA-ICP-MS data on base metal sulfides (25 grains analysed), coupled with the whole-rock S concentration (277 +/- 10 ppm) and modal composition of the BMS (90% pentlandite+accessory pyrite and secondary pyrrhotite + 10% chalcopyrite) allowed the contribution of the BMS phase to the PGE budget of FON B 93 to be estimated. Except Pt that exhibits a 95% deficit in the BMS phase, the PGE concentrations measured by ID-ICP-MS can be balanced by BMS while Al-spinel is a negligible contributor, accounting for less than 0.5% of the Ru budget. The occurrence of Pt in trace phases may bias the whole-rock Pt concentrations because 1) mechanical collection of Pt-rich trace phases remains problematic with the Nis button, and 2) Pt-Ir-Os alloys may be prone to digestion problems in conventional Carius tube procedures. Since they could be stable at mantle depth, such refractory alloys that contain Os and Ir may also have enhanced the heavy PGEs/light PGEs fractionation. Our observations likely pertain to orogenic lherzolites as a whole because BMS assemblages in these mantle rocks record evolution at low sulfur fugacity, which prevents Pt-Ir-Os alloy from entering the Mss in the mantle; moreover, at subsolidus temperature, pentlandite, the major BMS, cannot accommodate 0 valence state Pt.
ISSN: 0009-2541

hal-00411486
https://hal.archives-ouvertes.fr/hal-00411486
DOI : 10.1016/j.chemgeo.2007.06.030

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This study presents the geochemical composition of superficial sediment under oxic and suboxic bottom water conditions along the Chilean continental margin (SE Pacific), where evidence for benthic chemosynthetic activity associated with diffuse seeping of chemically reduced fluids has been reported. The exploration was carried out at: (1) the Chilean Triple Junction (CTJ), at a water depth of ∼2900 m, with the additional indication of hydrothermal activity near a methane-rich cold-seep area (46°S) (German et al., 2010); and (2) the El Quisco methane seep site (EQSS), at ∼340 m water depth (33°S) (Melo et al., 2007; Krylova et al., 2014). While the deeper CTJ is located within an oxic environment (dissolved oxygen in the bottom waters: 164 μM), the shallower EQSS lies within a suboxic environment (dissolved oxygen in bottom water: 23 μM), located within the lower limit of the SE Pacific oxygen minimum zone (OMZ).Pore water from short cores was analyzed for dissolved major, minor, and trace elements (Cl, Na, Mg, K, Ca, Sr, Si, B, P, Ba, Pb, Mn, Fe, Cd, U, and Mo), δ13DIC, sulfide, sulfate, and methane. The solid sediment fraction was likewise analyzed for total organic carbon (TOC), metals, and redox potential. Elevated sediment temperatures were found in superficial sediments (5–13 °C) at the CTJ site, which could be due to warm fluids associated with the proximity of the ridge, where hydrothermal vents may occur. Reduced fluids were also present here, indicated by higher Mn fluxes toward the water column even in oxidized sediments (RPD > 8 cm), which contrasted with the lower fluxes in reduced sediments of the EQSS site (RPD ∼ 2 cm). 13C-depleted DIC, anomalously low pore water Cl (∼15 ppb), and low concentrations of other major elements may be the result of dilution by fluid seeping and precipitation of major elements, producing authigenic enrichment (Ca, Mg, Sr). The fluid could also: (a) be diluted by pure water produced during methane hydrate dissociation, as observed in other cold-seep areas; and (b) correspond to clay mineral dehydration, as reported in plate subduction systems. The reducing conditions established at the CTJ conduct the Cd enrichment at a similar magnitude of that seen at the shallower suboxic site (EQSS). Evidence of chimney or vent fauna was not observed. At the EQSS, higher TOC and total sulfide contents were consistent with enhanced deposition of organic matter and reducing conditions developed in the OMZ, favoring the authigenic enrichment of Cd, U and Pb. The geochemical evidence, based only on methane concentrations and δ13DIC, is insufficient to establish the presence of methane seeps, as previously reported.
ISSN: 0079-6611

hal-01412700
https://hal.archives-ouvertes.fr/hal-01412700
DOI : 10.1016/j.pocean.2016.09.002

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Spinel lherzolite xenoliths from Mont Briancon, French Massif Central, retain evidence for multiple episodes of melt depletion and melt/fluid infiltration (metasomatism). Evidence for primary melt depletion is still preserved in the co-variation of bulk-rock major elements (MgO 38.7-46.1 wt.%; CaO 0.9-3.6 wt.%), and many samples yield unradiogenic bulk-rock Os isotope ratios (Os-187/Os-188 = 0.11541-0.12626). However, many individual xenoliths contain interstitial glasses and melt inclusions that are not in equilibrium with the major primary minerals. Incompatible trace element mass balance calculations demonstrate that metasomatic components comprise a significant proportion of the bulk-rock budget for these elements in some rocks, ranging to as much as 25%, of Nd and 40% of Sr Critically, for Re-Os geochronology, melt/fluid infiltration is accompanied by the mobilisation of Sulfide. Consequently, bulk-rock isotope measurements, whether using lithophile (e.g. Rb-Sr, Sm-Nd) or siderophile (Re-Os) based isotope systems, may only yield a perturbed and/or homogenised average of these multiple events.;Osmium mass balance calculations demonstrate that bulk-rock Os in peridotite is dominated by contributions from two populations of sulfide grain: (i) interstitial, metasomatic Sulfide with low [Os] and radiogenic Os-187/Os-188, and (ii) primary sulfides with high [Os] and unradiogenic Os-187/Os-188, which have been preserved within host silicate grains and shielded from interaction with transient melts and fluid. The latter can account for >97% of bulk-rock Os and preserve geochronological information of the melt from which they originally precipitated as an immiscible liquid. The Re-depletion model ages of individual primary sulfide grains preserve evidence for melt depletion beneath the Massif Central from at least 1.8 Gyr ago despite the more recent metasomatic event(s). (C) 2009 Elsevier Ltd. All rights reserved.
ISSN: 0016-7037

hal-00454537
https://hal.archives-ouvertes.fr/hal-00454537
DOI : 10.1016/j.gca.2009.09.031

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The platinum-group element (PGE) systematics of continental mantle peridotites show large variability, reflecting petrogenetic processing of the upper mantle during partial melting and melt/fluid percolation inside the lithosphere. By removing Pd-Cu-Ni rich sulfides, partial melting events that have stabilized the sub-continental mantle lithosphere fractionated PPGEs (Palladium-group PGE; Pt, Pd) relative to IPGEs (Iridium-group PGE; Os, Ir, Ru, Rh). Residual base-metal sulfides (BMS) survive as enclosed IPGE-enriched Monosulfide Solid Solutions (Mss), which otherwise decompose into Ru-Os-Ir-rich refractory platinum-group minerals (PGMs) once the partial melts become S-undersaturated. The small-scale heterogeneous distribution of these microphases may cause extreme nugget effects, as seen in the huge variations in absolute PGE concentrations documented in cratonic peridotites. Magmas fluxing through the lithospheric mantle may change the initial PGE budgets inherited from the melting events, resulting in the great diversity of PGE systematics seen in peridotites from the sub-continental lithosphere. For instance, melt-rock reactions at increasing melt/rock ratios operate as open-system melting processes removing residual BMS/PGMs. Highly percolated peridotites are characterized by extreme PGE depletion, coupled with PGE patterns and Os-isotope compositions that gradually evolve toward that of the percolating melt. Reactions at decreasing melt-rock ratios (usually referred to as "mantle metasomatism") precipitate PPGE-enriched BMS that yield suprachondritic Pd/Ir and occasionally affect Pt/Ir and Rh/Ir ratios as well. Moreover, volatile-rich, small volume melts fractionate Os relative to Ir and S relative to Se, thereby producing rocks with supra-chondritic Os/Ir and S/Se coupled with supra-chondritic Pd/Ir and Pt/Ir. Major magmatic inputs at the lithosphere-asthenosphere boundary may rejuvenate the PGE systematics of the depleted mantle. Integrated studies of "refertilized" peridotites with worldwide provenance provide evidence for mixing between old PGM-rich harzburgitic protoliths and newly-precipitated BMS. Long-lived PGMs carry the Os-isotope compositions of ancient melt‐depletion events into seemingly undepleted fertile lherzolites. Another diagnostic feature of major refertilization processes is the increasing modal abundance of Pt-Pd-Te-Bi or Pt-As-S microphases. Due to regional-scale refertilization processes, sizeable (> 100 km) domains of the upper lithospheric mantle are now significantly enriched in Pd, Au, Cu, Se, and other incompatible chalcophile elements that are of considerable importance in PGE-ore forming events.
ISSN: 0024-4937

hal-00828626
https://hal.archives-ouvertes.fr/hal-00828626
DOI : 10.1016/j.lithos.2012.08.017

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
The biogeochemistry of sulfur and carbon during early-diagenetic processes within organic-rich marine mangrove sediments was studied in the “Manche à Eau” lagoon, Guadeloupe, West Indies. These sediments are characterized by a total organic carbon content (TOC) mostly above 11 wt%, δ13CTOC below − 25‰ VPDB and C/Nmolar ratios exceeding 15. Rates of mangrove-derived organic carbon accumulation vary between ~ 200 and 400 gOC·m− 2·yr− 1, with highest rates at the shore of the lagoon. On the lagoon border, where colorless filamentous sulfur-oxidizing bacteria colonize the sediments, active sulfate reduction within the upper 20 cm, with a net removal rate of ~ 0.5 μmol·cm− 3·d− 1, is assumed to be essentially driven by organic carbon oxidation. This is expressed by relatively low apparent sulfur isotope fractionation (34εnet = − 33‰) and a gentle δ18O/δ34Ssulfate apparent slope of 0.36 ± 0.03 (2s). Further inside the lagoon, in the absence of sulfur-oxidizing bacteria, higher apparent sulfur isotope fractionation and a steeper δ18O/δ34Ssulfate slope (0.67 ± 0.20) suggest an overall lower sulfate removal rate that may be coupled to minor sulfur disproportionation. Spatial and vertical variation in sulfur cycling, reflected by oxygen and sulfur isotopic characteristics, seem to be mainly controlled by unsteady to relatively steady organic matter deposition and its reactivity. In all sediments, δ34S values of pyrite are positively correlated with the TOC/TS ratio and negatively correlated with δ13CTOC; suggesting a primary control of the quantity and quality of organic matter on the pyrite isotope records, despite potential iron-limiting conditions for the most active sites. Our results provide insights into the role of organic carbon input on sulfur cycling; stimulating sulfate reduction and in turn the presence of sulfur-oxidizing microbial mats, resulting in an intense cycling of both carbon and sulfur in these marine mangrove sediments.
ISSN: 0009-2541

hal-01507696
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01507696
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01507696/document
https://hal-univ-rennes1.archives-ouvertes.fr/hal-01507696/file/Cr%C3%A9mi%C3%A8re%20et%20al.%20-%20Sulfur%20diagenesis%20under%20rapid%20accumulation%20of%20orga.pdf
DOI : 10.1016/j.chemgeo.2017.02.017