Éditeur(s) : HAL CCSD Elsevier
Résumé : This contribution reports our preliminary work to determine Cu isotope ratios for various granite rocks and examine the Cu isotope systematics within granite suites. A chemical procedure, modified from Marechal [Marechal, C.N., Telouk, R and Albarede, F., 1999. Precise analysis of copper and zinc isotopic compositions by plasma-source mass spectrometry. Chemical Geology, 156(1-4): 251-273.], Was used to separate Cu from rock matrix. Quantitative recovery (100.6 +/- 1.6%), with a low total procedural blank (2.65 +/- 0.66 ng) for Cu, has been achieved, allowing Cu isotopic measurements on samples with as little as 10 ppm Cu. The Cu isotope ratios (delta Cu-65 relative to NIST SRM 976) of 32 rock samples, ranging from mafic to felsic compositions, from 3 batholiths (2 I-type, 1 S-type) from the Lachlan Fold Belt in southeastern Australia. vary from -0.46 parts per thousand to 1.51 parts per thousand. Most of them cluster around zero, With mean values for the I-type and S-type granites of 0.03 +/- 0.15 parts per thousand and - 0.03 +/- 0.42 parts per thousand (2 sigma) respectively. These data, together with Cu isotope ratios of two loess samples, provide preliminary evidence that the baseline Cu isotopic composition of the crystalline part of upper continental crust is close to zero. The tight clustering of Cu isotope ratios of rocks from the I-type suites Suggests that high-temperature magmatic processes do not produce significant Cu isotope fractionation. However, two granites with abnormally heavy Cu isotope signatures (up to 1.51 parts per thousand) appears to be the result of localized hydrothermal alteration. Measurable variation in Cu isotopic composition of the S-type granite may reflect isotopic heterogeneity in the sedimentary Source region as a result of redox processes or may be due to hydrothermal overprinting. Thus, Cu isotope geochemistry may be a useful tracer for studying hydrothermal alteration and Source heterogeneity of granitic rocks.
ISSN: 0009-2541

hal-00413130
https://hal.archives-ouvertes.fr/hal-00413130
DOI : 10.1016/j.chemgeo.2008.06.047

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) : 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

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) : HAL CCSD Elsevier
Résumé : International audience
Trace metals (Cd, U, Co, Ni, Cu, Ba, Fe, Mn), total organic carbon (TOC) and C and N stable isotope signatures (delta C-313 and delta N-15) were determined in short sediments cores from the inner and outer shelf off Concepcion, Chile (similar to 36 degrees S). The objectives were to establish the effect of environmental conditions on trace metal distributions at two shelf sites, one affected by seasonal oxygenation and the other by permanent low oxygen conditions due to the presence of the oxygen minimum zone (OMZ). We evaluate trace metals as proxies of past changes in primary productivity and the bottom water oxygen regime. Concentrations of pore water sulfides and NH4+ were also measured as indicators of the main diagenetic pathways at each site. Our results for the inner shelf (seasonal suboxia) suggest that the oxidative state of the sediments responds to seasonal pulses of organic matter and that seasonal oxygenation develops during high and low primary productivity in the water column. Here, positive fluxes (to the water column) estimated from pore water concentrations of several elements were observed (Ba, Co, Ni, Fe and Mn). The less reduced environment at this site produces authigenic enrichment of Cu associated with the formation of oxides in the oxic surface sediment layer, and the reduction of U within deeper sediment sections occur consistently with negative estimated pore water fluxes. In the outer shelf sediments (permanent suboxia, OMZ site), negative fluxes (to the sediment) were estimated for all elements, but these sediments showed authigenic enrichments only for Cd, Cu and U. The short oxygenation period during the winter season did not affect the accumulation of these metals on the shelf. The distribution of Cu, Cd and U have been preserved within the sediments and the authigenic accumulation rates estimated showed a decrease from the deep sections of the core to the surface sediments. This could be explained by a gradual decrease in the strength of the OMZ in the last 100 years, in combination with periods of strong oxygenations during El Nino events. (C) 2011 Elsevier Ltd. All rights reserved.
ISSN: 0278-4343

hal-00745672
https://hal.archives-ouvertes.fr/hal-00745672
DOI : 10.1016/j.csr.2011.11.006

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 Oxford University Press (OUP): Policy B - Oxford Open Option A Oxford University Press (OUP)
Résumé : International audience
Peridotites exhumed in the footwall of axial detachment faults at slow-spreading ridges are highly serpentinized. Most mid-ocean ridge detachment settings are magmatically active and hydrous fluid circulation in and near the fault has been shown to be influenced by the presence of melt or magmatic lithologies. Our working area along the Southwest Indian Ridge (62–65°E) is nearly amagmatic and represents an end-member to study the hydrous alteration of exhumed peridotites without these magmatic influences. We use an integrated petrological approach combining microstructural, mineralogical and chemical observations to unravel the sequence of serpentinization in 272 dredged samples of variably serpentinized peridotites and to document the circulation of serpentinizing fluids in and near the exhumation faults. We find that serpentine recrystallization and veins overprint the initial serpentinite mesh texture in ∼25% of the samples. Oxygen isotope data suggest that this sequence developed at relatively high temperatures (271–336°C) and under increasing fluid–rock ratios, from near stoichiometry for mesh texture formation to >10 during recrystallization. Increasing fluid supersaturation relative to serpentine favors the replacement of mesh texture lizardite by chrysotile and polygonal or polyhedral serpentine. We attribute local recrystallization into antigorite to moderate Si-metasomatism, possibly following pyroxene serpentinization. We do not observe the more pronounced Si-metasomatism leading to talc replacing serpentine that is reported for the more magmatically active Mid-Atlantic Ridge detachment settings and is attributed to prior leaching of magmatic rocks. Scales of preferential fluid pathways in our samples evolved from pervasive and close-spaced (<500 µm) microfractures during the formation of the initial serpentine mesh texture, to centimeter-thick planar domains of enhanced fluid flux, spaced at ∼10 cm intervals and probably grouped in corridors that may be up to ∼100 m across. Serpentine minerals are enriched in some fluid-mobile elements (Cl, B, U) relative to the peridotite protolith, and several elements (Al, Fe, Si, Cu, As, Sb, REE) are redistributed at the millimeter to decimeter scale. Serpentinizing fluids were seawater-derived, probably mildly alkaline (small to no europium anomalies), reducing and H2-enriched (formation of magnetite). These fluids may have been similar to, though warmer than, those venting at the ultramafic-hosted Lost City hydrothermal fluid (30°N, Mid-Atlantic Ridge).
ISSN: 0022-3530

hal-01174047
https://hal.archives-ouvertes.fr/hal-01174047
DOI : 10.1093/petrology/egv014