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
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
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
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
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
Highly siderophile elements (Platinum-group elements, Au and Re) are currently assumed to reside inside base metal sulfides (BMS) in the convecting upper mantle. However, fertile lherzolites sampled by Pyrenean orogenic peridotite massifs are unexpectedly rich in 0.5-3 mu m large micronuggets of platinum-group minerals (PGM). Among those, sulfides from the laurite-erlichmanite series (Ru, Os(Ir)S(As)2), Pt-Ir-Os alloys and Pt-Pd-Te-Bi phases (moncheite-merenskyite) are predominant. Not only the BMS phases but also the PGM micronuggets must be taken into account in calculation of the PGE budget of orogenic fertile lherzolites. Laurite is a good candidate for equilibrating the whole-rock budget of Os, it and Ru while accounting for supra-chondritic Ru/Ir-N. Textural relationships between PGMs and BMS highlight heterogeneous mixing between refractory PGMs (laurite/Pt-Ir-Os alloys) inherited from ancient refractory lithospheric mantle and late-magmatic metasomatic sulfides precipitated from tholeiitic melts. "Low-temperature" PGMs, especially Pt-Pd bismuthotellurides should be added to the list of mineral indicators of lithosphere refertilization process. Now disseminated within fertile lherzolites, "lithospheric" PGMs likely account for local preservation of ancient Os model ages (up to 2 Ga) detected in BMS by in-situ isotopic analyses. These PGMs also question the reliability of orogenic lherzolites for estimating the PGE signature of the Primitive Silicate Earth.
ISSN: 0012-821X

hal-00486109
https://hal.archives-ouvertes.fr/hal-00486109
DOI : 10.1016/j.epsl.2009.11.017

Éditeur(s) : HAL CCSD GeoScienceWorld
Résumé : International audience
Due to their "iron-loving" properties, platinum-group elements (PGE) are expected to be stored in the Earth's core. Although very low, at a few parts per billion, PGE concentrations measured in mantle-derived rocks are too high to be in chemical equilibrium with the core. The "late veneer" model offers the best explanation for this paradox-it postulates that a flux of primitive meteorites hit the early Earth after core formation had ceased. However, the inferred PGE composition of the hypothetical primitive mantle exhibits slight positive excesses of Ru, Rh, and Pd compared to the canonical chondritic signature. Such deviations have trigger debate about the composition of the late veneer and the extent of reworking of PGE signatures by igneous processes within the Earth's mantle.
ISSN: 1811-5209

hal-00411483
https://hal.archives-ouvertes.fr/hal-00411483
DOI : 10.2113/GSELEMENTS.4.4.247