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
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 Elsevier
Résumé : In situ analysis of major elements, platinum-group elements and Os isotope composition data for 170 grains of Ru–Os–Ir alloys from podiform chromitites in the Luobusa and Dongqiao ophiolites, Tibet, provide new constraints on the sources of the alloy grains, the Os-isotope composition of the Neo-Tethyan oceanic upper mantle, and the timing of melt–rock reactions in the ultramafic peridotites of the host ophiolites. Most alloy grains are osmiridium and iridosmine. Based on elemental and isotopic compositions, two populations can be identified. Group I, found in both ophiolite bodies, has fractionated PGE patterns typical of alloys and homogeneous 187Os/188Os 0.12645 ± 4 (2s; n = 145). Group II alloys from the Dongqiao ophiolites show smooth PGE patterns and 187Os/188Os ranges from 0.12003 to 0.12194 (yielding Re-depletion ages ≥ 1.1 Ga). Both the PGE patterns and the Os isotopic compositions of Group II resemble those of sulfides residual after melting. Group I alloys represent an early cumulate phase during the crystallization of magmas and are interpreted as derived from an asthenospheric melt. In contrast, Group II alloys are inferred to derive from the breakdown of residual sulfides from the mantle section of the ophiolite, which may represent relics of a sub-continental lithospheric mantle. The coexistence of the two groups of alloys in Dongqiao samples reflects interaction between asthenosphere-derived melts and old depleted lithospheric mantle and suggests that the chromitites originated through melt–rock reactions. The data on the Group I alloys support the hypothesis that the Re–Os evolution of the convective oceanic mantle resembles that of enstatite chondrites.
ISSN: 0012-821X

hal-00404967
https://hal.archives-ouvertes.fr/hal-00404967
DOI : 10.1016/j.epsl.2007.05.044