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
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 : 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 element concentrations (HSE: Re and platinum-group elements (PGE)) are presented for gabbros, gabbroic eclogites and basaltic eclogites from the high-pressure Zermatt-Saas ophiolite terrain, Switzerland. Rhenium and PGE (Os, Ir, Ru, Rh, Pt, Pd) abundances in gabbro- and eclogite-hosted sulphides, and Re-Os isotopes and elemental concentrations in silicate phases are also reported. This work, therefore, provides whole rock and mineral-scale insights into the PGE budget of gabbroic oceanic crust and the effects of subduction metamorphism on gabbroic and basaltic crust. Chondrite-normalised PGE patterns for the gabbros are similar to published mid-ocean ridge basalts (MORB), but show less inter-element fractionation. Mean Pt and Pd contents of 360 and 530 pg/g, respectively, are broadly comparable to MORB, but gabbros have somewhat higher abundances of Os, Ir and Ru (mean: 64, 57 and 108 pg/g). Transformation to eclogite has not significantly changed the concentrations of the PGE, except Pd which is severely depleted in gabbroic eclogites relative to gabbros (similar to 75% loss). In contrast, basaltic eclogites display significant depletion of Pt (>= 60%), Pd (>85%) and Re (50-60%) compared with published MORB, while Os, Ir and Ru abundances are broadly comparable. Thus, these data suggest that only Pt, Pd and Re, and not Os, Ir and Ru, may be significantly fluxed into the mantle wedge from mafic oceanic crust. Re-Os model ages for gabbroic and gabbroic eclogite minerals are close to age estimates for igneous crystallisation and high-pressure metamorphism, respectively, hence the HSE budgets can be related to both igneous and metamorphic behaviour. The gabbroic budget of Os, Ir, Ru and Pd (but not Pt) is dominated by sulphide, which typically hosts >90% of the Os, whereas silicates account for most of the Re (with up to 75% in plagioclase alone). Sulphides in gabbroic eclogites tend to host a smaller proportion of the total Os (10-90%) while silicates are important hosts, probably reflecting Os inheritance from precursor phases. Garnet contains very high Re concentrations and may account for >50% of Re in some samples. The depletion of Pd in gabbroic eclogites appears linked, at least in part, to the loss of Ni-rich sulphide. Both basaltic and gabbroic oceanic crust have elevated Pt/Os ratios, but Pt/Re ratios are not sufficiently high to generate the coupled Os-186-Os-187 enrichments observed in some mantle melts, even without Pt loss from basaltic crust. However, the apparent mobility of Pt and Re in slab fluids provides an alternative mechanism for the generation of Pt- and Re-rich mantle material, recently proposed as a potential source of Os-187-Os-186 enrichment.
ISSN: 0016-7037

hal-00420072
https://hal.archives-ouvertes.fr/hal-00420072
DOI : 10.1016/j.gca.2008.11.036

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Chromitite pods in the Mayarí-Cristal ophiolitic massif (eastern Cuba) were formed in the Late Cretaceous when island arc tholeiites and MORB-like back-arc basin basalts reacted with residual mantle peridotites and generated chromite-rich bodies enclosed in dunite envelopes. Platinum-group minerals (PGM) in the podiform chromitites exhibit important Os-isotope heterogeneities at the kilometric, hand sample and thin section scales. 187Os/188Os calculated at the time of chromitite crystallization (~90 Ma) ranges between 0.1185 and 0.1295 (γOs = −7.1 to +1.6, relative to enstatite chondrite), and all but one PGM have subchondritic 187Os/188Os. Grains in a single hand sample have initial 187Os/188Os that spans from 0.1185 to 0.1274, and in one thin section it varies between 0.1185 and 0.1232 in two PGM included in chromite which are only several millimeters apart. As the Os budget of a single micrometric grain derives from a mantle region that was at least several m3 in size, the variable Os isotopic composition of PGM in the Mayarí-Cristal chromitites probably reflects the heterogeneity of their mantle sources on the 10-100 m scale. Our results show that this heterogeneity was not erased by pooling and mingling of individual melt batches during chromitite crystallization but was transferred to the ore deposits on mineral scale. The distribution of the Os model ages calculated for PGM shows four main peaks, at ~100, 500, 750 and 1,000 Ma. These variable Os model ages reflect the presence of different depleted domains in the oceanic (Pacific-related) upper mantle of the Greater Antilles paleo-subduction zone. The concordance between the age of crystallization of the Mayarí-Cristal chromitites and the most recent peak of the Os model age distribution in PGM supports that Os in several grains was derived from fertile domains of the upper mantle, whose bulk Os isotopic composition is best approximated by that of enstatite chondrites; on the other hand, most PGM are crystallized by melts that tapped highly refractory mantle sources.
ISSN: 0010-7999

hal-00822742
https://hal.archives-ouvertes.fr/hal-00822742
DOI : 10.1007/s00410-010-0575-2

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