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
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 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

Éditeur(s) : HAL CCSD Springer Verlag
Résumé : International audience
Cobalt-bearing pyrite (0.5-2.0 wt.% Co) is abnormally abundant (up to 35 vol.% of the total volume of the sulfide phase) in some eastern Pyrenean peridotite massifs, compared to pieces of subcontinental mantle studied so far for sulfides. Pyrite occurs as vermicular intergrowths inside pentlandite and/or chalcopyrite or as coarser, blocky grains in the intergranular pores of host peridotites. Those different pyrites are characterized by different platinum-group element systematics (measured by laser ablation microprobe and ICP-MS). Vermicular pyrite intergrown with pentlandite displays Os-, Ir-, Ru- and Rh-enriched chondrite normalized PGE patterns of Monosulfide solid solution (Mss). In contrast, coarse-grained intergranular ("blocky") pyrites, are PGE-poor. Chalcophile trace elements (i.e. Zn, Pb, Ag, Au) that are not usually concentrated in mantle-derived sulfides were commonly detected. By contrast, selenium contents are generally low, yielding thus pyrite with high S/Se ratio (> 10(5)), consistent with a sedimentary sulfur source. Pyrite microtextures and chalcophile trace element contents support a process of assimilation of crustal sulfur from the metamorphosed sedimentary country rocks. These latter generated highly reactive CO2-S fluids, which were injected into structural discontinuities of the lherzolitic bodies. Sulfur has reacted at T = 300-550A degrees C with pre-existing, mantle-derived, metal-rich sulfide assemblages (pentlandite-chalcopyrite). Addition of crustal sulfur did produce Mss which, on cooling, exsolved the Os-rich pyrite in addition to pentlandite. The coarse-grained pyrite types have crystallized directly from S-rich fluids.
ISSN: 0010-7999

hal-00617425
https://hal.archives-ouvertes.fr/hal-00617425
DOI : 10.1007/s00710-010-0138-2

Éditeur(s) : HAL CCSD Oxford University Press (OUP)
Résumé : The Oman ophiolite consists of several massifs cropping out along a 500 km long band trending NW-SE along the coast of Oman; it is one of the best exposed sections of oceanic crust and mantle in the world. There is a gradient in igneous processes and composition in the ophiolite, with the northern massifs recording a polygenetic igneous history involving an increasingly important subduction component, whereas the southern massifs were formed primarily via a mid-ocean ridge basalt (MORB)-like, single-stage process at a submarine spreading ridge. In this study we use geochemical data from Wadi Tayin, which is one of the southern massifs of the Oman ophiolite, to constrain the composition and genesis of oceanic crust and upper mantle. The Wadi Tayin harzburgites are residues of partial melting that are as depleted as the most depleted mid-ocean ridge peridotites. They have low middle- to heavy rare earth element ratios, most probably reflecting melting close to and beyond the exhaustion of clinopyroxene. Like many abyssal peridotites, the Wadi Tayin samples show enrichment in highly incompatible elements, giving rise to U-shaped MORB-normalized trace element patterns. We favor the idea that this is caused by enrichment of highly incompatible elements along grain boundaries in peridotite, which may be the result of near-equilibrium partitioning between grain boundaries and grain interiors, rather than disequilibrium processes. Equilibrium partitioning between crystals and grain boundaries during melting and melt extraction is also our preferred explanation for ubiquitous high Pb contents relative to Ce and La in our samples as well as in most abyssal peridotites. The Wadi Tayin samples record substantial variability in terms of osmium isotopic composition and platinum group element (PGE) concentrations. The more radiogenic nature of the dunites and impregnated peridotites compared with the residual harzburgites may be due to relatively high Os-187/Os-188 in melt transported through the dunites. The presence of residual peridotites with whole-rock osmium isotopic compositions less radiogenic than MORB may be explained by melting of a veined (upwelling) mantle forming mixed melts in which much of the Os derives from veins with high Re/Os in a matrix of previously depleted peridotite. An important result of this study is that the shallowest samples are refertilized (i.e. anomalously enriched in incompatible elements), and record relatively high metamorphic closure temperatures. These observations suggest that migrating melt underwent crystallization during rapid cooling in the uppermost mantle during and immediately after ridge magmatism. A variety of geothermometers all yield the result that the stratigraphically highest harzburgites equilibrated at higher temperature than the deeper ones. The systematic decrease in closure temperature with increasing depth below the Moho transition zone probably reflects systematic variation in cooling rate as a function of depth in the mantle section. We hypothesize that the refertilization and higher closure temperatures recorded by the uppermost mantle samples are linked. More rapid cooling led to higher closure temperatures, and to partial crystallization of migrating melts in the shallowest part of the mantle section, yielding slightly elevated abundances of elements such as Ca and Na, and incompatible trace elements.
ISSN: 0022-3530

hal-00456056
https://hal.archives-ouvertes.fr/hal-00456056
DOI : 10.1093/petrology/egp077

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 : 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

Éditeur(s) : HAL CCSD Wiley
Résumé : International audience
We report trace element analyses by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) of metal grains from nine different CR chondrites, distinguishing grains from chondrule interior ("interior grains"), chondrule surficial shells ("margin grains"), and the matrix ("isolated grains"). Save for a few anomalous grains, Ninormalized trace element patterns are similar for all three petrographic settings, with largely unfractionated refractory siderophile elements and depleted volatile Au, Cu, Ag, S. All three types of grains are interpreted to derive from a common precursor approximated by the least-melted, fine-grained objects in CR chondrites. This also excludes recondensation of metal vapor as the origin of the bulk of margin grains. The metal precursors were presumably formed by incomplete condensation, with evidence for high-temperature isolation of refractory platinum-group-element (PGE)-rich condensates before mixing with lower temperature PGE-depleted condensates. The rounded shape of the Ni-rich, interior grains shows that they were molten and that they equilibrated with silicates upon slow cooling (1-100 K h 1), largely by oxidation/evaporation of Fe, hence their high Pd content, for example. We propose that Ni-poorer, amoeboid margin grains, often included in the pyroxene-rich periphery common to type I chondrules, result from less intense processing of a rim accreted onto the chondrule subsequent to the melting event recorded by the interior grains. This means either that there were two separate heating events, which formed olivine/ interior grains and pyroxene/margin grains, respectively, between which dust was accreted around the chondrule, or that there was a single high-temperature event, of which the chondrule margin records a late "quenching phase," in which case dust accreted onto chondrules while they were molten. In the latter case, high dust concentrations in the chondrule-forming region (at least three orders of magnitude above minimum mass solar nebula models) are indicated.
ISSN: 1086-9379

hal-01003975
https://hal.archives-ouvertes.fr/hal-01003975
DOI : 10.1111/maps.12212

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