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 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 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 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
We carried out detailed petrographic, major and trace element geochemical, microstructural and FTIR analyses on eight characteristic ultramafic xenoliths from Nyos and Barombi Mbo Lakes in the continental sector of the Cameroon Volcanic Line (CVL). The studied xenoliths are spinel lherzolites showing lithologies similar to the other xenoliths reported previously along the CVL. They have protogranular and porphyroclastic textures. One of the Barombi xenolith contains amphibole, which had not been previously reported in this locality. Amphibole is common in the Nyos xenoliths suite. Peridotite xenoliths from both localities show some chemical heterogeneity, but Barombi xenoliths generally are less depleted in basaltic elements with respect to Nyos xenoliths. Trace element compositions of Nyos spinel lherzolites show a moderately depleted initial (premetasomatic) composition and variable enrichment in REE. Evidence for both modal and cryptic metasomatism is present in Nyos xenoliths. Rare earth element patterns of clinopyroxene suggest that interaction between mafic melts and the upper mantle occurred beneath the Nyos locality. Barombi Mbo xenoliths, on the other hand, record a small degree of partial melting. The Barombi Mbo xenoliths have weak, dominantly orthorhombic olivine crystal preferred orientations, whereas Nyos ones have strong axial-[010] patterns, which may have formed in response to transpression. Nominally anhydrous mantle minerals (NAMs) of the Barombi Mbo xenoliths show generally higher bulk concentrations of ‘water’ (70–127 ppm) than Nyos xenoliths (32–81 ppm). The Barombi Mbo xenoliths could originate from a juvenile segment of the lithospheric mantle, which had been originally part of the asthenosphere. It became a part of the lithosphere in response to thermal relaxation following the extension, forming a weakly deformed lower lithospheric mantle region along the CVL. The Nyos xenoliths, however, represent a shallow lithospheric mantle bearing imprints of several depletion and enrichment events probably prior or following the extension (at ∼30 Ma).
ISSN: 0899-5362

hal-01236039
https://hal.archives-ouvertes.fr/hal-01236039
DOI : 10.1016/j.jafrearsci.2015.07.006