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 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
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