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 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 Elsevier
Résumé : International audience
Type I and Type II eclogite xenoliths from the Roberts Victor kimberlite (South Africa) show marked differences in terms of microstructures, mineralogy, major-and trace-element compositions and oxygen-isotope compositions. The unequilibrated microstructures of Type I eclogites, their typical accessory assemblages (phologopite, diamond, sulphides, fluid inclusions) and the ubiquitous presence of "melt pockets" in garnets provide strong evidence of metasomatism. Type II eclogites systematically lack such features and are microstructurally more equilibrated. Type I eclogites are more magnesium-rich than most Type II (mean Mg# = 0.56 vs. 0.46), while Type II eclogites are generally more Ca-rich (mean CaO = 9 vs. 12 wt%) and Fe-rich (mean FeO = 10 vs. 12 wt%). Type I eclogites are systematically enriched in LREE, Sr, Ba, alkali elements, HFSE, Th and U compared to the more depleted Type II eclogites. Calculated trace-element patterns of fluids in equilibrium with Type I eclogites are closely similar to those of volatile-rich small-volume mantle melts in the carbonatite-kimberlite spectrum commonly inferred to be responsible for mantle metasomatism. Although oxygen isotopes are often used to argue for a subduction origin of mantle eclogites, correlations between delta O-18 of garnet and typical metasomatic tracers suggest that the metasomatic process also has shifted the oxygen-isotope compositions of the Type I eclogites toward heavier values. Roberts Victor Type I eclogites thus carry the imprint of a metasomatic process that strongly modified their major-element, trace-element and isotopic compositions, while the more pristine Type II eclogites escaped this modification. Therefore, attempts to constrain the origin of Roberts Victor eclogites should not be based on the much more abundant Type I eclogites, which retain little geochemical memory of their protoliths. The most suitable materials for such investigations may be the less metasomatised, but more rare, Type II eclogites.
ISSN: 0016-7037

hal-00669867
https://hal.archives-ouvertes.fr/hal-00669867
DOI : 10.1016/j.gca.2011.08.035