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 (>100km) 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.
► Petrogenetic processing may generate a wide range of PGE systematics inside the continental lithosphere. ► PGE budgets inherited from melting events are highly sensitive to magma fluxes ► Major magmatic inputs may rejuvenate the PGE systematic of depleted mantle. ► Sizeable domains of the continental lithosphere are significantly enriched in Pd, Au, Cu, and Se.
The Paris chondrite provides an excellent opportunity to study CM chondrules and refractory inclusions in a more pristine state than currently possible from other CMs, and to investigate the earliest ...stages of aqueous alteration captured within a single CM bulk composition. It was found in the effects of a former colonial mining engineer and may have been an observed fall. The texture, mineralogy, petrography, magnetic properties and chemical and isotopic compositions are consistent with classification as a CM2 chondrite. There are ∼45vol.% high-temperature components mainly Type I chondrules (with olivine mostly Fa0–2, mean Fa0.9) with granular textures because of low mesostasis abundances. Type II chondrules contain olivine Fa7 to Fa76. These are dominantly of Type IIA, but there are IIAB and IIB chondrules, II(A)B chondrules with minor highly ferroan olivine, and IIA(C) with augite as the only pyroxene. The refractory inclusions in Paris are amoeboid olivine aggregates (AOAs) and fine-grained spinel-rich Ca–Al-rich inclusions (CAIs). The CAI phases formed in the sequence hibonite, perovskite, grossite, spinel, gehlenite, anorthite, diopside/fassaite and forsterite. The most refractory phases are embedded in spinel, which also occurs as massive nodules. Refractory metal nuggets are found in many CAI and refractory platinum group element abundances (PGE) decrease following the observed condensation sequences of their host phases. Mn–Cr isotope measurements of mineral separates from Paris define a regression line with a slope of 53Mn/55Mn=(5.76±0.76)×106. If we interpret Cr isotopic systematics as dating Paris components, particularly the chondrules, the age is 4566.44±0.66Myr, which is close to the age of CAI and puts new constraints on the early evolution of the solar system. Eleven individual Paris samples define an O isotope mixing line that passes through CM2 and CO3 falls and indicates that Paris is a very fresh sample, with variation explained by local differences in the extent of alteration. The anhydrous precursor to the CM2s was CO3-like, but the two groups differed in that the CMs accreted a higherproportion of water. Paris has little matrix (∼47%, plus 8% fine grained rims) and is less altered than other CM chondrites. Chondrule silicates (except mesostasis), CAI phases, submicron forsterite and amorphous silicate in the matrix are all well preserved in the freshest domains, and there is abundant metal preserved (metal alteration stage 1 of Palmer and Lauretta (2011)). Metal and sulfide compositions and textures correspond to the least heated or equilibrated CM chondrites, Category A of Kimura et al. (2011). The composition of tochilinite–cronstedtite intergrowths gives a PCP index of ∼2.9. Cronstedtite is more abundant in the more altered zones whereas in normal highly altered CM chondrites, with petrologic subtype 2.6–2.0 based on the S/SiO2 and ∑FeO/SiO2 ratios in PCP or tochilinite–cronstedtite intergrowths (Rubin et al., 2007), cronstedtite is destroyed by alteration. The matrix in fresh zones has CI chondritic volatile element abundances, but interactions between matrix and chondrules occurred during alteration, modifying the volatile element abundances in the altered zones. Paris has higher trapped Ne contents, more primitive organic compounds, and more primitive organic material than other CMs. There are gradational contacts between domains of different degree of alteration, on the scale of ∼1cm, but also highly altered clasts, suggesting mainly a water-limited style of alteration, with no significant metamorphic reheating.
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
µm 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, Ir 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.
Abstract Northwest Africa (NWA) 14672, the most highly shocked Martian meteorite so far, has experienced >50% melting, compatible with peak pressure >~65 Gpa, at a transition stage 6/7. Despite these ...extreme shock conditions, the meteorite still preserves a population of “large” Fe sulfide blebs from the pre‐shock igneous assemblage. These primary blebs preserve characteristics of basaltic shergottites in term of modal abundance, preferential occurrence in interstitial pores along with late‐crystallized phases (ilmenite, merrillite), and Ni‐free pyrrhotite compositions. Primary sulfides underwent widespread shock‐induced remelting, as indicated by perfect spherical morphologies when embedded in fine‐grained silicate melt zones and a wealth of mineral/glass/vesicle inclusions. Extensive melting of Fe‐sulfides is consistent with the decompression path experienced by NWA 14672 after the peak shock pressure at ~70 GPa. Primary sulfides acted as preferential sites for nucleation of vesicles of all sizes which helped sulfur degassing during decompression, leading to partial resorption of Fe‐sulfide blebs and reequilibration of pyrrhotite metal/sulfur ratios (0.96–0.98) toward the low oxygen fugacity conditions indicated by Fe‐Ti oxides hosted in fine‐grained materials. The extreme shock intensity also provided suitable conditions for widespread in situ redistribution of igneous sulfur as micrometric globules concentrated in glassy portions of fine‐grained lithologies. These globules exsolved early on quenching, allowing dendritic skeletal Fe‐Ti oxide overgrowths to nucleate on sulfides.
Eighteen samples from the south-western part of the Ronda lherzolitic massif have been analysed with bulk-rock and in-situ techniques to unravel the fate of Cu, platinum-group element and chalcogens ...(S, Se) in a middle Proterozoic subcontinental lithospheric mantle segment variably overprinted by kilometre-scale porous flow percolation of asthenosphere-derived silicate melts during the Alpine orogeny. Chalcogen elements (S, Se Cu) and PGE systematics fit well the published data base for orogenic mantle peridotites as a whole. Positive correlations between S, Se, Cu and fertility result from progressive removal of sulfides from the mantle at increasing degrees of melting. A few harzburgites preserved the S-, Se- and Pd-depleted (Pd/Ir < 1)-chondrite normalized PGE patterns of residues after partial melting. The Oligocene thermo-mechanical erosion event triggered secondary partial melting of the sulfide phase liberating a Cu-Ni-rich sulfide melt now identified through Cu-Ni-rich sulfide inclusions (pentlandite + chalcopyrite ± bornite) and a wide range of intergranular Cu-rich sulfides and alloys. Residual monosulfide solid solution (coexisting with refractory platinum group minerals (laurite-erlichmanite) in spinel tectonites) survived throughout all of the tectonometamorphic domains, thus preserving relative and absolute abundances of compatible platinum group elements (Os, Ir, Ru, Rh). Local scale redistribution of the Cu-Ni-rich sulfide melt accounts for the enrichment/depletion trends of Te, Pd, Pt, Au, Ag, Cu identified in granular peridotites. On cooling, the sulfide melt produced pentlandite by reacting with monosulfide solid solution at T < 870 °C while transfering incompatible elements that generated micrometric Pt-Cu-Te-As-bearing platinum-group mineral inclusions (e.g. malanite CuPt2IrS4, moncheite PtTe2, Pt arsenide, secondary Pt–Cu alloys), in addition to superchondritic Pd/Ir and nearly chondritic Se/Te identified in mantle sulfides of metasomatic origin. By contrast, micrometer-sized Au particles identified in Au-enriched spinel harzburgites are clearly primary precipitates from volatile-rich small melt fractions.
•Western Ronda lherzolites show mantle-melting derived S, Se, Cu and PGE contents.•Residual Mss (+ laurite in spinel tectonites) survived thermo-mechanical erosion.•Secondary partial melting produced Cu–Ni sulfide melt in the Granular domain.•The Cu–Ni sulfide melt redistributed Mss-incompatible elements (Te, Pd, Pt, Cu).•Volatile-rich small melt fractions precipitated gold in spinel tectonite harzburgites.
Abstract
This paper explores the unusual sulphide–graphite association of a selection of Beni Bousera garnet clinopyroxenites that initially equilibrated within the diamond stability field. Compared ...with common graphite-free garnet pyroxenites analysed so far, these rocks display tenfold S enrichment with concentrations up to 5550 μg g–1. Fe–Ni–Cu sulphides (up to 1·5 wt%) consist of large (up to 3 mm across), low-Ni pyrrrhotite (<0·1 wt% Ni) of troilite composition, along with volumetrically minor chalcopyrite and pentlandite. Such assemblages are interpreted as low-temperature (<100 °C) subsolidus exsolution products from homogeneous monosulphide solid solution. Troilite compositions of the pyrrhotite indicate strongly reducing conditions that are estimated to be slightly above the iron–wüstite (IW) buffer. Bulk-sulphide compositions are closer to the FeS end-member (i.e. Cu- and Ni-depleted) than other sulphide occurrences in mantle-derived pyroxenites described so far. Moreover, troilite contains trace metal microphases (Pb and Ag tellurides, molybdenite) that have never been reported before from mantle-derived garnet pyroxenites but occur in diamond-hosted eclogitic sulphide inclusions. Beni Bousera sulphides also show strong similarities to diamond-hosted sulphide inclusions of eclogitic affinity for a wide range of chalcophile–siderophile trace element contents. In view of the widespread molybdenite exsolution, coupled with Mo and S/Se/Te systematics of sulphide compositions (7872 < S/Se < 19 776; 15 < Se/Te < 31), black-shale pyrite is a potential sedimentary component to contribute to the petrogenesis of Beni Bousera garnet clinopyroxenites. Black shales would have recycled along with cumulates from the oceanic crust in the mantle source of Beni Bousera pyroxenites. Pyrite underwent desulfidation and replacement by troilite during subduction and prograde metamorphism, releasing its fluid-mobile elements (As, Sb, Pb) while suffering minimum S loss because of the strongly reduced conditions. Taken as a whole, our body of data supports a common origin for carbon (−27 ‰ < δ13C < −17 ‰) and sulphur and concomitant formation of diamond and sulphides. Both elements were delivered by an extraneous sedimentary component mixed with the altered oceanic crust rocks that was involved in the genesis of Beni Bousera garnet pyroxenites, prior to a Proterozoic partial melting event.
Despite a relatively 'uniform' fertile composition (Al2O3 = 2·19-4·47 wt %; Fo% = 89·2 ± 0·3%; Cr#Spl = 8·9 ± 1·5%), 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 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 (1·2-1·9; where subscript N indicates normalized to chondrite), (Pd/Pt)N between 1·5 and 2·2, and (Os/Ir)N up to 1·85. Despite the relative uniform fertile composition of the xenoliths, Re/Os ranges between 0·02 and 0·18. 187Os/188Os is extremely variable even within a single sample and can be as high as 0·1756 for the most S-rich samples. Sulphides show highly fractionated and variable abundances of the highly siderophile elements (HSE) 0·03 (Pd/Ir)N < 1283 and Re-Os isotopic composition (0·115 < 187Os/188Os < 0·172). 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 ( 187Os/ 188Os > 0·17) would imply that such fluids are derived from an uncommon type of mantle source possibly related to carbonatite melts.
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