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.
The Chassigny meteorite, a Martian dunite, contains trace amounts (0.005 vol.%) of Fe-Ni sulfides, which were studied from two polished mounts in reflected light microscopy, Scanning Electron Microscope (SEM) and Electron Microprobe (EMP).The sulfide phases are, by decreasing order of abundance, nickeliferous (0-3 wt% Ni) pyrrhotite with an average composition M0.88±0.01S(M = Fe+Ni+Co+Cu+Mn), nickeliferous pyrite (0-2.5 wt% Ni), pentlandite, millerite and unidentified Cu sulfides.Pyrrhotite is enclosed inside silicate melt inclusions in olivine and disseminated as polyhedral or near spherical blebs in intergranular spaces between cumulus and postcumulus silicates and oxides.This sulfide is considered to be a solidification product of magmatic sulfide melt.The pyrrhotite Ni/Fe ratios lie within the range expected for equilibration with the coexisting olivine at igneous temperatures.Pyrite occurs only as intergranular grains, heterogeneously distributed between the different pieces of the Chassigny meteorite.Pyrite is interpreted as a by-product of the low-T (200°C) hydrothermal alteration events on Mars that deposited Ca sulfates + carbonates well after complete cooling.The shock that ejected the meteorite from Mars generated post-shock temperatures high (300°C) enough to anneal and rehomogenize Ni inside pyrrhotite while pyrite blebs were fractured and disrupted into subgrains by shock metamorphism.The negligible amount of intergranular sulfides and the lack of solitary sulfide inclusions in cumulus phases (olivine, chromite) indicate that, like other Martian basalts so far studied for sulfur, the parental melt of Chassigny achieved sulfide-saturation at a late stage of its crystallization history.Once segregated, the pyrrhotite experienced a late-magmatic oxidation event that reequilibrated its metal-to-sulfur ratios.
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.
Abstract Shergottites have provided abundant information on the volcanic and impact history of Mars. Northwest Africa (NWA) 14672 contributes to both of these aspects. It is a vesicular ophitic depleted olivine–phyric shergottite, with average plagioclase An 61 Ab 39 Or 0.2 . It is highly ferroan, with pigeonite compositions En 49‐25 Fs 41‐61 Wo 10‐14 like those of basaltic shergottites, for example, NWA 12335. Olivine (Fo 53‐15 ) has discrete ferroan overgrowths, more ferroan when in contact with plagioclase than when enclosed by pyroxene. The pyroxene (a continuum of augite, subcalcic augite, and pigeonite) is patchy, with ragged “cores” enveloped or invaded by ferroan pyroxene. Magma mixing may be responsible for capture of olivine and formation of pyroxene mantles. The plagioclase is maskelynite‐like in appearance, but the original laths were (congruently) melted and the melt partly crystallized as fine dendrites. Most of the 14% vesicles occur within plagioclase. Olivine, pyroxene, and ilmenite occur in part as fine aggregates crystallized after congruent melting with limited subsequent liquid mixing. There are two fine‐grained melt components, barred plagioclase with interstitial Fe‐bearing phases, and glass with olivine dendrites, derived by melting of mainly plagioclase and mainly pyroxene, respectively. Rare silica particles contain coesite and/or quartz, and silica glass. The rock has experienced >50% melting, compatible with peak pressure >~65 GPa. It is the most highly shocked shergottite so far, at shock stage S6/7. It may belong to the group of depleted shergottites ejected at ~1 Myr from Tooting Crater.
Abstract Northwest Africa 7533, a polymict Martian breccia, consists of fine‐grained clast‐laden melt particles and microcrystalline matrix. While both melt and matrix contain medium‐grained noritic‐monzonitic material and crystal clasts, the matrix also contains lithic clasts with zoned pigeonite and augite plus two feldspars, microbasaltic clasts, vitrophyric and microcrystalline spherules, and shards. The clast‐laden melt rocks contain clump‐like aggregates of orthopyroxene surrounded by aureoles of plagioclase. Some shards of vesicular melt rocks resemble the pyroxene‐plagioclase clump‐aureole structures. Submicron size matrix grains show some triple junctions, but most are irregular with high intergranular porosity. The noritic‐monzonitic rocks contain exsolved pyroxenes and perthitic intergrowths, and cooled more slowly than rocks with zoned‐pyroxene or fine grain size. Noritic material contains orthopyroxene or inverted pigeonite, augite, calcic to intermediate plagioclase, and chromite to Cr‐bearing magnetite; monzonitic clasts contain augite, sodic plagioclase, K feldspar, Ti‐bearing magnetite, ilmenite, chlorapatite, and zircon. These feldspathic rocks show similarities to some rocks at Gale Crater like Black Trout, Mara, and Jake M. The most magnesian orthopyroxene clasts are close to ALH 84001 orthopyroxene in composition. All these materials are enriched in siderophile elements, indicating impact melting and incorporation of a projectile component, except for Ni‐poor pyroxene clasts which are from pristine rocks. Clast‐laden melt rocks, spherules, shards, and siderophile element contents indicate formation of NWA 7533 as a regolith breccia. The zircons, mainly derived from monzonitic (melt) rocks, crystallized at 4.43 ± 0.03 Ga (Humayun et al. ) and a 147 Sm‐ 143 Nd isochron for NWA 7034 yielding 4.42 ± 0.07 Ga (Nyquist et al. ) defines the crystallization age of all its igneous portions. The zircon from the monzonitic rocks has a higher Δ 17 O than other Martian meteorites explained in part by assimilation of regolith materials enriched during surface alteration (Nemchin et al. ). This record of protolith interaction with atmosphere‐hydrosphere during regolith formation before melting demonstrates a thin atmosphere, a wet early surface environment on Mars, and an evolved crust likely to have contaminated younger extrusive rocks. The latest events recorded when the breccia was on Mars are resetting of apatite, much feldspar and some zircons at 1.35–1.4 Ga (Bellucci et al. ), and formation of Ni‐bearing pyrite veins during or shortly after this disturbance (Lorand et al. ).
Abstract Konservat‐Lagerstätten are seen as snapshots of past biodiversity for a given location and time. However, processes leading to the exceptional morphological preservation of fossils in these deposits remain incompletely understood. This results in a deficient assessment of taphonomic biases and limits the robustness/relevance of palaeobiological reconstructions. Here, we report the mineralogical characterization of crustacean fossils preserved within carbonate‐rich concretions from the Jurassic Konservat‐Lagerstätte of La Voulte‐sur‐Rhône (Ardèche, France). The combination of SEM ‐ EDS , TEM , synchrotron‐based XRF , XRD and XANES allows the mineralogical phases composing these fossils (i.e. fluorapatite, Fe‐sulfides (pyrite, pyrrhotite) and Mg‐calcite) and the surrounding matrix (i.e. Mg‐calcite, clays and detrital silicates) to be identified. Fluorapatite and pyrite (and pyrrhotite) precipitated during decay under anoxic conditions, replacing delicate organic structures and preserving anatomical details. These mineral structures were subsequently consolidated by a Mg‐calcite cement. Of note, histologically similar tissues were replaced by the same mineral phases, confirming that fossilization (in La Voulte) occurred rapidly enough to be influenced by tissue composition. Altogether, the present study shows that exceptional preservation requires fast biodegradation, thereby confirming recent experimental evidence.
Assessing the biogenicity of Precambrian putative remnants of life requires solid criteria. Among possible criteria, searching for evidence of pristine biological signatures and identifying various biological organic matter (OM) precursors in close association with microfossil morphology are of interest. Nano-scale Secondary Ion Mass Spectrometry (NanoSIMS) can provide a quantitative geochemical proxy at the scale of the individual microfossil but its use has remained limited because of potential analytical biases related to matrix effects and microtopography that may result in inaccurate NanoSIMS-derived measurement. No study so far has assessed whether these potential analytical biases were strong enough to preclude any identification of pristine OM degradation products and of organic precursors in ancient sediments. In this study, we characterized the geochemical composition of organic-walled microfossils from the early Neoproterozoic Liulaobei Formation in North China using NanoSIMS. The 12CH−/12C2− ionic ratio allows us to distinguish filament from spheroid acritarchs, revealing the co-occurrence of two distinct pristine OM signatures that differ by their H and/or aliphatic contents. In addition, NanoSIMS data show that morphological degradation was tightly linked to a loss of H and/or hydrogenated organic compounds in spheroid acritarchs. In contrast, in situ N/C atomic ratios are homogeneous across all organic-walled microfossils studied. Although highly coherent with Proterozoic N/C atomic ratios from the literature, such homogeneity may alternatively reflect (i) a similar N content for different organic precursors or (ii) an extensive homogenization related to early degradation. Overall, these data obtained on microfossils from the Proterozoic Liulaobei Formation are the first to demonstrate that the quantitative capability of NanoSIMS can be used to track ancient OM precursors and to probe the effects of degradation on pristine OM. These findings open up tremendous perspectives and put forward new criteria for assessing the biogenicity of the putative early traces of life found in Archean metasediments.
