The role of sulfides in the fractionation of highly siderophile and chalcophile elements during the formation of martian shergottite meteorites

1Raphael J. Baumgartner, 1Marco L. Fiorentini, 2Jean-Pierre Lorand, 3,4David Baratoux, 5Federica Zaccarini, 6Ludovic Ferrière, 7Marko K. Prašek,8Kerim Sener
Geochimica et Cosmochimica Acta (in Press) Link to Article [http://doi.org/10.1016/j.gca.2017.04.011]
1Centre for Exploration Targeting, School of Earth Sciences, ARC Centre of Excellence for Core to Crust Fluid Systems, University of Western Australia, 6009 Crawley, Australia
2Laboratoire de Planétologie et Géodynamique de Nantes, Université de Nantes and Centre National de la Recherche Scientifique, UMR 6112 44322 Nantes, France
3Géosciences Environnement Toulouse, CNRS, IRD and University of Toulouse, 31400 Toulouse, France
4Institut Fondamental d’Afrique Noire Cheikh Anta Diop, 5005 Dakar, Senegal
5Department of Applied Geological Sciences and Geophysics, University of Leoben, 8700 Leoben, Austria
6Natural History Museum Vienna, 1010 Vienna, Austria
7McGill University, Department of Earth and Planetary Sciences, H3A 0E8, Montreal, Canada
8Matrix Exploration Pty Ltd, 6112 Armadale, Australia
Copyright Elsevier

The shergottite meteorites are ultramafic to mafic igneous rocks whose parental magmas formed from partial melting of the martian mantle. This study reports in-situ laser ablation inductively coupled plasma mass spectrometry analyses for siderophile and chalcophile major and trace elements (i.e., Co, Ni, Cu, As, Se, Ag, Sb, Te, Pb, Bi, and the highly siderophile platinum-group elements, PGE: Os, Ir, Ru, Rh, Pt and Pd) of magmatic Fe-Ni-Cu sulfide assemblages from four shergottite meteorites. They include three geochemically similar incompatible trace element- (ITE-) depleted olivine-phyric shergottites (Yamato-980459, Dar al Gani 476 and Dhofar 019) that presumably formed from similar mantle and magma sources, and one distinctively ITE-enriched basaltic shergottite (Zagami). The sulfides in the shergottites have been variably modified by alteration on Earth and Mars, as well as by impact shock-shock related melting/volatilization during meteorite ejection. However, they inherit and retain their magmatic PGE signatures. The CI chondrite-normalized PGE concentration patterns of sulfides reproduce the whole-rock signatures determined in previous studies. These similarities indicate that sulfides exerted a major control on the PGE during shergottite petrogenesis. However, depletions of Pt (and Ir) in sulfide relative to the other PGE suggest that additional phases such discrete Pt-Fe-Ir alloys have played an important role in the concentration of these elements. These alloys are expected to have enhanced stability in reduced and FeO-rich shergottite magmas, and could be a common feature in martian igneous systems. A Pt-rich PGM was found to occur in a sulfide assemblage in Dhofar 019. However, its origin may be related to impact shock-related sulfide melting and volatilisation during meteorite ejection. In the ITE-depleted olivine-phyric shergottites, positive relationships exist between petrogenetic indicators (e.g., whole-rock Mg-number) and most moderately to strongly siderophile and chalcophile elements in sulfides. These variations extend to incompatible elements like Te and Pd. The whole-rock concentrations of Pd derived from mass-balance calculations decrease by one order of magnitude in the order Y-980459, DaG 476 and Dhofar 019, and broadly overlap the trends in previously published whole-rock analyses. Mantle heterogeneities, and the timing of sulfide saturation as function of mantle melting and/or magma fractionation following ascent from the mantle, may have been the controlling factors of the siderophile and chalcophile element systematics in the analyzed shergottites.

The origin of volatile element depletion in early solar system material: Clues from Zn isotopes in chondrules

1Emily A. Pringle, 1,2Frédéric Moynier, 2,3Pierre Beck, 4Randal Paniello, 5,6Dominik C. Hezel
Earth and Planetary Science Letters 468. 62-71 Link to Article [http://doi.org/10.1016/j.epsl.2017.04.002]
1Institut de Physique du Globe de Paris, Université Paris Diderot, Sorbonne Paris Cité, CNRS UMR 7154, 1 rue Jussieu, 75238 Paris, France
2Institut Universitaire de France, Paris, France
3Institut d’Astrophysique et de Planétologie de Grenoble, Université Grenoble Alpes, France
4Department of Earth and Planetary Sciences, Washington University in St. Louis, USA
5University of Cologne, Department of Geology and Mineralogy, Zülpicher Str. 49b, 50674 Köln, Germany
6Department of Mineralogy, Natural History Museum, Cromwell Road, London, SW7 5BD, UK
Copyright Elsevier

Volatile lithophile elements are depleted in the different planetary materials to various degrees, but the origin of these depletions is still debated. Stable isotopes of moderately volatile elements such as Zn can be used to understand the origin of volatile element depletions. Samples with significant volatile element depletions, including the Moon and terrestrial tektites, display heavy Zn isotope compositions (i.e. enrichment of 66Zn vs. 64Zn), consistent with kinetic Zn isotope fractionation during evaporation. However, Luck et al. (2005) found a negative correlation between δ66Zn and 1/[Zn] between CI, CM, CO, and CV chondrites, opposite to what would be expected if evaporation caused the Zn abundance variations among chondrite groups.

We have analyzed the Zn isotope composition of multiple samples of the major carbonaceous chondrite classes: CI (1), CM (4), CV (2), CO (4), CB (2), CH (2), CK (4), and CK/CR (1). The bulk chondrites define a negative correlation in a plot of δ66Zn vs 1/[Zn], confirming earlier results that Zn abundance variations among carbonaceous chondrites cannot be explained by evaporation. Exceptions are CB and CH chondrites, which display Zn systematics consistent with a collisional formation mechanism that created enrichment in heavy Zn isotopes relative to the trend defined by CI–CK.

We further report Zn isotope analyses of chondrite components, including chondrules from Allende (CV3) and Mokoia (CV3), as well as an aliquot of Allende matrix. All chondrules are enriched in light Zn isotopes (∼500 ppm on 66Zn/64Zn) relative to the bulk, contrary to what would be expected if Zn were depleted during evaporation, on the other hand the matrix has a complementary heavy isotope composition. We report sequential leaching experiments in un-equilibrated ordinary chondrites, which show sulfides are isotopically heavy compared to silicates and the bulk meteorite by ca. +0.65 per mil on 66Zn/64Zn. We suggest isotopically heavy sulfides were removed from either chondrules or their precursors, thereby producing the light Zn isotope enrichments in chondrules.