Chalcophile Element Constraints on the Sulfur Content of the Martian Mantle

The sulfur content of the Martian mantle is critical to understanding volcanic volatiles supplied to the surface of Mars and possibly climate. In the absence of Martian mantle rocks, sulfur content of the mantle has been inferred from S contents of Martian meteorites or from sedimentary sulfate abundances. Estimates of the sulfur content of the Martian mantle vary from 390-2,000 ppm, all of which are higher than that of the terrestrial mantle (~250 ppm;). Residual sulfide in the Martian mantle controls the distribution of chalcophile elements during partial melting. In this study, we report new analyses of Martian meteorites, and use the incompatible behavior of As, Tl and Pb to infer the sulfide mode of the Martian mantle using a different set of assumptions than those of prior studies

Do nebular fractionations, evaporative losses, or both, influence chondrule compositions?

We have made observations and performed heating experiments to determine the relative importance of several processes which may have influenced the compositions of chondrules. As heating destroys nuclei, the number density of olivine and pyroxene crystals gives an indication of the extent of melting. We determined number densities of Semarkona type I chondrules and converted them to nominal grain size, for use as a measure of intensity of heating. Bulk compositions of the chondrules show correlations with nominal grain size. Na, K, Fe, Ni, P and S decrease as grain size (degree of melting) increases, and we interpret this as evidence of evaporative loss. The evidence is less clear for Mn, Cr and Si. SiO_2/MgO ratios show very large variations even in fine-grained type I chondrules containing FeS, and we interpret those variations as due to nebular fractionations affecting precursors. Experiments show that Na and S losses increase with higher temperatures and lower cooling rates. It is hard to preserve any sulfide at all, without flash heating. Na, however, can be retained at close to chondritic levels (as in type II chondrules) with flash heating and high cooling rate, provided also that the oxygen fugacity is high. Type II chondrules can retain much more Na than type I under identical thermal conditions, because of higher fO_2 (either due to non-nebular gas or possibly internal buffering by FeO content) and melt structure (higher SiO_2/MgO). Gas reduction experiments show that type II compositions can be converted to IB by Fe loss, but evaporative loss of SiO_2 (so as to approach IA composition) is not achieved without prolonged isothermal heating. Precursors of type I and II chondrules were probably close to chondritic in composition, but with higher Fa in the type II case. They consisted of olivine, pyroxene, plagioclase, Fe (Ni) S and carbon compounds, probably with insignificant metal. Sulfur loss generated much chondrule metal in ordinary chondrites. C is a possible alternative to gas reduction to explain dusty relict grains and the lower olivine Fa in the more melted type I chondrules. We agree with J. N. GROSSMAN and J. T. WASSON (Geochim. Cosmochim. Acta, 47,759,1983) that variations in Mg/Si are due to nebular fractionations and with S. HUANG et al. (Icarus, 122,316,1996) that variations in Na and Fe in type I chondrules are mainly due to evaporative losses

Paris: The slightly altered, slightly metamorphosed CM that bridges the gap between CMs and Cos

A fresh, 1.3 kilo stone was found in Paris. It is a CM chondrite with metal, Fe-sulfide, FeS-rich PCPs and relict mesostasis and is ~3.0 ± 0.1. Petrographic and oxygen isotope evidence indicates that it has affinities with the CO chondrites

Tin Abundances Require that Chassignites Originated from Multiple Magmatic Bodies Distinct from Nakhlites

Meteorites from Mars lack field context but chemical and chronologic studies have revealed remarkable links between nakhlites and chassignites. A widely held consensus is that nakhlites and chassignites originated from a large, single differentiated flow or shallow intrusive [1-5]. An Ar-Ar study assumed multiple flows based on resolvable age differences between meteorites [6], but did not address the possibility of differential cooling in a large, shallowly emplaced intrusion [1]. REE abundances in pyroxenes from nakhlites and Chassigny led [7] to argue for derivation of these rocks from distinct magmas. Volatile abundances (F, Cl, OH) in chlorapatites indicated that the entire suite of nakhlites and chassignites experienced hydrothermal interaction with a single fluid supporting a single body origin [4]. The discovery of a new chassignite, NWA 8694, extended the Mg# range from 80-54, providing a closer link to nakhlites but revealed the petrological difficulty of fractionating a single body of liquid to yield a series of olivine cumulates with such a large Mg# range [8]. When mafic magmas are emplaced into the crust, crustal assimilation can impart distinct elemental signatures if the country rock has experienced sedimentary or hydrothermal processing [9]. In this work, we used Sn abundances of nakhlites and chassignites to show that these rocks were crystallized from distinct magma batches, providing vital contextual clues to their origin

Formation of oxygen isotope reservoirs by mixing chondritic components

Published versio

An accretionary origin for ordinary chondrite groups

Accepted versio

The Germanium Dichotomy in Martian Meteorites

Germanium is a moderately volatile and siderophile element that follows silicon in its compatibility during partial melting of planetary mantles. Despite its obvious usefulness in planetary geochemistry germanium is not analyzed routinely, with there being only three prior studies reporting germanium abundances in Martian meteorites. The broad range (1-3 ppm) observed in Martian igneous rocks is in stark contrast to the narrow range of germanium observed in terrestrial basalts (1.5 plus or minus 0.1 ppm). The germanium data from these studies indicates that nakhlites contain 2-3 ppm germanium, while shergottites contain approximately 1 ppm germanium, a dichotomy with important implications for core formation models. There have been no reliable germanium abundances on chassignites. The ancient meteoritic breccia, NWA 7533 (and paired meteorites) contains numerous clasts, some pristine and some impact melt rocks, that are being studied individually. Because germanium is depleted in the Martian crust relative to chondritic impactors, it has proven useful as an indicator of meteoritic contamination of impact melt clasts in NWA 7533. The germanium/silicon ratio can be applied to minerals that might not partition nickel and iridium, like feldspars. We report germanium in minerals from the 3 known chassignites, 2 nakhlites and 5 shergottites by LAICP- MS using a method optimized for precise germanium analysis

Experimental Behavior of Sulfur Under Primitive Planetary Differentiation Processes, the Sulfide Formations in Enstatite Meteorites and Implications for Mercury.

Enstatite meteorites are the most reduced naturally-occuring materials of the solar system. The cubic monosulfide series with the general formula (Mg,Mn,Ca,Fe)S are common phases in these meteorite groups. The importance of such minerals, their formation, composition and textural relationships for understanding the genesis of enstatite chondrites (EC) and aubrites, has long been recognized (e.g. [1]). However, the mechanisms of formation of these sulfides is still not well constrained certainly because of possible multiple ways to produce them. We propose to simulate different models of formation in order to check their mineralogical, chemical and textural relevancies. The solubility of sulfur in silicate melts is of primary interest for planetary mantles, particularly for the Earth and Mercury. Indeed, these two planets could have formed, at least partly, from EC materials (e.g. [2, 3, 4]). The sulfur content in silicate melts depends on the melt composition but also on pressure (P), temperature (T) and oxygen fugacity fO2. Unfortunately, there is no model of general validity in a wide range of P-T-fO2-composition which describes precisely the evolution of sulfur content in silicate melts, even if the main trends are now known. The second goal of this study is to constrain the sulfur content in silicate melts under reducing conditions and different temperatures

Anticancer and antibacterial potential of robust Ruthenium(II) arene complexes regulated by choice of α-diimine and halide ligands

Several complexes of general formula [Ru(halide)(η6-p-cymene)(α-diimine)]+, in the form of nitrate, triflate and hexafluorophosphate salts, including a newly synthesized iodide compound, were investigated as potential anticancer drugs and bactericides. NMR and UV–Vis studies evidenced remarkable stability of the complexes in water and cell culture medium. In general, the complexes displayed strong cytotoxicity against A2780 and A549 cancer cell lines with IC50 values in the low micromolar range, and one complex (RUCYN) emerged as the most promising one, with a significant selectivity compared to the non-cancerous HEK293 cell line. A variable affinity of the complexes for BSA and DNA binding was ascertained by spectrophotometry/fluorimetry, circular dichroism, electrophoresis and viscometry. The performance of RUCYN appears associated to enhanced cell internalization, favored by two cyclohexyl substituents, rather than to specific interaction with the evaluated biomolecules. The chloride/iodide replacement, in one case, led to increased cellular uptake and cytotoxicity at the expense of selectivity, and tuned DNA binding towards intercalation. Complexes with iodide or a valproate bioactive fragment exhibited the best antimicrobial profiles

A Two Gigayear History of Germanium Outgassing from Shergottites

Germanium (Ge) and Zn enrichment in martian sedimentary rocks has been reported from rocks at Gale Crater, showing concentrations of Ge from tens to hundreds ppm [1]. The Ge concentrations in martian meteorites are significantly lower (0.5-2.5 ppm) [2]. Our recent studies [3-4] have revealed that Ge is lost from shergottites due to volatility. Recent experimental studies confirm that Ge and Zn are both significantly volatile under magmatic conditions [5-7]. Further, Ge is moderately incompatible during magmatic differentiation [8] so Ge contents in olivines or pyroxenes increase during igneous fractionation in nakhlites and chassignites [4]. Shergottites for which Ge abundances had been determined included rocks with ages of 150-600 Ma, while the enrichments reported from Gale Crater rocks likely occurred over 3 Ga ago. The recent discovery of two unpaired ancient (2.4 Ga) depleted shergottites, NWA 7635 [9] and NWA 8159 [10], afforded the prospect of obtaining an extended history of martian volcanic outgassing. Both of the ancient shergottites are depleted in incompatible elements and share a similar GCR exposure age to younger depleted shergottites implying derivation from a single, long-lived (>2 Ga) volcanic center [9]