It is generally believed that the Martian mantle and core are rich in sulfur and that shergottites originated from sulfide-saturated magma. However, recent work suggests that the high FeO contents ...would require very high S concentrations in shergottite parent magmas at sulfide saturation. Here we combine new and published data on chalcophile elements in shergottites, nakhlites and ALH84001 to constrain the sulfide saturation state of the parent magmas and the chalcophile element concentrations in their mantle sources.
Regardless of the MgO content and the long-term depletion history of incompatible lithophile elements as indicated by initial ε143Nd, different groups of shergottites display limited variations in ratios of Pt, Pd, Re, Cu, S, Se and Te. The emplacement of most shergottites within the crust and limited variations of ratios of chalcophile elements with substantial differences in volatility during eruption (e.g., Cu/S, Cu/Se and Pt/Re) indicate little degassing losses of S, Se, Te and Re from shergottites. Limited variations in ratios of elements with very different sulfide–silicate melt partition coefficients and negative correlations of chalcophile elements with MgO require a sulfide-undersaturated evolution of the parent magmas from mantle source to emplacement in the crust, consistent with the FeO-based argument. Sulfide petrography and the komatiite-like fractionation of platinum group elements (PGE) in shergottites also support this conclusion. The absence of accumulated sulfides in the ancient Martian cumulate ALH84001 results in very low contents of PGE, Re, Cu, Se and Te in this meteorite, hinting that sulfide-undersaturated magmas may have occurred throughout the Martian geological history. The negative correlation of Cu and MgO contents in shergottites suggests approximately 2±0.4(1s) μg/g Cu in the Martian mantle. The ratios of Cu, S, Se and Te indicate 360±120 μg/g (1s) S, 100±27 ng/g (1s) Se and 0.50±0.25 ng/g (1s) Te in the Martian mantle. At such low S concentrations, all S in Martian mantle sources may dissolve in basaltic melts that form at >5 % partial melting.
Assuming equilibrium metal–silicate partitioning, and provided that the compositional model of the Martian mantle based on SNC meteorites is correct, Martian mantle inventories of Cu, S and Se were mostly established by core formation and the Martian core should contain <5–10 wt.% S only (depending on the choice of metal–silicate partition coefficients). The low S content in the Martian interior is consistent with the low Zn content in the Martian mantle, which indicates about 5 wt.% S in the core. In contrast, the highly siderophile PGE, Re and Te were added to the mantle by late accreted material after the Martian core formed. The near chondritic PGE ratios and the very low ratio of volatile Te to refractory PGE reflect a strongly volatile element-depleted late veneer and imply that the delivery of Martian water, presumably from carbonaceous chondrite like materials, must have occurred before accretion of the late veneer, likely within 2–3 million years after formation of the solar system.
•Ratios of Cu, S, Se, Te, Re, Pt and Pd in Martian meteorites are relatively constant.•Martian meteorites show very limited eruptive losses of volatile Re, S, Se and Te.•The parent magmas of most Martian meteorites were sulfide-undersaturated.•Martian mantle and core have a low sulfur content.•Low Te/PGE ratios in Martian meteorites reflect a strongly volatile element-depleted Martian late veneer.
The Earth’s mantle has a complex history of partial melting and melt-peridotite reaction that have redistributed Ca and other elements between residues and melting products. Given the considerable Ca ...isotopic variation reported in mantle rocks, evaluation of the fractionation of stable Ca isotopes in magmatic processes in the mantle is critical to decode mantle evolution and the effect of recycled materials. We have performed precise and accurate Ca isotopic analyses on a series of well-characterized spinel-facies mantle peridotites (lherzolite, harzburgite and dunite, n = 29), pyroxenites (websterite, clinopyroxenite and orthopyroxenite, n = 15) and their mineral constituents (n = 8) from the Balmuccia and Baldissero peridotite massifs of the Ivrea Zone in the Italian Alps. These peridotites underwent variable degrees of melting and melt-peridotite reaction, whereas the pyroxenites are mainly the products of melt-peridotite reaction and crystallization of migrating basic melts from the asthenosphere. The lherzolites from Balmuccia and Baldissero show δ44/40Ca values of 0.94 ± 0.11‰ (2sd, n = 22), which are uniform within long-term external reproducibility (±0.14‰, 2sd). The δ44/40Ca values of the harzburgites (0.83‰ to 0.92‰) do not differ from those of lherzolites, including those with a history of intensive melt-peridotite reaction to form replacive dunites. The websterites and spinel clinopyroxenites display δ44/40Ca of 0.86 ± 0.10‰ (n = 14), within the range of the lherzolites and harzburgites. The indistinguishable δ44/40Ca among these very diverse mantle rocks is the consequence of the overwhelming control of stable Ca isotopes by clinopyroxene in the magmatic processes involved, because clinopyroxene dominates the budget of Ca (>90% for harzburgites; 93% to 99% for lherzolites, websterites and clinopyroxenites). Only the clinopyroxene-poor (<3 wt.%) dunites and orthopyroxenite show higher δ44/40Ca (e.g., 1.11‰ to 1.81‰ and 1.13‰, respectively). This reflects the signatures of olivine and orthopyroxene which display higher δ44/40Ca than clinopyroxene. These results and modeling suggest that negligible Ca isotope fractionation (<0.12‰) occurs during <25% of partial melting, silicate melt-peridotite reaction, or magmatic differentiation in the upper mantle. Only highly depleted harzburgite residues that formed by >25% melting and replacive dunites tend to display slightly heavier Ca isotopic compositions. Consequently, irrespective of their magmatic history, most fertile mantle rocks from different geological settings display a homogenous Ca isotope composition, summarized as, δ44/40Ca of 0.94 ± 0.10‰ (2sd, n = 47) for the Earth’s mantle. The deviations in Ca isotopic variations observed in other mantle rocks may be attributed to kinetic isotope fractionation and metasomatism by melts with isotopic compositions influenced by recycled crustal materials.
The concentrations of Rh, Au and other highly siderophile elements (HSE: Re, Os, Ir, Ru, Pt, Rh, Pd and Au), and
187Os/
188Os isotope ratios have been determined for samples from peridotite massifs ...and xenoliths in order to further constrain HSE abundances in the Earth's mantle and to place constraints on the distributions processes accounting for observed HSE variations between fertile and depleted mantle lithologies. Concentrations of Re, Os, Ir, Ru, Pt and Pd were determined by isotope dilution ICP-MS and N-TIMS. The monoisotopic elements Rh and Au were quantified by standardization relative to the concentrations of Ru and Ir, respectively, and were determined from the same digestion aliquot as other HSE. The measurement precision of the concentration data under intermediate precision conditions, as inferred from repeated analyses of 2
g test portions of powdered samples, is estimated to be better than 10% for Rh and better than 15% for Au (1
s).
Fertile lherzolites display non-systematic variation of Rh concentrations and constant Rh/Ir of 0.34
±
0.03 (1
s,
n
=
57), indicating a Rh abundance for the primitive mantle of 1.2
±
0.2
ng/g. The data also suggest that Rh behaves as a compatible element during low to moderate degrees of partial melting in the mantle or melt–mantle interaction, but may be depleted at higher degrees of melting. In contrast, Au concentrations and Au/Ir correlate with peridotite fertility, indicating incompatible behaviour of Au during magmatic processes in the mantle. Fertile lherzolites display Au/Ir ranging from 0.20 to 0.65, whereas residual harzburgites have Au/Ir <
0.20. Concentrations of Au and Re are correlated with each other and suggest similar compatibility of both elements. The primitive mantle abundance of Au calculated from correlations displayed by Au/Ir with Al
2O
3 and Au with Re is 1.7
±
0.5
ng/g (1
s).
The depletion of Pt, Pd, Re and Au relative to Os, Ir, Ru and Rh displayed by residual harzburgites, suggests HSE fractionation during partial melting. However, the HSE abundance variations of fertile and depleted peridotites cannot be explained by a simple fractionation process. Correlations displayed by Pd/Ir, Re/Ir and Au/Ir with Al
2O
3 may reflect refertilization of previously melt depleted mantle rocks due to reactive infiltration of silicate melts.
Relative concentrations of Rh and Au inferred for the primitive mantle model composition are similar to values of ordinary and enstatite chondrites, but distinct from carbonaceous chondrites. The HSE pattern of the primitive mantle is inconsistent with compositions of known chondrite groups. The primitive mantle composition may be explained by late accretion of a mixture of chondritic with slightly suprachondritic materials, or alternatively, by meteoritic materials mixed into mantle with a HSE signature inherited from core formation.
► Precise concentration data for Rh and Au together with other HSE and
187Os/
188Os. ► Rhodium behaves compatible during magmatic processes in the mantle. ► Gold behaves incompatible indicated by correlation of Au and Au/Ir with Al
2O
3. ►Primitive mantle (PM) abundances: 1.2
±
0.2
ng/g Rh, 1.7
±
0.5
ng/g Au. ► Rh/Ir
PM and Au/Ir
PM similar to ordinary and enstatite chondrites.
Various lines of evidence suggest that material isotopically similar to enstatite chondrites may have accreted to the terrestrial planets. However, the enrichment of light Si isotopes in bulk ...enstatite chondrites is not easy to reconcile with the heavy Si isotopic composition of the Bulk Silicate Earth (BSE). To investigate the origin of the light Si isotopic composition of enstatite chondrites, we have obtained in situ Si isotope data and simultaneously major- and trace element data in silicate and metal phases of chondrules, a metal-troilite spherule, and matrix from the enstatite chondrites Sahara 97072 (EH3) and Indarch (EH4) using laser ablation split stream-ICP-MS, which combines femto-second LA-MC-ICP-MS and Quadrupole-ICP-MS. Silicates in chondrules show variations in δ30Si (‰ variations of 30Si/28Si relative to NBS-28) ranges from −1.06 ± 0.13‰ (2 S.E.) to −0.38 ± 0.11‰. δ30Si in matrix silicates ranges from −0.96 ± 0.18‰ to −0.22 ± 0.12‰. The δ30Si-value of silicate phases varies independently of Mg/Si, ruling out simple equilibrium condensation from nebular gas. Some silicates in both enstatite chondrites have δ30Si-values like CI chondrites, whereas Si in other silicates is isotopically lighter, suggesting that the precursor materials of EH chondrites were already depleted in heavy Si isotopes.
The metal phases in the matrix show average δ30Si of −6.0 ± 0.6‰. In spite of different metamorphic grades, the fractionation of Si isotopes between matrix metal and silicates in Sahara 97072 and Indarch shows no systematic differences, and thus no re-equilibration of Si isotopes occurred between silicates and metal at metamorphic temperatures below 900 K. The δ30Si-value of metal from a metal-troilite spherule from Sahara 97072 (−8.24 ± 0.12‰) is lower than that of matrix metals. These differences were likely inherited from different formation environments of matrix- and spherule metal. If metal formation occurred under equilibrium conditions, then matrix metal may have formed at higher temperatures than the MTS metal. or at similar temperatures but slightly lower oxygen fugacities, or the MTS metal equilibrated with gas or silicates which were not incorporated into EH chondrites because they were lost from the EH chondrite formation region. Alternatively, the differences in δ30Si of different metals could also reflect variable kinetic isotope fractionation during the formation of metal and exsolution of perryite.
The considerably lower δ30Si-values of bulk EH chondrites compared to CI- and other chondrites partly reflects the presence of Si bearing metal and partly silicates with isotopically light Si. The latter indicate loss of a heavy Si-rich silicate component from the EH3 formation region, presumably together with refractory elements. Although the Si isotopic composition of bulk EH chondrites precludes that these represent major building material of the Earth, the combination of complementary heavy Si isotope- and refractory element-enriched reduced materials and carbonaceous or ordinary chondrites could provide a match for the heavy Si isotopic composition of Earth.
The occurrence of shallow and deep-water sedimentary facies has established the Yangtze Platform in South China as a key site for the study of Neoproterozoic ocean oxidation and Ediacaran animal ...evolution following the Marinoan glaciation. The Yanwutan section in Hunan Province is one of the few coherent sections on the Yangtze Platform where Ediacaran deep-water carbonate sediments (predominantly dolostones) are preserved together with organic carbon-rich shales. Here we present new major and trace element abundance data as well as Sr-, O- and C-isotope compositions of leachates from carbonates of the Doushantuo Formation. We evaluate the role of diagenetic modification of the carbonate rocks and constrain the redox evolution of Ediacaran seawater in space and time. 87Sr/86Sr systematically varies with δ18Ocarb, Sr- and Ba abundances, indicating variable but mostly strong modification of fluid-mobile elements by continental basin fluids. In contrast, REE+Y patterns have preserved seawater-like compositions. Cap dolostones (unit I) on top of the Nantuo diamictites differ from cap dolostones at shallow-water sections on the Yangtze Platform in that they show no Ce-anomalies, and little alteration near the top (87Sr/86Sr=0.7078, δ18O=−4.0, δ13Ccarb=1.1), suggesting that δ13Ccarb and δ18O of cap dolostones at many other sections were compromised by hydrothermal alteration. The overlying organic carbon poor micritic dolostone (unit II) shows negative Ce-anomalies that disappear towards the top of the unit. No Ce-anomalies occur in subsequent organic carbon-rich muddy dolostone units (units III to IV). These observations, enrichments in TOC that correlate with variations in redox-sensitive metals in the carbonates, negative δ13Ccarb in units II to IV and the decoupling of δ13Ccarb from δ13Corg argue for the existence of mostly anoxic deep-water at the Yangtze passive continental margin during the Ediacaran. The negative Ce-anomalies at the base of unit II (with negative δ13Ccarb) may reflect fluctuations towards suboxic or oxic conditions or an allochthonous origin of this unit. However, trace metal enrichments in carbonates of the same unit argue for reducing conditions in pore-water, whereas the carbonates may have preserved the REE+Y signatures inherited from suboxic- to oxic seawater. The trace element and negative δ13Ccarb values in units II to IV are consistent with a stratified basin model with a large partially remineralised organic matter reservoir in anoxic bottom and pore-waters.
The conditions at which melt percolation and reactive infiltration of depleted mantle peridotites fractionate highly siderophile elements (HSE) and cause re-equilibration of 187Os/188Os in mantle ...rocks are still poorly constrained. In a comparative study of the Paleozoic Balmuccia (BM) and Baldissero (BD) peridotite tectonites (Ivrea-Verbano Zone, Northern Italy), the influence of partial melting and melt infiltration on abundances of HSE, chalcogens (S, Se and Te) and 187Os/188Os have been studied.
At BM, Re depletion ages (TRD) of lherzolites and replacive dunites display a uniform distribution with a maximum near 400–500Ma. BD peridotites also display a Paleozoic distribution peak but a significant number of samples yielded Proterozoic TRD. The predominance of Paleozoic Re depletion ages in both bodies is consistent with Sm–Nd ages and the late Paleozoic magmatic and geodynamic evolution of the Ivrea-Verbano Zone. The different extents of preservation of ancient 187Os/188Os in BM and BD peridotites are interpreted to reflect different degrees of isotopic homogenization and chemical re-equilibration with incompatible element-depleted infiltrating melt during the Paleozoic. The differences between the two bodies are also reflected by differences in HSE and chalcogen abundances, with BD displaying large scatter among HSE patterns, slight re-enrichment of Re relative to Au, and linear trends of Pd, Se and Te with Al2O3. The differences in distributions of model ages and heterogeneity in HSE abundances support the view that the lithophile element, HSE and chalcogen variations of different suites of lherzolites likely reflect different extents of reactive melt infiltration in mantle peridotites, with partial re-equilibration and melt extraction in open system environments. However, the variable re-equilibration of BM and BD lherzolites apparently did not produce significant differences in HSE ratios such as Os/Ir, Ru/Ir, Rh/Ir, and Pd/Pt, which are in the range of primitive mantle values, whereas Au, Re and S are somewhat depleted.
The good linear correlation of S with Al2O3 in both suites reflects sulfide removal controlled by sulfur solubility in silicate melt, or co-precipitation with pyroxenes and spinel, and indicates very similar bulk partition coefficients for S and Al. S/Se and Se/Te in the lherzolites change little with decreasing Al2O3. Results for BM lherzolites are consistent with sulfide–silicate melt partitioning as the dominant control on abundances of the HSE, S, Se and Te during low to moderate degrees of melt extraction (DPt>DPd>DTe⩾DSe⩾DS≈DRe).
Replacive dunites at Balmuccia have low abundances of Re, Au, Pd and chalcogens, but variable and higher abundances of Os, Ir and Ru, high S/Se and Se/Te, yet 187Os/188Os similar to BM lherzolites. The residual HSE and chalcogen compositions differ from those in dunites of subduction-related ophiolites. The composition and contact relations of the BM dunites with the host rocks likely reflect focused flow of sulfur-undersaturated melt after open system melting and re-equilibration of the lherzolites. The compositional record of the Balmuccia massif thus reflects the composition of different types of melts and their interaction with the peridotites at different P–T conditions.
Abundances of highly siderophile elements (HSE: Re, platinum group elements and Au), chalcogens (Te, Se and S), 187Os/188Os and the major and minor elements Mg, Ca, Mn, Fe, Ni and Co were determined ...in the components of Sahara 97072 (EH3, find) and Kota Kota (EH3, find) in order to understand the element fractionation processes. In a 187Re–187Os isochron diagram, most magnetic components lie close to the 4.56Ga IIIA iron meteorite isochron, whereas most other components show deviations from the isochron caused by late redistribution of Re, presumably during terrestrial weathering. Metal- and sulfide rich magnetic fractions and metal-sulfide nodules are responsible for the higher 187Os/188Os in bulk rocks of EH chondrites compared to CI chondrites. The HSE and chalcogens are enriched in magnetic fractions relative to slightly magnetic and nonmagnetic fractions and bulk compositions, indicating that Fe–Ni metal is the main host phase of the HSE in enstatite chondrites. HSE abundance patterns indicate mixing of two components, a CI chondrite like end member and an Au-enriched end member. Because of the decoupled variations of Au from those of Pd or the chalcogens, the enrichment of Au in EH metal cannot be due to metal–sulfide–silicate partitioning processes. Metal and sulfide rich nodules may have formed by melting and reaction of pre-existing refractory element rich material with volatile rich gas. A complex condensation and evaporation history is required to account for the depletion of elements having very different volatility than Au in EH chondrites. The depletions of Te relative to HSE, Se and S in bulk EH chondrites are mainly caused by the depletion of Te in metal. S/Se and S/Mn are lower than in CI chondrites in almost all components and predominantly reflect volatility-controlled loss of sulfur. The latter most likely occurred during thermal processing of dust in the solar nebula (e.g., during chondrule formation), followed by the non-systematic loss of S during terrestrial weathering.
Enstatite achondrites (including aubrites) are the only differentiated meteorites that have similar isotope compositions to the Earth-Moon system for most of the elements. However, the origin and ...differentiation of enstatite achondrites and their parent bodies remain poorly understood. Here, we report high-precision mass-independent and mass-dependent Cr isotope data for 10 enstatite achondrites, including eight aubrites, Itqiy and one enstatite-rich clast in Almahatta Sitta, to further constrain the origin and evolution of their parent bodies. The ε54Cr (per 10,000 deviation of the mass bias corrected 54Cr/52Cr ratio from a terrestrial standard) systematics define three groups: main-group aubrites with ε54Cr = 0.06 ± 0.12 (2SD, N = 7) that is similar to the enstatite chondrites and the Earth-Moon system, Shallowater aubrite with ε54Cr = −0.12 ± 0.04 and Itqiy-type meteorites with ε54Cr = −0.26 ± 0.03 (2SD, N = 2). This shows that there were at least three enstatite achondrite parent bodies in the Solar System. This is confirmed by their distinguished mass-dependent Cr isotope compositions (δ53Cr values): 0.24 ± 0.03‰, 0.10 ± 0.03‰ and −0.03 ± 0.03‰ for main-group, Shallowater and Itqiy parent bodies, respectively. Aubrites are isotopically heavier than chondrites (δ53Cr = −0.12 ± 0.04‰), which likely results from the formation of an isotopically light sulfur-rich core. We also obtained the abundance of the radiogenic 53Cr (produced by the radioactive decay of 53Mn, T1/2 = 3.7 million years). The radiogenic ε53Cr excesses correlate with the 55Mn/52Cr ratios for aubrites (except Shallowater and Bustee) and also the Cr stable isotope compositions (δ53Cr values). We show that these correlations represent mixing lines that also hold chronological significance since they are controlled by the crystallization of sulfides and silicates, which mostly reflect the main-group aubrite parent body differentiation at 4562.5 ± 1.1 Ma (i.e., 4.8 ± 1.1 Ma after Solar System formation). Furthermore, the intercept of these lines with the ordinate axis which represent the initial ε53Cr value of main-group aubrites (0.50 ± 0.16, 2σ) is much higher than the average ε53Cr value of enstatite chondrites (0.15 ± 0.10, 2SD), suggesting an early sulfur-rich core formation that effectively increased the Mn/Cr ratio of the silicate fraction of the main-group aubrite parent body.
PDF
