A synthesis of geochemical constraints on the inventory of light elements in the core of Mars

Accurate constraints on the light element composition of the Martian core are required for models of the Martian core dynamo, the conditions under which the Martian core formed (i.e. the existence and extent of a magma ocean) and the overall volatile inventory of Mars. Here, we present a synthesis of geochemical constraints on the abundances of light elements S, C and O in the Martian core using mass balance calculations combined with published expressions that predict their high-pressure metal–silicate partitioning behaviour. We incorporate recently proposed bulk S Martian mantle abundances and find that the Martian core must be S-rich, virtually independent of the type of bulk composition considered and the P-T conditions during core-mantle differentiation of Mars. The core contains at least 7 wt % S and may be up to stoichiometric FeS in composition, depending on which P-T conditions (and bulk compositions) are assumed. If bulk Mars was formed from chondritic building blocks, the core S content is constrained to 13.5 ± 3.5 wt.%, in good agreement with geophysical models of the Martian interior and with measured siderophile element depletions in SNC meteorites. Our calculations yield O contents for the Martian core of < 4 wt.%, with the highest concentrations for the highest P-T conditions of Martian core formation. Carbon contents in the Martian core are expected to be low (< 1.4 wt.%) given the abundance of C in chondritic meteorite groups. The calculated solubility limit for C in Fe-Ni-S alloys is higher than calculated core C contents in virtually all cases, suggesting the Martian primitive mantle is not graphite saturated if the bulk Mars C budget is (close to) chondritic. The estimated depletions of volatile elements Se and Te in the Martian interior can be reconciled easily with formation of a Martian S-rich core. This implies that these volatile elements may not have been lost from Mars by degassing in Mars early history. The calculated Martian core S contents cannot be used to distinguish between the two different proposed modes of core crystallization, but do suggest the Martian core may still be fully liquid today

Experimental constraints on the solidification of a nominally dry lunar magma ocean

The lunar magma ocean (LMO) concept has been used extensively for lunar evolution models for decades, but to date the full cooling and crystallization path of the LMO has not been studied experimentally. Here we present results of a high-pressure, high-temperature experimental study of the mineralogical and geochemical evolution accompanying the full solidification of a nominally dry LMO. Experiments used a bulk composition based on geophysical data, and assumed an initial LMO depth of 700 km. The effect of pressure within a deep magma ocean on solidification at different levels in the ocean was explicitly taken into account, by performing experiments at multiple pressures and constant temperature during each solidification step. Results show formation of a deep harzburgite (olivine + low-Ca pyroxene) layer in the first ∼50% of equilibrium crystallization. The crystallising mineral assemblage does not change until plagioclase and clinopyroxene appear at 68 PCS (per cent solid by volume), while low-Ca pyroxene stops forming. Olivine disappears at 83 PCS, and ilmenite and β-quartz start crystallizing at 91 and 96 PCS, respectively. At 99 PCS, we observe an extremely iron-rich (26.5 wt.% FeO) residual LMO liquid. Our results differ substantially from the oft-cited LMO solidification study of Snyder et al. (1992), which was based on a limited number of experiments at a single pressure. Differences include the mineralogy of the deepest sections of the solidified LMO (harzburgitic instead of dunitic), the formation of SiO2 in the lunar interior, and the development of extreme iron enrichment in the last remaining dregs of the LMO. Our findings shed new light on several aspects of lunar petrology, including the formation of felsic and iron-rich magmas in the Moon. Finally, based on our experiments the lunar crust, consisting of the light minerals plagioclase and quartz, would reach a thickness of ∼67.5 km. This is far greater than crustal thickness estimates from recent GRAIL mission gravitational data (34–43 km, Wieczorek et al., 2013). Although the initial depth of the LMO has an effect on the thickness of crust produced, this effect is not large enough to explain this discrepancy. Inefficient plagioclase segregation, trapping of magma in cumulate reservoirs, and Al sequestration in spinel cannot explain the discrepancy either. As plagioclase crystallization can be suppressed by the presence of H2O, this implies that the lunar magma ocean was water-bearing

Thermal Stability of F-Rich Phlogopite and K-Richterite During Partial Melting of Metasomatized Mantle Peridotite With Implications for Deep Earth Volatile Cycles

Phlogopite and K-richterite constitute important carrier phases for H and F in Earth's lithosphere and mantle. The relative importance depends on their stabilities at high pressure and temperature, which in turn depends on bulk composition. Most previous experimental studies focused on the thermal stability of phlogopite and K-richterite were conducted using simplified chemical compositions. Here, partial melting experiments on metasomatized and carbonated, OH ± F-bearing near-natural peridotite were performed at high pressures (2 and 5 GPa) and temperatures (1,100–1,350°C) to assess the thermal stability of F-free versus F-bearing phlogopite and K-richterite. Experimental results demonstrate that the thermal stability of F-bearing phlogopite is increased by >55°C/wt.% F, relative to F-free phlogopite, whereas K-richterite is absent in all experiments with significant degrees of melting (>2%). The thermal stability of phlogopite containing several wt.% F exceeds continental and oceanic geotherms within the upper 150 km. Fluorine-rich phlogopite would therefore be stable in virtually all of the continental lithosphere, only to be decomposed during large, regional melting events such as continental break-up, thereby acting as a major long-term sink for F and/or H. This could even be the case for the oceanic asthenosphere, depending on the oceanic geotherm of the area of interest.ISSN:2169-9313ISSN:0148-0227ISSN:2169-935

Analysis of the CHARM Cu-alloy reference materials using excimer ns-LA-ICP-MS: Assessment of matrix effects and applicability to artefact provenancing

Excimer nano-second laser ablation inductively coupled plasma mass spectrometry (ns-LA-ICP-MS) is an important tool in chemical characterization of Cu alloys. However, variable matrix-induced elemental fractionation in Cu alloys poses a significant challenge. We systematically investigate this issue by analysing the Cultural Heritage Alloy Reference Material Set (CHARM) of Cu alloy targets. The extent to which silicate glass reference materials can be used when analysing Cu alloy targets is determined, as is the optimal internal standard, for a wide range of Cu alloy compositions. Analyses were further optimized by quantitative assessments of the use of CHARM end-member materials as external standards for other CHARM Cu alloy targets. The variable magnitude of the observed matrix effects is most readily explained by variations in Cu/Zn ratios and resulting differences in melting and boiling points, compared with external reference materials, making the Zn-rich Cu alloy targets most prone to matrix effects. With the correct choice of an external matrix-matched standard (Pb-rich CHARM reference material 32X LB14F) and internal element standardization, an accuracy of < 20% can be achieved for virtually all elements of interest in brass and bronze artefacts, which is a significant improvement compared with the use of glass external reference materials

Analysis of the CHARM Cu-alloy reference materials using excimer ns-LA-ICP-MS: Assessment of matrix effects and applicability to artefact provenancing

Excimer nano-second laser ablation inductively coupled plasma mass spectrometry (ns-LA-ICP-MS) is an important tool in chemical characterization of Cu alloys. However, variable matrix-induced elemental fractionation in Cu alloys poses a significant challenge. We systematically investigate this issue by analysing the Cultural Heritage Alloy Reference Material Set (CHARM) of Cu alloy targets. The extent to which silicate glass reference materials can be used when analysing Cu alloy targets is determined, as is the optimal internal standard, for a wide range of Cu alloy compositions. Analyses were further optimized by quantitative assessments of the use of CHARM end-member materials as external standards for other CHARM Cu alloy targets. The variable magnitude of the observed matrix effects is most readily explained by variations in Cu/Zn ratios and resulting differences in melting and boiling points, compared with external reference materials, making the Zn-rich Cu alloy targets most prone to matrix effects. With the correct choice of an external matrix-matched standard (Pb-rich CHARM reference material 32X LB14F) and internal element standardization, an accuracy of < 20% can be achieved for virtually all elements of interest in brass and bronze artefacts, which is a significant improvement compared with the use of glass external reference materials

The effect of alkalinity on Ni–O bond length in silicate glasses: Implications for Ni isotope geochemistry

Equilibrium mass-dependent (“stable”) isotopic fractionation of an element during magmatic processes is driven by a contrast in bonding environment between minerals and silicate melt, which is expressed as an isotopic fractionation factor. A quantitative understanding of such isotopic fractionation factors is vital to interpret observed isotopic variations in magmatic rocks. It is well known that the local environment and the bond strength of an element dictate the sign and magnitude of isotopic fractionation between minerals, but it is uncertain how the structure and chemical composition of a silicate melt can affect mineral-melt isotopic fractionation factors. To explore this, we studied the coordination environment of nickel (Ni) in different silicate glasses using extended X-ray absorption fine structure (EXAFS) measurements at the German synchrotron X-ray source (DESY).We determined –Ni–O bond lengths in a suite of synthetic but near-natural silicate glasses using EXAFS and found that the former vary systematically with melt alkalinity, which is best described by the parameter ln[1 + (Na + K)/Ca]. With increasing melt alkalinity, Ni occupies more IV-fold coordinated sites, which are associated with a shorter –Ni–O bond length. Next, we use the ionic model, which allows to predict isotopic fractionation factors based on the difference in bond length between two phases. We find that more alkaline melts have a stronger preference for the heavier isotopes of Ni than less alkaline melts. This implies that the magnitude of mineral-melt Ni isotope fractionation factors, for instance between olivine and melt, will depend on the alkalinity of the melt. At magmatic temperatures, however, the variation in fractionation factors caused by melt alkalinity will rarely exceed 0.05 ‰ and is thus mostly negligible, in particular in the realm of basaltic melt compositions. Nevertheless, the relationship between melt alkalinity and fractionation factor reported here can be used to extrapolate empirical data for mineral-melt Ni isotope fractionation factors, once such data become available, to the full range of magma compositions on Earth and other Solar System bodies

Evidence for an early wet Moon from experimental crystallization of the lunar magma ocean

The Moon is thought to have been covered initially by a deep magma ocean, its gradual solidification leading to the formation of the plagioclase-rich highland crust. We performed a high-pressure, high-temperature experimental study of lunar mineralogical and geochemical evolution during magma ocean solidification that yields constraints on the presence of water in the earliest lunar interior. In the experiments, a deep layer containing both olivine and pyroxene is formed in the first ∼450% of crystallization, β-quartz forms towards the end of crystallization, and the last per cent of magma remaining is extremely iron rich. In dry experiments, plagioclase appears after 68 vol.% solidification and yields a floatation crust with a thickness of ∼468 km, far above the observed average of 34-43 km based on lunar gravity. The volume of plagioclase formed during crystallization is significantly less in water-bearing experiments. Using the relationship between magma water content and the resulting crustal thickness in the experiments, and considering uncertainties in initial lunar magma ocean depth, we estimate that the Moon may have contained at least 270 to 1,650 ppm water at the time of magma ocean crystallization, suggesting the Earth-Moon system was water-rich from the start