Martian Magmas Research Articles

Evidence for a liquid silicate layer atop the Martian core

Seismic recordings made during the InSight mission1 suggested that Mars’s liquid core would need to be approximately 27% lighter than pure liquid iron2,3, implying a considerable complement of light elements. Core compositions based on seismic and bulk geophysical constraints, however, require larger quantities of the volatile elements hydrogen, carbon and sulfur than those that were cosmochemically available in the likely building blocks of Mars4. Here we show that multiply diffracted P waves along a stratified core–mantle boundary region of Mars in combination with first-principles computations of the thermoelastic properties of liquid iron-rich alloys3 require the presence of a fully molten silicate layer overlying a smaller, denser liquid core. Inverting differential body wave travel time data with particular sensitivity to the core–mantle boundary region suggests a decreased core radius of 1,675 ± 30 km associated with an increased density of 6.65 ± 0.1 g cm−3, relative to previous models2,4–8, while the thickness and density of the molten silicate layer are 150 ± 15 km and 4.05 ± 0.05 g cm−3, respectively. The core properties inferred here reconcile bulk geophysical and cosmochemical requirements, consistent with a core containing 85–91 wt% iron–nickel and 9–15 wt% light elements, chiefly sulfur, carbon, oxygen and hydrogen. The chemical characteristics of a molten silicate layer above the core may be revealed by products of Martian magmatism.

Sulfur and chlorine in nakhlite clinopyroxenes: Source region concentrations and magmatic evolution

The volatile concentrations of the martian mantle and martian magmas remain important questions due to their role in petrogenesis and planetary habitability. The sulfur and chlorine concentrations, and their spatial distribution, in clinopyroxenes from nakhlites MIL 03346, Nakhla, and NWA 998 were measured to provide insight into these volatiles in the parental melts and source regions of nakhlites, and to constrain the evolution of the nakhlite melts. Sulfur and chlorine in four clinopyroxene crystals from MIL 03346, four from Nakhla, and five from NWA 998 were measured in crystal cores and rims by synchrotron X-ray fluorescence using beamline I18 at the Diamond Light Source. Portions of two crystals from MIL 03346 and one from Nakhla were mapped for S and Cl; a few reconnaissance analyses of Cl and F in MIL 03346 and Nakhla were made by ion microprobe. Clinopyroxene cores in Nakhla and NWA 998 contain ∼10 ppm S, ∼10 ppm Cl and ∼74 ppm F (only Nakhla analyzed), whereas the cores of MIL 03346 contain ∼10 ppm S, ∼5 ppm Cl and ∼53 ppm F.Using the volatile concentrations in the cores combined with previously determined partition coefficients we calculate that these clinopyroxenes crystallized from evolved basaltic melts containing ∼500 ppm S, ∼500–1900 ppm Cl, and 160–420 ppm F. These evolved melts can be used to calculate primitive melts in equilibrium with martian peridotite and the concentrations of S, Cl and F in the mantle source region of the nakhlite melts. Depending upon the extent of melting (5–30%) necessary to produce the primary melts associated with nakhlites, our calculations indicate that the nakhlite source region has a S concentration between 20 (5% melting) to 120 ppm (30% melting), Cl between 16 and 97 ppm, and F between 14 and 48 ppm. These concentrations in the nakhlite magma source region are similar to previous estimates for the martian mantle; our calculated source region concentrations of F and Cl agree best with previous estimates if the martian mantle undergoes 10–20% melting to produce primary magmas that evolve to be parental to nakhlites. However, our maximum estimated sulfur concentration of the source (calculated for 30% melting) is near previous minimum estimates for the martian mantle, suggesting the possibility that the nakhlite source region is depleted in sulfur relative to much of Mars’ mantle.Mapping the spatial distribution of volatiles in three clinopyroxene crystals demonstrates that S and Cl concentrations of the evolving melts changed significantly from the core to the rim, particularly those in MIL 03346. Increasing S and Cl concentrations between the core and rim of MIL 03346 crystals are attributed to incorporation of additional volatiles through assimilation, but the Nakhla crystal shows no such evidence. However, concentrations of Cl and S at some outer crystal rims of one MIL 03346 crystal decrease, most probably due to volatile degassing during the final stages of clinopyroxene growth.

Samples Collected From the Floor of Jezero Crater With the Mars 2020 Perseverance Rover

AbstractThe first samples collected by the Mars 2020 mission represent units exposed on the Jezero Crater floor, from the potentially oldest Séítah formation outcrops to the potentially youngest rocks of the heavily cratered Máaz formation. Surface investigations reveal landscape‐to‐microscopic textural, mineralogical, and geochemical evidence for igneous lithologies, some possibly emplaced as lava flows. The samples contain major rock‐forming minerals such as pyroxene, olivine, and feldspar, accessory minerals including oxides and phosphates, and evidence for various degrees of aqueous activity in the form of water‐soluble salt, carbonate, sulfate, iron oxide, and iron silicate minerals. Following sample return, the compositions and ages of these variably altered igneous rocks are expected to reveal the geophysical and geochemical nature of the planet's interior at the time of emplacement, characterize martian magmatism, and place timing constraints on geologic processes, both in Jezero Crater and more widely on Mars. Petrographic observations and geochemical analyses, coupled with geochronology of secondary minerals, can also reveal the timing of aqueous activity as well as constrain the chemical and physical conditions of the environments in which these minerals precipitated, and the nature and composition of organic compounds preserved in association with these phases. Returned samples from these units will help constrain the crater chronology of Mars and the global evolution of the planet's interior, for understanding the processes that formed Jezero Crater floor units, and for constraining the style and duration of aqueous activity in Jezero Crater, past habitability, and cycling of organic elements in Jezero Crater.

The effects of oxygen fugacity and sulfur on the pressure of vapor-saturation of magma

Abstract Geobarometers are commonly used to determine the pressure (and hence depth) of magmatic bodies. For instance, at equilibrium, the concentration of dissolved volatiles in a vapor-saturated melt can be used as a barometer: this is the pressure of vapor-saturation (Psatv). Most determinations of Psatv assume that melt and vapor contain only oxidized C-O-H species. However, sulfur is the third most abundant volatile element in magmas, and oxygen fugacity (fO2) exerts a strong influence on the speciation of the melt and vapor. To explore how S and fO2 affect calculations of Psatv, we model a Hawaiian tholeiite that contains both reduced and oxidized C-O-H-S species in the melt and vapor. We find that excluding reduced C-O-H species in the system can result in significant underestimations of Psatv under reducing conditions (ΔFMQ < 0). The effect of S on Psatv is small except in the vicinity of the “sulfur solubility minimum” (SSmin; 0 < ΔFMQ < +2), where excluding S-bearing species can result in underestimates of Psatv. The implications of these results depend on the volatile concentration of the system being investigated, its fO2, and the melt composition and temperature. Our results suggest there will be little impact on Psatv calculated for mid-ocean ridge basalts because their fO2 is above where reduced C-O-H species become important in the melt and vapor and yet below the SSmin. However, the fO2 of ocean island and arc basalts are close enough to the SSmin and their S concentrations high enough to influence Psatv. However, high-CO2 and high-H2O concentrations are predicted to reduce the effect of the SSmin. Hence, Psatv calculated for shallowly trapped melt inclusions and matrix glass are more affected by the SSmin than deeply trapped melt inclusions. Lunar and martian magmas are typically more reduced than terrestrial magmas, and therefore accurate Psatv calculations for them require the inclusion of reduced C-O-H species.

Early differentiation processes on Mars inferred from silicon isotopes

Accretion of terrestrial planets involved partial or global melting events such as magma oceans or magma ponds. Mars experienced large-scale differentiation very early in its history, as shown by its 146Sm-142Nd and 182Hf-182W record. The broad variations in ε142Nd and ε142W of SNC meteorites highlight the presence of mantle sources that must have remained isolated, at least partly, after the crystallization of a global magma ocean. In this study, we have investigated whether the crystallization of the martian magma ocean could have generated mantle reservoirs characterized by different silicon isotope signatures, as the fractionation of Si isotopes between minerals and melts is known to depend on pressure. Thus, the goal of this study was to investigate whether there were any relationships between magma ocean crystallisation and possible variations in the Si isotope record of SNC meteorites. High resolution silicon isotope measurements were performed on twelve meteorites from the Shergottite, Nakhlite and Chassignite groups using a Neptune Plus MC-ICP-MS in dry plasma mode. The δ30Si values are in good agreement with previous studies but display a narrower range of variations with a mean value at −0.46 ‰ ± 0.07 (2SD). A magma ocean crystallization model shows that the range of δ30Si in SNCs is consistent with that generated by magma ocean crystallisation. In particular, there is a correlation between calculated 147Sm/144Nd for the moderately depleted mantle sources with δ30Si values; this correlation is consistent with the crystallization model if one includes trapped melt in the cumulates. In contrast, enriched shergottites displayed a very homogenous composition in Sm/Nd ratios, despite significant variability in δ30Si. This observation could be related to either fluid-rock interactions or redox effect during magma differentiation. Altogether, silicon isotope compositions of SNC provide new constraints about magma ocean crystallization processes in Mars.

This One Simple Trick Helps Us Understand How Much Water Is in Martian Lavas

Understanding how much water is in Martian magma is vital for understanding whether the Red Planet had seas in its early history.

A primordial atmospheric origin of hydrospheric deuterium enrichment on Mars

The deuterium-to-hydrogen (D/H or 2H/1H) ratio of Martian atmospheric water (∼6× standard mean ocean water, SMOW) is higher than that of known sources, requiring planetary enrichment. A recent measurement by NASA's Mars Science Laboratory rover Curiosity of Hesperian-era (>3 Ga) clays yields a D/H ratio ∼3×SMOW, demonstrating that most of the enrichment occurs early in Mars's history, reinforcing the conclusions of Martian meteorite studies. As on Venus, Mars's D/H enrichment is widely thought to reflect preferential loss to space of 1H (protium) relative to 2H (deuterium), but both the cause and the global environmental context of large and early hydrogen losses remain to be determined. Here, we apply a recent model of primordial atmosphere evolution to Mars, link the magma ocean of the accretion epoch with a subsequent water-ocean epoch, and calculate the behavior of deuterium for comparison with the observed record. In contrast to earlier works that consider Martian D/H fractionation in atmospheres in which hydrogen reservoirs are present exclusively as H2O or H2, here we consider 2-component (H2O-H2) outgassed atmospheres in which both condensing (H2O) and escaping (H2) components – and their interaction – are explicitly calculated. We find that a ≈2-3× hydrospheric deuterium-enrichment is produced rapidly if the Martian magma ocean is chemically reducing at last equilibration with the primordial atmosphere, making H2 and CO the initially dominant species, with minor abundances of H2O and CO2. Reducing gases – in particular H2 – can cause substantial greenhouse warming and prevent a water ocean from freezing immediately after the magma ocean epoch. We find that greenhouse warming due to plausible H2 inventories (pH=21−102 bars) yields surface temperatures high enough (T=s290−560 K) to stabilize a water ocean and produce an early hydrological cycle through which surface water can be circulated. Moreover, the pressure-temperature conditions are high enough to produce ocean-atmosphere H2O-H2 isotopic equilibrium through gas-phase deuterium exchange such that surface H2O strongly concentrates deuterium relative to H2, which preferentially takes up protium and escapes from the primordial atmosphere. The efficient physical separation of deuterium-rich (H2O) and deuterium-poor (H2) species via condensation permits equilibrium isotopic partitioning and early atmospheric escape to be recorded in modern crustal reservoirs. The proposed scenario of primordial H2-CO-rich outgassing and escape suggests significant durations (>Myr) of chemical conditions on the Martian surface conducive to prebiotic chemistry immediately following magma ocean crystallization.

The History of Water in Martian Magmas From Thorium Maps.

Water inventories in Martian magmas are poorly constrained. Meteorite‐based estimates range widely, from 102 to >104 ppm H2O, and are likely variably influenced by degassing. Orbital measurements of H primarily reflect water cycled and stored in the regolith. Like water, Th behaves incompatibly during mantle melting, but unlike water Th is not prone to degassing and is relatively immobile during aqueous alteration at low temperature. We employ Th as a proxy for original, mantle‐derived H2O in Martian magmas. We use regional maps of Th from Mars Odyssey to assess variations in magmatic water across major volcanic provinces and through time. We infer that Hesperian and Amazonian magmas had ∼100–3,000 ppm H2O, in the lower range of previous estimates. The implied cumulative outgassing since the Hesperian, equivalent to a global H2O layer ∼1–40 m deep, agrees with Mars’ present‐day surface and near‐surface water inventory and estimates of sequestration and loss rates.

Magma oceans, iron and chromium redox, and the origin of comparatively oxidized planetary mantles

The mantles of both Earth and Mars are more oxidized than would be expected based on low pressure equilibration of molten silicate and alloy during their magma ocean stages. High pressure silicate-alloy equilibration in a magma ocean can produce appreciable ferric iron in the silicate, leading to comparatively oxidized near surface conditions and overlying atmospheres. Upon crystallization, this may feasibly be sufficient to account for oxygen fugacities prevailing in basalt source regions of Earth and Mars. Experiments and first principles studies affirm that Fe3+ is stabilized at high pressure, but to date there has been no model that accounts accurately for the combined effects of melt composition, temperature, pressure, and oxygen fugacity on magma ocean Fe3+/FeT. We calibrate a new model for Fe3+/FeT as a function of temperature, pressure, melt composition, and fO2 which reproduces Fe3+/FeT for experimental peridotite liquids and which incorporates differences in FeO and Fe2O3 liquid heat capacities into a potentially realistic temperature function. For the effects of pressure, two versions of the model are implemented based on recent equations of state (EOS), though only the EOS of Deng et al. (2020) is applicable to pressures relevant to metal-silicate equilibration in a deep terrestrial magma ocean. For Earth, metal-silicate equilibration at 28–53 GPa, 2300–4100 K, and fO2 set by plausible mantle and core compositions produces Fe3+/FeT between 0.034 and 0.10, with variation mostly owing to differences in assumed temperatures. For Mars, different proposed mantle compositions produce Fe3+/FeT ratios that range from 0.026 for FeO* of 13.5 wt.% up to 0.038 for FeO* of 18.1 wt.%.Although significant Fe3+ may be present in magma oceans owing to high pressure equilibration with alloy, the budget of Fe2O3 in crystallized mantles is expected to be modified from that in the molten state. An important additional factor is the influence of Cr, which is Cr2+ in molten silicate equilibrated with alloy and Cr3+ in terrestrial upper mantles. Production of Cr3+ and Fe2+ by reaction with Cr2+ and Fe3+ during crystallization can destroy much of the Fe2O3 present during the magma ocean stage. Considering the stability of Cr2+ in olivine and the temperature-dependent partitioning of Cr3+ between mantle silicates, we construct an empirical model for the fraction of Cr that is Cr2O3 in solid spinel peridotite as a function of temperature and fO2. For Earth, at least 0.35 wt.% Fe2O3 is destroyed by oxidation of magma ocean CrO and for Mars, more than 0.55 wt.% Fe2O3 should be destroyed. Consequently, either the terrestrial and martian magma oceans were significantly more enriched in Fe2O3 than their present-day upper mantles or other processes contributed to oxidation of the latter. Over-enrichment of Fe2O3 in the magma oceans is plausible only if terrestrial metal-silicate equilibration occurred above 3300 K and if the martian mantle contains >17 wt.% FeO*. Subsolidus disproportionation of ferrous iron may have contributed to the present-day redox state of the Earth’s mantle, and late accretion of chondrite-like material and hydrogen degassing also likely affected the solidified mantles of both Earth and Mars.

Nickel–manganese variability in olivine and Al‐in‐olivine thermometry for olivine‐phyric shergottites

AbstractOlivine‐phyric shergottites represent primitive Martian magmas, but they commonly contain excess olivine and rarely represent primary mantle melts. Olivine chemistry, however, tracks magma evolution and preserves information on the original parent magma composition. Here, we investigate the applicability of the Al‐in‐olivine thermometer in tandem with olivine chemistry in a suite of 13 olivine‐phyric shergottites to constrain the compositions and conditions of their mantle sources and parental magmas. We show that the Al‐in‐olivine thermometer is a robust method for constraining crystallization temperatures in shergottites, yielding temperatures in agreement with experimental work. In contrast, we do not recommend olivine–spinel thermometry relying on Mg‐Fe in olivine, which underestimates crystallization temperatures by 160–380 °C. Olivine chemistry reveals distinct differences in Ni concentrations between shergottite groups, with enriched shergottites generally having higher Ni at a given forsterite (Fo) content. Nickel variations in terrestrial olivine are often accredited to contributions from a pyroxenite source; however, the same mechanism is not responsible for Ni variations in Martian olivine. Here, we favor a model for variable olivine modal abundance, caused by multiple melting episodes in the depleted mantle source, affecting Ni partitioning during melting to account for the Ni variations observed. In addition, we show that olivine Ni‐Mn variations in depleted shergottites indicate variable petrogenetic histories and parental magmas. Tissint contains elevated Ni in olivine more similar to the enriched shergottites whereas DaG 1037 has elevated Mn in olivine suggesting an Mn‐enriched parent magma relative to other depleted shergottites.

Melt inclusions in chassignite NWA 2737: A link between processes recorded in Martian meteorites and rocks at Gale crater

AbstractNorthwest Africa (NWA) 2737, one of the only three discovered Martian chassignites, provides critical constraints on the evolution of the Martian mantle and crust. Because of chassignites’ cumulative nature, they contain abundant melt inclusions (MI). MI are small droplets of melts trapped by crystals during the cooling of magma. They are critical to the study of pre‐eruptive parental magma compositions, and thus, provide snapshots of the composition and evolution of Martian magmatic systems. Here, we present fractional crystallization models using parental magma composition calculated from NWA 2737 melt inclusions as starting compositions. We used the thermodynamic modeling software MELTS to model fractional crystallization of NWA 2737 parental magma compositions with a wide range of parameters (pressure, water content, oxygen fugacity). Our models show that the felsic compositions recently analyzed at the Martian surface in Gale crater, especially Sparkle and Angmaat, the two rocks thought to be analogous to the earliest continental crust on Earth, can be obtained by fractional crystallization of chassignite‐like parental melts. Our results suggest a link between the processes that resulted in chassignites and the rocks analyzed in situ at Gale crater. To assess the possible scenarios for Martian magma migration and storage processes, we compared chassignites to terrestrial analogs formed via various mechanisms and proposed two mechanisms that may explain the intrusive and effusive rocks found in situ at Gale crater: (1) emplacement and fractionation in a closed‐system crustal reservoir and (2) eruption of mafic to intermediate lavas of a relatively open system subject to constant replenishment.

Effect of sulfur on siderophile element partitioning between olivine and a primary melt from the martian mantle

AbstractNi and Co variations in primary martian magmas exhibit anomalous incompatible behavior, which has remained an unexplained conundrum. Because martian magmas are S-rich, and some trace metals are reported to have enhanced solubility in S-bearing magmas, we have carried out a series of experiments to evaluate the effect of high-S melts on the olivine/melt partitioning of Ni, Co, Mn, V, and Cr. Near-liquidus experiments on a synthetic primary martian mantle melt (Yamato-980459 [Y98]) were completed in a piston-cylinder apparatus at 0.75 GPa. Previous studies in S-free systems illustrate that the partition coefficients for these elements are dependent chiefly on DMg(Ol/melt) (the partition coefficient defined as wt% Mg in olivine/wt% Mg in melt, a proxy for temperature), and were used to calibrate a predictive expression that includes the effects of temperature [i.e., DMg(Ol/melt)], melt composition, and oxygen fugacity. These predictive expressions are then used to isolate any effect in DM olivine/melt due to dissolved sulfur. The results show that S might have a small effect for Co, but not enough to change Co partitioning from compatible to incompatible in our experiments. The addition of a sulfur term to the DCo predictive expressions shows that nearly 8000 ppm of sulfur would be required in the melt (at liquidus temperature of Y98) for DCo to become <1. These S contents are two times higher than those of a sulfide-saturated melt at the P-T conditions of a martian mantle source region. Therefore, the anomalous incompatible behavior observed in these primary magma suites must be due to another mechanism. High temperature, oxygen fugacity, and diffusion are not viable mechanisms, but magma mixing, assimilation, or kinetic crystallization effects remain possibilities.

Highly siderophile elements in shergottite sulfides and the sulfur content of the martian mantle

Shergottite meteorites are ultramafic to mafic igneous rocks derived from partial melting of distinct regions of the martian mantle. As such, they trace magmatic processes, including fractional crystallization and mixing processes in Mars. New chalcophile (Cu, Se, Zn, Pb), siderophile (Ni, Co, W), and highly siderophile element (HSE: Au, Re, Pd, Rh, Pt, Ru, Ir, Os) abundance data are reported for sulfide assemblages in a suite of thirteen incompatible trace-element depleted, intermediate and enriched shergottites, along with new whole-rock HSE abundance and 187Os/188Os data for seven shergottites. Sulfide grains in depleted and intermediate shergottites typically have the highest absolute abundances of HSE, with broadly flat CI-chondrite normalized patterns. Enriched shergottite sulfide grains typically have highly variable Au, elevated Pd and Rh and are relatively depleted in Zn, Ir and Os. The new HSE whole-rock data for enriched (Northwest Africa [NWA] 7397, NWA 7755, NWA 11043), and intermediate shergottites (NWA 10961, NWA 11065, NWA 12241, and NWA 12536) are generally consistent with existing 187Os/188Os and HSE abundance data for these geochemical groupings. Enriched shergottites with >1 ppb bulk rock Os have measured 187Os/188Os ranging between 0.1296 and 0.1471, with variable Pd and Pt contents. Intermediate shergottites with >1 ppb bulk rock Os have chondrite-relative proportions of the HSE at ∼0.01 to 0.001 × CI chondrites and 187Os/188Os from 0.1284 and 0.1295. Sulfides are the major host of the HSE, and they control the behavior of the HSE during petrogenetic processes in shergottite magmas, enabling the determination of HSE compatibility for martian magmatism in the order: Os > Ir ≥ Ru ≥≥ Rh ≥ Pd ≥ Re ≥ Pt ≥ Au. Fractionation models of removal of an olivine-dominated cumulate recreate HSE patterns for the whole-rock shergottites. Enriched shergottites are best reproduced by 25 to 30% of fractionation from a degassed parent melt (250 ± 50 ppm of S), whereas depleted and intermediate shergottites can be explained by slightly lower fractionation (10 to 15%) from higher S content parent melts (350 ± 100 ppm of S). Sulfur contents in the melt that are ∼50% higher than these estimates yield earlier S-saturation during fractional crystallization, leading to an abrupt decrease of the more compatible HSE (Ru, Ir, Os), which is not observed. These results indicate that the martian mantle and partial melts derived from it, are probably not anomalously enriched in S, and instead are similar to slightly higher than those of the terrestrial mantle and its partial melts.

Onset of magma ocean solidification on Mars inferred from Mn-Cr chronometry

The mantle of Mars probably differentiated through the crystallization of a magma ocean during the first tens of million years (Ma) of Solar System evolution. However, the exact timescale of large-scale silicate differentiation of the martian mantle is debated, and in particular, it remains unclear when differentiation commenced. Here we applied the short-lived 53Mn-53Cr system to martian meteorites in order to date the onset of large-scale mantle differentiation on Mars. The new Cr isotope data demonstrate that martian meteorites exhibit no resolvable radiogenic 53Cr variations, and instead have a uniform +20.2±1.2 (95% conf.) parts-per-million excess in 53Cr/52Cr relative to the terrestrial mantle. The investigated groups of martian meteorites are lithologically varied and derive from diverse mantle sources that probably had variable Mn/Cr. Hence, the lack of 53Cr variability among martian meteorites demonstrates that silicate differentiation on Mars occurred after the extinction of 53Mn. Provided that the sources of the martian meteorites have Mn/Cr variations that are typical of the terrestrial planets, this result implies that the onset of large-scale silicate differentiation must have occurred later than 20±5 Ma after Solar System formation. The onset of silicate differentiation on Mars inferred here is significantly later than time estimates for segregation of the martian core which conservatively occurred within <10 Ma after Solar System formation. Thus, the new Mn-Cr data imply that there was a small, but resolvable, time gap of at least 5 Ma between core formation and magma ocean solidification on Mars. If the age of core segregation is taken at face value, our results imply that the martian magma ocean remained mostly molten over several Ma. This inferred longevity of the magma ocean is inconsistent with thermal models predicting rapid (<1 Ma) solidification of the martian magma ocean. Although there is currently no unique solution to this conundrum, our results can potentially be explained by a protracted history of impact bombardment that delayed differentiation in a shallow magma ocean on Mars, or perhaps more readily, by the presence of an early and dense atmosphere that acted as an insulator and prevented the magma ocean from cooling quickly.

Convective activity in a Martian magma chamber recorded by P‐zoning in Tissint olivine

AbstractThe Tissint Martian meteorite is an unusual depleted olivine‐phyric shergottite, reportedly sourced from a mantle‐derived melt within a deep magma chamber. Here, we report major and trace element data for Tissint olivine and pyroxene, and use these data to provide new insights into the dynamics of the Tissint magma chamber. The presence of irregularly spaced oscillatory phosphorous (P)‐rich bands in olivine, along with geochemical evidence indicative of a closed magmatic system, implies that the olivine grains were subject to solute trapping caused by vigorous crystal convection within the Tissint magma chamber. Calculated equilibration temperatures for the earliest crystallizing (antecrystic) olivine cores suggest a Tissint magma source temperature of 1680 °C, and a local Martian mantle temperature of 1560 °C during the late Amazonian—the latter being consistent with the ambient mantle temperature of Archean Earth.

Geochemically heterogeneous Martian mantle inferred from Pb isotope systematics of depleted shergottites

Radiogenic isotopic compositions of shergottite meteorites suggest that early planetary differentiation processes, which are related to the crystallization of the Martian Magma Ocean (MMO), resulted in the geochemically heterogeneous Martian mantle. In order to understand the early geochemical evolution of Mars, we investigated the Pb isotope systematics in the depleted Martian mantle on the basis of the analyses of two geochemically depleted shergottites, Dar al Gani (DaG) 476 and Yamato 980459 (Y-980459). Their initial Pb isotopic compositions were estimated from geochemical analyses of highly leached acid residues and age-correction calculations using reference crystallization ages. This yielded μ-values (238U/204Pb) for the DaG 476 and Y-980459 source reservoirs of 2.33 ± 0.07 and 2.32 ± 0.06, respectively. These μ-values are distinct from those of other depleted shergottite source reservoirs (e.g., 1.4 ± 0.1 for the Tissint meteorite) and show a negative correlation with corresponding 147Sm/144Nd, 176Lu/177Hf, ɛ182W, and ε142Nd compositions. Such correlations between long- and short-lived isotopic signatures suggest that a geochemically heterogeneous depleted shergottite source mantle was formed on the early Mars. This geochemical heterogeneity would have been formed by variable mixing of depleted and enriched end-member components that originally formed by fractional crystallization in the MMO. Local remelting in the geochemically depleted Martian mantle after the crystallization of the MMO is another possible explanation for the formation of a geochemically heterogeneous depleted shergottite source mantle.

Fractional Crystallization of Martian Magma Oceans and Formation of a Thermochemical Boundary Layer at the Base of the Mantle

AbstractWe examine the fractional crystallization of intermediate depth (~160–260 km), impact‐induced magma oceans on Mars, and find that residual liquids become denser than normal Martian mantle. Fractional crystallization near 3 GPa establishes inverted density distributions that can generate melt descent within the mantle. Liquid compositions produced by ~45–80 wt% crystallization become dense enough to descend to the core‐mantle boundary and could form a stably stratified thermochemical boundary layer (TCBL). If this layer crystallizes, its mineralogy would be dominated by either garnet and ferropericlase or stishovite and ringwoodite. Although the size of Mars' core remains uncertain, the addition of such a thermal boundary layer would impede stabilization of (Mg, Fe)SiO3‐perovskite at the base of the mantle. A TCBL would both elevate the inferred temperature of the core and inhibit heat flow out of the core, with a potentially causal relation with the current lack of an internally generated Martian magnetic field.

Partition coefficient of phosphorus between liquid metal and silicate melt with implications for the Martian magma ocean

Phosphorus in Martian mantle is believed to be five to ten times more abundant than in Earth's mantle, and the distribution of this essential ingredient for life between different deep reservoirs is critical for understanding the habitability of the red planet. In this study, we investigated the behavior of phosphorus in a Martian magma ocean scenario, and measured the partition coefficient of phosphorus (DP) between liquid metal and silicate melt within the pressure range of 3–8 GPa, temperatures between 1973 and 2173 K and oxygen fugacity ranging from −1.5 to ~ −2.5 as normalized to the iron-wüstite oxygen buffer. Our results show DP increasing with pressure but decreasing with temperature. A decrease of oxygen fugacity has a negative effect on DP. The moderately siderophile character of phosphorus indicates that the Martian core might be an important reservoir of phosphorous. Based on our experimental results and phosphorus abundance in Martian mantle and bulk Mars, a minimum pressure of 5.8–10.4 GPa is estimated at the base of Martian magma ocean or during the impact melting if a contribution from the late accretion scenario is taken into account. The shallow Martian magma ocean would avail the preservation of volatiles after the rapid solidification of the planet.

CaCl and CaF emission in LIBS under simulated martian conditions

Chlorine and fluorine play an important role in the geological history of Mars due to their high concentration in Martian magmas and their influence on the generation and evolution of Martian basalts. Chlorine-bearing salts could also facilitate the formation of eutectic brines that could be important for the fluvial history of Mars. The LIBS instruments of ChemCam and SuperCam can detect emission lines of Cl and F, but the intensity of these emission lines is comparatively low, making it difficult to quantify them correctly. A promising alternative is the quantification by molecular emission of diatomic molecules like CaCl and CaF, which can be observed as intense molecular bands in LIBS spectra if Ca is also present. However, the nonlinear dependence of the band intensity on the concentrations of both elements needs to be considered. In this study, we expand upon our previous analysis of molecular bands by investigating samples which produce CaCl bands, CaF bands, or both. We find that the highest CaCl band intensities are found in samples containing more Ca than Cl, while the strongest CaF bands are found in samples with roughly equal concentrations of Ca and F. Both observations can be described by the model that we present here. We also find that the CaCl band is significantly stronger for a sample containing CaCl2 than it is for a sample containing the same concentrations of Ca and Cl in separate bonds. The opposite is true for the CaF band, which is significantly weaker for the sample containing CaF2 bonds than it is for the sample that does not contain CaF2 bonds. These matrix effects are partially attributed to fragmentation during the ablation process and differences in the dissociation energies. Furthermore, we observe that CaF formation is not affected by competing CaCl formation, while CaCl is strongly affected by competing CaF formation. All measurements are done in simulated Martian atmospheric conditions in order to assist the analysis of Martian LIBS data.

Syneruptive incorporation of martian surface sulphur in the nakhlite lava flows revealed by S and Os isotopes and highly siderophile elements: implication for mantle sources in Mars

Martian lava flows likely acquired S-rich material from the regolith during their emplacement on the planet’s surface. We investigated five of the twenty known nakhlites (Nakhla, Lafayette, Miller Range (MIL) 090032, Yamato 000593, and Yamato 000749) to determine whether these lavas show evidence of regolith assimilation, and to constrain the potential implications that this process has on chemical tracing of martian mantle source(s). To establish the proportionate influence of atmospheric, hydrothermal, and volcanic processes on nakhlite isotopic systematics we obtained in situ sulphur isotope data (Δ33S and δ34S) for sulphide grains (pyrrhotite and pyrite) in all five nakhlite samples. For Nakhla, Lafayette, and MIL 090032, these data are integrated with highly siderophile element (HSE) abundances and Os-isotope compositions, as well as textural information constrained prior to isotopic analysis. This work thereby provides the first Re-Os isotope systematics for two different nakhlites, and also the first Re-Os isotope data for martian sample for which detailed petrographic information was constrained prior to digestion.We report the largest variation in δ34S yet found in martian meteorites (−13.20‰ to +15.16‰). The relatively positive Δ33S and δ34S values of MIL 090032 (δ34S = +10.54 ± 0.09‰; Δ33S = −0.67 ± 0.10‰) indicate this meteorite assimilated sulphur affected by UV-photochemistry. In contrast, the strongly negative values of Lafayette (δ34S = −10.76 ± 0.14‰; Δ33S = −0.09 ± 0.12‰) are indicative of hydrothermal processes on Mars. Nakhla, Yamato 000593, and Yamato 000749 sulphides have a narrower range of sulphur isotope compositions (Δ33S and δ34S ∼ 0) that is consistent with no assimilation of martian surface materials during lava flow emplacement. Consequently we used this second group of Δ33S values to approximate the Δ33S of the nakhlite source, yielding a Δ33S value of −0.1‰.Nakhlite HSE patterns result from a sulphide-saturated melt where Ru-Os-Ir alloys/sulphide were likely crystallized during earlier phases of magmatic processing in Mars to result in the fractionated HSE patterns of the nakhlites. Our data, alongside a synthesis of previously published data, suggest assimilation of an enriched component to the primary nakhlite melt, potentially a late-stage crystallization cumulate from the martian magma ocean stage. In the context of this model, and within large uncertainties, our data hint at perturbation and potential decoupling of nakhlite Re-Os isotope systematics from other isotopic systems as a result of small degrees of assimilation of a regolith component with highly radiogenic 187Os/188Os.