Martian Mantle Research Articles

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.

Defects in olivine

Abstract. Olivine, a ferromagnesian orthosilicate, is the most abundant mineral in Earth's upper mantle and is stable down to the olivine–wadsleyite phase transition, which defines the 410 km depth mantle transition zone. Olivine also occurs in crustal environments in metamorphic and hydrothermal rocks and is expected to be the major mineral constituent of the Martian and Venusian mantles. The olivine atomic structure is also used in materials science to manufacture lithium batteries. Like any other crystalline solid, including minerals, olivine never occurs with a perfect crystalline structure: defects in various dimensions are ubiquitous, from point, line, and planar defects to three-dimensional (3-D) inclusions. In this contribution, I review the current state of the art of defects in olivine and several implications for key processes occurring in Earth's mantle. Intrinsic and extrinsic point defects are detailed, exemplifying the astonishing diversity of atomic impurities in mantle-derived olivine. Linear defects, one of the key defect types responsible for ductile deformation in crystalline solids, are examined in light of recent progress in 3-D transmission electron microscopy, which has revealed an important diversity of dislocation slip systems. I summarize the principal characteristics of interface defects in olivine: the free surface, grain and interface boundaries, and internal planar defects. As the least-studied defects to date, interface defects represent an important challenge for future studies and are the main application of numerical simulation methods in materials science. I provide an overview of melt, fluid, and mineral inclusions, which are widely studied in volcanology and igneous petrology. Special attention is given to new crystalline defects that act as deformation agents: disclinations (rotational defects) and the potential occurrence of disconnections in olivine, both of which are expected to occur along or near grain boundaries. Finally, I detail outstanding questions and research directions that will further our understanding of the crystalline specificities and paradoxes of olivine and olivine-rich rocks and ultimately their implications for the dynamics of Earth's upper mantle.

An Algorithm for Thermodynamic Parameter Optimization: Application to the Martian Mantle

AbstractThe compilation of thermodynamic models for geophysical applications is such a tedious and complex process that it is generally impractical for researchers to refit parameters in existing models in light of new constraints. To mitigate this difficulty, we develop a Bayesian algorithm that permits the modification of a thermodynamic model to account for additional observational constraints. This algorithm can be applied to any thermodynamic dataset and can utilize a wide variety of experimental constraints. To demonstrate the applicability of the algorithm it is used to revise the Stixrude and Lithgow‐Bertelloni (2011, https://doi.org/10.1111/j.1365‐246x.2010.04890.x), whole‐mantle terrestrial thermodynamic model, using phase equilibrium constraints provided by Bertka and Fei (1997, https://doi.org/10.1029/96jb03270), for the more iron‐rich compositions that are thought to be relevant to the Martian mantle. The revised thermodynamic model provides a more reliable prediction of phase equilibria in the Martian mantle. Seismic properties are calculated in an internally self‐consistent manner along hot and cold areotherms to constrain the upper and lower bounds of these properties for different bulk silicate Mars compositional models.

The Thermo‐Chemical Evolution of Mars With a Strongly Stratified Mantle

AbstractThe Martian mantle probably experienced an early global magma ocean stage. The crystallization and the fractionation and overturn of such a magma ocean likely led to the formation of a compositionally distinct layer at the bottom of the mantle. This layer would have been heavily enriched in iron and in heat‐producing elements (HPE). The significant iron enrichment can lead to long‐term stability with little mixing between the layer and the overlying mantle. We studied the influence of such an enriched basal layer on the thermal and chemical evolution of the Martian mantle using both 2‐D finite‐volume modeling at mantle scale, and a parameterized convection approach at the entire planetary scale. The basal layer is most likely stably stratified because of its moderate thickness and/or its gradual enrichment in iron with depth that prevents the development of convection in this region. We explored a wide parameter space in our parameterized models, including the layer thickness and the mantle rheology. We show that the presence of an enriched basal layer has a dramatic influence on the thermo‐chemical evolution of Mars, strongly delaying deep cooling, and significantly affecting nearly all present‐day characteristics of the planet (heat flux, thermal state, crustal and lithospheric thickness, Love number and tidal dissipation). In particular, the enrichment of the layer in iron and HPE generates large volumes of stable melt near the core‐mantle boundary. Due to their intrinsic low viscosity and seismic velocities, these regions of silicate melt could be erroneously interpreted as core material.

Uniform oxygen fugacity of shergottite mantle sources and an oxidized martian lithosphere

Martian meteorites are the only available samples that can be directly measured to constrain the geological evolution of Mars. It has been suggested that the oxygen fugacity (fO2) of martian shergottite meteorites, which have low (∼7 wt.%) to high-MgO (∼30 wt.%) compositions, correlates with incompatible trace element enrichment (i.e., La/Yb), and 87Sr/86Sr, 143Nd/144Nd, 187Os/188Os and 176Hf/177Hf at the time of crystallization. These relationships have been interpreted to result from early magmatic processes segregating enriched and more oxidized from depleted and more reduced reservoirs in Mars. Here we use the V-in-olivine oxybarometer to constrain the fO2 of shergottites and the dunitic chassignites. These data, utilizing early crystallizing silicate phases, constrain the shergottite fO2 range to between −3.72 ± 0.07 and −0.21 ± 0.55 ΔFMQ (log units relative to the fayalite-magnetite-quartz buffer), with no correlation with trace element enrichment or Nd isotope systematics. Previously employed oxybarometers that use later-formed or multiple mineral phases, and that show such correlations, likely differ from the V-in-olivine oxybarometer in that they record effects from late-stage magmatic processes. In contrast to shergottites, chassignites are relatively oxidized, at +2.1 ± 0.4 to +2.2 ± 0.5 ΔFMQ. The chassignites, along with the nakhlites, have been proposed to be sourced from metasomatized lithospheric mantle, and their high fO2 strengthens this model. The new data implies that the martian mantle sources of shergottites have fO2 of −2.1 ± 1.8 ΔFMQ. This estimate indicates that the mantle and core of Mars are not in redox equilibrium and therefore that oxidation of the martian mantle following core formation is required.

Martian core heat flux: Electrical resistivity and thermal conductivity of liquid Fe at martian core P-T conditions

The present-day Mars has no magnetic field which suggests that the heat carried out of its liquid core is largely driven by conduction. To constrain the heat flux from Martian core, we measured the temperature (T) dependent electrical resistivity of solid and liquid Fe devoid of contamination in large volume press at various fixed pressure (P) up to 22.5 GPa, corresponding to the P at the top of the Martian core. We also measured its P-dependent resistivity up to 22.5 GPa at room T. At a P range between 18 and 20 GPa, we observed a drop in the electrical resistivity of ~35 μΩcm which is attributed to a loss in long range order magnetic structure. This loss gives rise to an overall decrease in the electron scattering processes induced by magnon. The transition from long- to short-range order magnetic structure occurs in association with the completion of crystallographic transformation from α-bcc (ferromagnetic) to ε-hcp (paramagnetic). The decrease in the electrical resistivity at the same P range corresponds to an increase in thermal conductivity of ~30 Wm−1 K−1. The resistivity and thermal conductivity of liquid Fe at the Martian core mantle boundary (CMB) on the cores side are estimated to be ~68 ± 3 μΩcm and ~82 ± 3 Wm−1 K−1, respectively. The heat conducted along its core adiabat is found to be ~45 mW−1 m−2. With a core radius of ~1700 km, we obtain a value of 0.3 TW for its total surface heat flux. In comparison with the resistivity of Fe at the Earth's core conditions reported by a recent study, our result indicates that pure liquid Fe is electrically more conductive in the Martian core than in the Earth's core. Our results will complement the HP3 subsurface heat flux measurements in the on-going NASA InSight Mission.

Martian Mantle Heat Flow Estimate From the Lack of Lithospheric Flexure in the South Pole of Mars: Implications for Planetary Evolution and Basal Melting

AbstractHeat flow measurements are important for our understanding of planetary interior composition, structure, and evolution. In the absence of direct measurement, a first‐order estimate of a planet's interior heat flow can be made by modeling the lithosphere's viscoelastic response to stress exerted by large surface loads. Here, we model the Martian lithosphere's viscoelastic response to the south polar layered deposits and estimate the local mantle heat flow to be less than ∼10 mW/m2. Combined with our previous estimate of the low mantle heat flow from the north polar region (∼7 mW/m2), our results suggest that the Martian mantle may be globally depleted in heat‐producing elements. The relatively low mantle heat flow has significant implications for Mars' long‐term thermal evolution and on the possibility of basal melting in the south polar region.

Mantle–melt partitioning of the highly siderophile elements: New results and application to Mars

AbstractTrace elements and extant and extinct isotopic attributes in Martian meteorites have been used to argue that Mars accreted quickly, differentiated into core and mantle, and established several mantle reservoirs, possibly within 10 Ma of T0. The partitioning of trace elements in the deep mantle has been relatively unstudied, despite the need for such knowledge in understanding magma ocean crystallization and the origin of depleted and enriched mantle reservoirs. The siderophile element composition of the Martian mantle and lithophile isotopic systems such as Sr, Hf, and Nd are thought to record evidence for early metal–silicate equilibrium and deep magma ocean at an intermediate depth and pressure of 800 km or 14 GPa. We have carried out experiments across this pressure range to better understand the mineral/melt partitioning of a wide range of elements. These new data are used to evaluate differentiation models for Mars and to help interpret the available isotopic data. The relatively incompatible nature of Re compared to mildly compatible Os means that the crystallization of a deep magma ocean will lead to residual liquids with superchondritic Re/Os, and solids with subchondritic Re/Os. Such material available in the mantle could be the source of enriched isotopic reservoir that produced shergottites with +γOs values. Slightly subchondritic Re/Os ratios in the crystallizing solids would provide a reservoir that could produce −γOs values. Melting of mixtures of these two enriched and depleted endmembers could explain the Nd‐Os isotopic correlations and systematics of shergottites.

Detection of the Chandler Wobble of Mars From Orbiting Spacecraft

AbstractFor the first time for any planetary body other than the Earth, the free wobble of the pole called the Chandler wobble has been detected for Mars with a period of 206.9 ± 0.5 days and amplitude of 10 cm from radio tracking observations of Mars Odyssey, Mars Reconnaissance Orbiter (MRO), and Mars Global Surveyor (MGS), in order of decreasing sensitivity. The motion of the rotation pole location on the surface of Mars, or polar motion, is observed using two different approaches: (1) joint global estimates of Mars' orientation and its gravity field and (2) time series solutions of C21 and S21. For Mars interior models, the Chandler wobble period is combined with other measurements including the moments of inertia from our estimated precession rate and tidal Love number k2 = 0.169 ± 0.006. The Chandler wobble period constrains the rheology of the Martian mantle and in particular its long‐term frequency dependence.

Electrical and seismological structure of the martian mantle and the detectability of impact-generated anomalies

We derive synthetic electrical conductivity, seismic velocity, and density distributions from the results of martian mantle convection models affected by basin-forming meteorite impacts. The electrical conductivity features an intermediate minimum in the strongly depleted topmost mantle, sandwiched between higher conductivities in the lower crust and a smooth increase toward almost constant high values at depths greater than 400km. The bulk sound speed increases mostly smoothly throughout the mantle, with only one marked change at the appearance of β-olivine near 1100km depth. An assessment of the detectability of the subsurface traces of an impact suggests that its signature would be visible in both observables at least if efficient melt extraction from the shock-molten target occurs, but it will not always be particularly conspicuous even for large basins; observations with extensive spatial and temporal coverage would improve their detectability. Electromagnetic sounding may offer another possibility to investigate the properties of the mantle, especially in regions of impact structures. In comparison with seismology and gravimetry, its application to the martian interior has received little consideration so far. Of particular interest is its potential for constraining the water content of the mantle. By comparing electromagnetic sounding data of an impact structure with model predictions, it might also be possible to answer the open question of the efficiency of extraction of impact-generated melt.

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.

Ag isotopic and chalcophile element evolution of the terrestrial and martian mantles during accretion: New constraints from Bi and Ag metal-silicate partitioning

The Earth's timing of accretion and acquisition of moderately volatile compounds is uncertain. Hafnium-W and Mn-Cr isotopic data can bracket the timing of early planetary differentiation and core formation. The Ag-Pd system has also been utilized but its application has been limited by a lack of high pressure and temperature metal-silicate partitioning for Pd and Ag. Because Ag (and Bi) are volatile chalcophile siderophile elements, understanding their early distribution can constrain the origin of volatile elements in differentiated bodies and planets. Unfortunately, neither Ag or Bi have been studied across the wide range of pressure and temperature conditions that are relevant to accretion and core-mantle differentiation. Here, new high-pressure and temperature multi-anvil metal-silicate equilibrium experiments for Bi and Ag have been carried out at conditions relevant to planetary accretion and metal silicate differentiation that allow a more refined and complete understanding of element partitioning during core formation. The new metal-silicate partitioning data are combined with previously reported data, and utilized to predict the distributions of Bi, Pd, and Ag at conditions of accretion relevant for Earth and Mars. Application of the new partitioning results to Earth shows that D(Bi) and D(Ag) (D = metal/silicate concentration ratio) are lowered due to the effect of pressure and Si alloyed in the metallic liquid, resulting in higher predicted mantle Bi and Ag abundances than in the bulk silicate Earth (BSE), as well as high and variable Pd/Ag. The unradiogenic Ag isotopic composition of the BSE could have been generated by early accretion of volatile-poor (high Pd/Ag) pre-cursors, followed by later accretion of volatile–rich (low Pd/Ag) material, in agreement with earlier studies of Pd-Ag and Mn-Cr (Schönbächler et al., 2010). However, these main accretion phases would have to be followed by segregation of a sulfide liquid (at least 1.5% of magma ocean) at high pressures (>30 GPa), to explain the primitive upper mantle (PUM) Bi, Pd, and Ag, as well as Au, Pt, Cu and Ni concentrations as proposed previously. If the early accreted bulk Earth was volatile depleted with high Pd/Ag ratios, portions of the mantle may contain ancient domains that developed positive 107Ag isotopic anomalies (as also argued by noble gases, Nd, W, and Os isotopes). In comparison, Bi, Pd, and Ag concentrations in the martian mantle could have been set by simple metal-silicate equilibrium. Mars accreted and differentiated relatively rapidly, while also developing a deep magma ocean with a high Pd/Ag ratio that could have evolved positive 107Ag anomalies, in contrast to Earth. Measurements on shergottites may reveal these predicted Ag isotopic anomalies.

Deuterium and 37Chlorine Rich Fluids on the Surface of Mars: Evidence From the Enriched Basaltic Shergottite Northwest Africa 8657

AbstractApatite, a major hydrous mineral in Martian meteorites, has the potential to reveal history of volatiles on Mars. Here we report the H and Cl isotopic systematics of apatite from the enriched basaltic shergottite Northwest Africa (NWA) 8657 to better understand the processes influencing volatiles at or near the Martian (sub)surface. The apatite in NWA 8657 has the highest reported δD value (up to 6,509‰) of any phosphates in Martian meteorites. The positive correlation between the H2O contents (72–2,251 ppm) and δD values (3,965–6,509‰) as well as between the Cl contents (1.28–6.17wt%) and δ37Cl values (−1.7–4.0‰) in NWA 8657 apatite are consistent with mixing between volatiles derived from the Martian mantle and meteoric water/fluid. The D‐ and 37Cl‐enrichment of apatite in NWA 8657 implies isotopic exchange with subsurficial fluids during postcrystallization hydrothermal event(s).

Petrogenesis, alteration, and shock history of intermediate shergottite Northwest Africa 7042: Evidence for hydrous magmatism on Mars?

Northwest Africa (NWA) 7042 is an intermediate, permafic shergottite consisting of two generations of olivine (early zoned olivine Fo41-76, and late-stage fayalitic olivine Fo46-56), complexly zoned pyroxene (En35-64Fs22-46Wo5-34), shock-melted or maskelynitized feldspar (An5-30Ab16-61Or1-47), and accessory merrillite, apatite, ilmenite, titanomagnetite, Fe-Cr-Ti spinels, pyrrhotite, and baddeleyite. The zoned olivine grains have been pervasively modified, containing conspicuous brown Mg-rich cores surrounded by colorless, unaltered Fe-rich overgrowth rims. This textural relationship suggests that the cores were altered at magmatic temperatures prior to crystallization of the rims on Mars. Launch-generated shock veins in NWA 7042 also crosscut and displace several of the altered olivine grains indicating that alteration occurred before ejection of the meteorite. While this type of olivine alteration is rare in shergottites, it is similar to deuterically altered olivine in basalts and gabbros on Earth, caused by residual water-rich magmatic fluids. Transmission electron microscopy analysis of the olivine alteration did not reveal the high-temperature phases expected from this process; however, NWA 7042 has also been subjected to extensive terrestrial weathering, which may explain their absence. The potential presence of deuterically altered olivine in NWA 7042 has significant implications, as it is the third martian meteorite where deuteric alteration of olivine has been observed (the others being NWA 10416, and Allan Hills 77005). The different mantle sources for the parental melts of these three meteorites would suggest many, if not all martian mantle reservoirs have the potential to produce water-rich magmas.

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.

Insights into the chemical diversity of the martian mantle from the Pb isotope systematics of shergottite Northwest Africa 8159

Shergottite Northwest Africa (NWA) 8159 is a basaltic rock derived from a mantle source with chemical characteristics that are unique in the martian meteorite suite. To further investigate this source reservoir, the Pb isotope compositions of plagioclase/maskelynite, pyroxene, phosphates, and shock melt-glass in NWA 8159 have been measured in situ by Secondary Ion Mass Spectrometry (SIMS). Due to the limited spread in Pb isotope data, these Pb isotope compositions have been used to calculate an imprecise PbPb isochron age of 3.4 ± 2.1 Ga (2σ), which is broadly consistent with the crystallization age of 2.37 ± 0.25 Ga determined previously by 147Sm143Nd. The lack of radiogenic in-growth within individual minerals since 2.4 Ga means that this sample is depleted in U, which is in agreement with NWA 8159's positive initial ε143Nd. An initial Pb composition was calculated using an x-y weighted average of the least radiogenic Pb isotope population measured in the sample. This initial Pb composition is not consistent with the model for Pb growth in the shergottite mantle at 2.4 Ga. This composition is, however, consistent with the model for the Nakhla-Chassigny mantle. Using the latter model, a source μ (238U/204Pb) of 2.6 ± 0.6 has been calculated. This μ-value is in contrast with the other depleted shergottites (1.4-1.5) and falls significantly off the array of source ε143Nd vs. μ defined by the rest of the martian meteorite suite and thus, necessitates a differentiation history distinct from the other martian meteorites. Sequestering Pb in sulphides during differentiation is the only mechanism to fractionate U from Pb and create a low-μ reservoir. Consequently, the relatively high μ-value of the source of NWA 8159 is in contrast with the positive initial ε143Nd and indicates that its mantle source region likely lacked significant sulphur. This is consistent with the lack of sulphides in the sample itself and could have played a role in its complicated oxidation history.

The Solidus and Melt Productivity of Nominally Anhydrous Martian Mantle Constrained by New High Pressure‐Temperature Experiments—Implications for Crustal Production and Mantle Source Evolution

AbstractWe constrained the solidus of a model Martian composition with low bulk Mg# (molar MgO/(MgO + FeOT) × 100 ~75) and high total alkali (Na2O + K2O = 1.09 wt.%) concentration at 2 to 5 GPa by experiments. Based on the new solidus brackets, we provide a new parameterization of the solidus temperature as a function of pressure of Martian mantle: Ts(°C) = − 5P (GPa)2 + 107P(GPa) + 1,068. The newly constrained solidus of the Lodders and Fegley (1997; https://doi.org/10.1006/icar.1996.5653) model Martian composition (LF composition) is 20 to 90 °C lower than the previous solidus of model Martian mantle with lower total alkali (~0.54 wt.%). The supersolidus experiments yield an average isobaric melt productivity, dF/dT, of 20 ± 6 wt.%/100 °C. We also bracketed the solidi of model Martian mantle compositions with low Mg# (~75) and low alkali (~0.54 wt.%), and with high Mg# (~80) and low alkali (~0.54 wt.%) at a constant pressure of 3 GPa. We find that bulk Mg# enhances the solidus temperature and bulk total alkalis suppress it. A parameterization that estimates the effect of bulk Mg# and total alkalis on peridotite solidus, including Mars and Earth, at 3 GPa can be described as: Ts(°C) = 4.23Mg # − 85(Na2O(wt. %) + K2O(wt. %)) + 1,120. Based on the new solidus parameterizations, 10–40 km more Martian crust would be produced by columnar decompression melting for LF model composition compared to the low Mg#‐low alkali model composition. The quantitative constraints on the solidus shift with Mg# and total alkalis from this study can be used to assess the Martian mantle solidus change through melting and melt extraction over time and the role of mantle heterogeneity in crustal production.

Multiple early-formed water reservoirs in the interior of Mars.

The abundance and distribution of water within Mars through time plays a fundamental role in constraining its geological evolution and habitability. The isotopic composition of martian hydrogen provides insights into the interplay between different water reservoirs on Mars. However, D/H (deuterium/hydrogen) ratios of martian rocks and of the martian atmosphere span a wide range of values. This has complicated identification of distinct water reservoirs in and on Mars within the confines of existing models that assume an isotopically homogenous mantle. Here we present D/H data collected by secondary ion mass spectrometry for two martian meteorites. These data indicate that the martian crust has been characterized by a constant D/H ratio over the last 3.9 billion years. The crust represents a reservoir with a D/H ratio that is intermediate between at least two isotopically distinct primordial water reservoirs within the martian mantle, sampled by partial melts from geochemically depleted and enriched mantle sources. From mixing calculations, we find that a subset of depleted martian basalts are consistent with isotopically light hydrogen (low D/H) in their mantle source, whereas enriched shergottites sampled a mantle source containing heavy hydrogen (high D/H). We propose that the martian mantle is chemically heterogeneous with multiple water reservoirs, indicating poor mixing within the mantle after accretion, differentiation, and its subsequent thermochemical evolution.

Heavy halogen geochemistry of martian shergottite meteorites and implications for the halogen composition of the depleted shergottite mantle source

AbstractVolatile elements (e.g., H, C, N) have a strong influence on the physical and chemical evolution of planets and are essential for the development of habitable conditions. Measurement of the volatile and incompatible heavy halogens, Cl, Br, and I, can provide insight into volatile distribution and transport processes, due to their hydrophilic nature. However, information on the bulk halogen composition of martian meteorites is limited, particularly for Br and I, largely due to the difficulty in measuring ppb-level Br and I abundances in small samples. In this study, we address this challenge by using the neutron irradiation noble gas mass spectrometry (NI-NGMS) method to measure the heavy halogen composition of five olivine-phyric shergottite meteorites, including the enriched (Larkman Nunatak LAR 06319 and LAR 12011) and depleted (LAR 12095, LAR 12240, and Tissint) compositional end-members. Distinct differences in the absolute abundances and halogen ratios exist between enriched (74 to136 ppm Cl, 1303 to 3061 ppb Br, and 4 to 1423 ppb I) and depleted (10 to 26 ppm Cl, 46 to 136 ppb Br, and 3 to 329 ppb I) samples. All halogen measurements are within the ranges previously reported for martian shergottite, nakhlite, and chassignite (SNC) meteorites. Enriched shergottites show variable and generally high Br and I absolute abundances. Halogen ratios (Br/Cl and I/Cl) are in proportions that exceed those of both carbonaceous chondrites and the martian surface. This may be linked to a volatile-rich martian mantle source, be related to shock processes or could represent a small degree of heavy halogen contamination (a feature of some Antarctic meteorites, for example). The differences observed in halogen abundances and ratios between enriched and depleted compositions, however, are consistent with previous suggestions of a heterogeneous distribution of volatiles in the martian mantle. Depleted shergottites have lower halogen abundances and Br and Cl in similar proportions to bulk silicate Earth and carbonaceous chondrites. Tissint in particular, as an uncontaminated fall, allows an estimate of the depleted shergottite mantle source composition to be made: 1.2 ppm Cl, 7.0 ppb Br, and 0.2 ppb I. The resultant bulk silicate Mars (BSM) estimate (22 ppm Cl, 74 ppb Br, and 6 ppb I), including the martian crust and depleted shergottite mantle, is similar to estimates of the bulk silicate earth (BSE) halogen composition.