Nakhlite Meteorites Research Articles

Sulfur in apatite from the Nakhla meteorite record a late-stage oxidation event

Estimates of the oxygen fugacity (fO2) recorded by the Martian nakhlite meteorites from direct observations of the main igneous phenocryst assemblages range from values similar to that recorded by the quartz-fayalite-magnetite oxygen buffer to ∼two orders of magnitude lower. Inferences of changes in fO2 during the late stages of crystallization, volcanic degassing, and emplacement of the nakhlite cumulate pile have been made based on variable sulfide and apatite chemistry. We present S-XANES measurements of the oxidation state of sulfur in apatite and associated mesostasis glass in Nakhla to place direct constraints on the magnitude of changes in fO2 experienced by the Nakhla portion of the nakhlite cumulate pile during apatite crystallization. Nakhla apatites range from containing dominantly S2− to containing dominantly S6+. This, together with correlations between S2−, Cl, and FeO in the mesostasis glass near these apatites, suggest that our measurements capture directly the oxidation of the interstitial late-stage Nakhla magmas as the result of Cl-saturation and degassing. As the result of this degassing, at least part of the nakhlite cumulate pile experienced an increase in fO2 of ∼1.5–2.5 orders of magnitude during apatite crystallization and final mesostasis cooling. Based on these measurements, the sulfur oxidation states of apatites in the other nakhlite meteorites are predicted to range from exclusively S2−-bearing to exclusively S6+-bearing.

Constraints on the Emplacement of Martian Nakhlite Igneous Rocks and Their Source Volcano From Advanced Micro‐Petrofabric Analysis

AbstractThe Martian nakhlite meteorites, which represent multiple events that belong to a single magma source region represent a key opportunity to study the evolution of Martian petrogenesis. Here 16 of the 26 identified nakhlite specimens are studied using coupled electron backscatter diffraction (EBSD) and emplacement end‐member calculations. EBSD was used to determine shape preferred orientation of contained augite (high Ca‐clinopyroxene) phenocrysts by considering their crystallographic preferred orientation (CPO). Parameters derived from EBSD, and energy dispersive X‐ray spectroscopy spectra were used in basic emplacement models to assess their dominant mechanism against three end‐member scenarios: thermal diffusion, crystal settling, and crystal convection. Results from CPO analyses indicate low intensity weak‐moderate CPO. In all samples, a consistent foliation within the <001> axes of augite are observed typically coupled with a weaker lineation CPO in one of the other crystallographic axes. These CPO results agree best with crystal settling being the dominant emplacement mechanism for the nakhlites. Modeled crystal settling results identify two distinguishable groups outside of the model's resolution indicating the presence of secondary emplacement mechanisms. Comparison of the two identified groups against CPO, geochemical, and age parameters indicate random variability between individual meteorites. Therefore, coupled CPO and emplacement modeling results identify an overarching characteristic of a dominant crystal settling emplacement mechanism for the nakhlite source volcano despite exhibiting random variation with each discharge through time.

Can the Magmatic Conditions of the Martian Nakhlites be Discerned via Investigation of Clinopyroxene and Olivine Intracrystalline Misorientations?

AbstractDeformation is a near ubiquitous process that is observed within nearly all naturally forming rocks. Electron backscatter diffraction (EBSD) is a technique that enables slip‐systems (a form of plastic deformation) to be inferred from intracrystalline misorientations at a comparable scale to the representative CPO analysis (≥300 crystals for the nakhlites). Extensive laboratory and studies on naturally occurring samples have identified preferential mantle condition extrinsic parameters for specific slip‐system signatures within olivine and clinopyroxene. Intracrystalline misorientation patterns for olivine and augite (high Ca‐clinopyroxene) for 16 different Martian nakhlite meteorites (21 sections) were analyzed and assessed against these known parameters. Investigation of high and low deformation regions within the nakhlites revealed a shift in intracrystalline misorientation patterns for 10 of the 21 sections. Interpreted as both shock (high deformations) and emplacement (low deformation) signatures, the observed variations in deformation patterns for the two main regimes of deformation indicate heterogeneous sampling of the nakhlite source crater. Our findings indicate that shock deformation is prevalent throughout the nakhlites, and that great care needs to be taken when interpreting intracrystalline misorientations of crystals within apparent lower deformation regions.

The scale of a martian hydrothermal system explored using combined neutron and x-ray tomography.

Nakhlite meteorites are igneous rocks from Mars that were aqueously altered ~630 million years ago. Hydrothermal systems on Earth are known to provide microhabitats; knowledge of the extent and duration of these systems is crucial to establish whether they could sustain life elsewhere in the Solar System. Here, we explore the three-dimensional distribution of hydrous phases within the Miller Range 03346 nakhlite meteorite using nondestructive neutron and x-ray tomography to determine whether alteration is interconnected and pervasive. The results reveal discrete clusters of hydrous phases within and surrounding olivine grains, with limited interconnectivity between clusters. This implies that the fluid was localized and originated from the melting of local subsurface ice following an impact event. Consequently, the duration of the hydrous alteration was likely short, meaning that the martian crust sampled by the nakhlites could not have provided habitable environments that could harbor any life on Mars during the Amazonian.

Boom boom pow: Shock-facilitated aqueous alteration and evidence for two shock events in the Martian nakhlite meteorites.

Nakhlite meteorites are ~1.4 to 1.3 Ga old igneous rocks, aqueously altered on Mars ~630 Ma ago. We test the theory that water-rock interaction was impact driven. Electron backscatter diffraction demonstrates that the meteorites Miller Range 03346 and Lafayette were heterogeneously deformed, leading to localized regions of brecciation, plastic deformation, and mechanical twinning of augite. Numerical modeling shows that the pattern of deformation is consistent with shock-generated compressive and tensile stresses. Mesostasis within shocked areas was aqueously altered to phyllosilicates, carbonates, and oxides, suggesting a genetic link between the two processes. We propose that an impact ~630 Ma ago simultaneously deformed the nakhlite parent rocks and generated liquid water by melting of permafrost. Ensuing water-rock interaction focused on shocked mesostasis with a high density of reactive sites. The nakhlite source location must have two spatially correlated craters, one ~630 Ma old and another, ejecting the meteorites, ~11 Ma ago.

Understanding the emplacement of Martian volcanic rocks using petrofabrics of the nakhlite meteorites

In order to validate calculated ages of the Martian crust we require precise radiometric dates from igneous rocks where their provenance on the Martian surface is known. Martian meteorites have been dated precisely and quantitatively, but the launch sites are currently unknown. Inferring the formation environment of a correlated suite of Martian meteorites can constrain the nature and complexity of the volcanic system they formed from. The nakhlite meteorites are such a suite of augite-rich rocks that sample the basaltic crust of Mars, and as such can provide unique insights into its volcanic processes. Using electron backscatter diffraction we have determined the shape-preferred and crystallographic-preferred orientation petrofabrics of four nakhlites (Governador Valadares, Lafayette, Miller Range 03346 and Nakhla) in order to understand the conditions under which their parent rocks formed. In all samples, there is a clear link between the shape-preferred orientation (SPO) and crystallographic-preferred orientation (CPO) of augite phenocrysts. This relationship reveals the three-dimensional shape of the augite crystals using CPO as a proxy for 3D SPO, and also enables a quantitative 3-dimensional petrofabric analysis. All four nakhlites exhibit a foliation defined by the CPO of the augite <c> axis in a plane, although individual meteorites show subtle textural variations. Nakhla and Governador Valadares display a weak CPO lineation within their <c> axis foliation that is interpreted to have developed in a combined pure shear/simple shear flow regime, indicative of emplacement of their parent rock as a subaerial hyperbolic lava flow. By contrast, the foliation dominated CPO petrofabrics of Lafayette and Miller Range 03346 suggest formation in a pure shear dominated regime with little influence of hyperbolic flow. These CPO petrofabrics are indicative of crystal settling in the stagnant portion of cooling magma bodies, or the flattening area of spreading lava flows. The CPO foliation of Lafayette's is substantially weaker than Miller Range 03346, probably due to its higher phenocryst density causing grain-grain interactions that hindered fabric development. The CPO petrofabrics identified can also be used to determine the approximate plane of the Martian surface and the line of magma flow to within ∼20°. Our results suggest that the nakhlite launch crater sampled a complex volcanic edifice that was supplied by at least three distinct magmatic systems limiting the possible locations these rocks could have originated from on Mars.

Evidence for oxidation at the base of the nakhlite pile by reduction of sulfate salts at the time of lava emplacement

The assimilation of sulfate by Martian melts could explain the highly oxidized state of some Martian nakhlite meteorites, such as those paired with MIL 03346 (MIL 090030, MIL 090032, and MIL 090136). Here, a combination of new sulfur isotope data, mineral composition and abundance data, and consideration of mineral textures is used to link assimilation of surface-derived Martian sulfate to oxidation of nakhlite melts. The magnitudes of the mass independent sulfur isotope signatures (negative Δ33S) and the abundance of sulfide minerals accounts for much of the added oxygen implied by the occurrence of abundant skeletal titanomagnetite in the MIL pairs. Assimilation and reduction of sulfate amounts equivalent to that from 10′s of centimeters of Martian sediment are required to account for an oxidation front extending ∼1 m into the flow, a position previously proposed for MIL 03346, and implies a position at the bottom, rather than the top of a nakhlite flow. A similar positional and amount constraint is required for an alternative path for assimilation of sulfate from sulfate-rich brine. Assimilation and reduction of sulfate is therefore inferred to play a critical role in establishing both the enrichment in skeletal titanomagnetite within the lower portion of the nakhlite pile and the large Δ33S anomalies of the MIL pairs. Other nakhlites with smaller Δ33S anomalies and less titanomagnetite would occupy positions farther away from the source of sulfate.

Aqueous alteration of the Martian meteorite Northwest Africa 817: Probing fluid–rock interaction at the nakhlite launch site

AbstractThe nakhlite meteorites characteristically contain iddingsite, a hydrous iron–magnesium silicate that formed by aqueous alteration on Mars. Iddingsite is most abundant in Northwest Africa (NWA) 817, and alteration products in this meteorite also have the lowest deuterium/hydrogen ratio of any nakhlite. Taken together, these distinctive properties could be interpreted to show that NWA 817 was altered under different physico‐chemical conditions than the other nakhlites and by liquid water from a separate reservoir. Here this interpretation is tested through a petrographic, mineralogical, chemical, and isotopic study of NWA 817. We find that its iddingsite occurs as olivine‐hosted veins of nanocrystalline smectite and Fe‐oxyhydroxide. Strong similarities in the mineralogy of iddingsite between NWA 817 and other nakhlites suggest that these meteorites were altered under comparable physico‐chemical conditions, with the Fe‐rich composition of NWA 817 olivine grains rendering them especially susceptible to aqueous alteration. Analyses of NWA 817 bulk samples by stepwise pyrolysis confirm that its iddingsite has unusually low deuterium/hydrogen ratios, but owing to terrestrial weathering of this meteorite, the hydrogen isotopic data cannot be used with confidence to infer the origin of Martian aqueous solutions. NWA 817 was most probably altered along with the other nakhlites over a short time period and in a common aqueous system. One interpretation of a correlation between the eruption ages of three of the nakhlites and the chemical composition of their iddingsite is that water originated from close to the surface of Mars and flowed through the nakhlite lava pile under the influence of gravity.

Hydrothermal activity recorded in post Noachian‐aged impact craters on Mars

AbstractHydrothermal systems have previously been reported in ancient Noachian and Hesperian‐aged craters on Mars using CRISM but not in Amazonian‐aged impact craters. However, the nakhlite meteorites do provide evidence of Amazonian hydrothermal activity. This study uses CRISM data of 144 impact craters of ≥7 km diameter and 14 smaller craters (3–7 km diameter) within terrain mapped as Amazonian to search for minerals that may have formed as a result of impact‐induced hydrothermal alteration or show excavation of ancient altered crust. No evidence indicating the presence of hydrated minerals was found in the 3–7 km impact craters. Hydrated minerals were identified in three complex impact craters, located at 52.42°N, 39.86°E in the Ismenius Lacus quadrangle, at 8.93°N, 141.28°E in Elysium, and within the previously studied Stokes crater. These three craters have diameters 20 km, 62 km, and 51 km. The locations of the hydrated mineral outcrops and their associated morphology indicate that two of these three impact craters—the unnamed Ismenius Lacus Crater and Stokes Crater—possibly hosted impact‐induced hydrothermal systems, as they contain alteration assemblages on their central uplifts that are not apparent in their ejecta. Chlorite and Fe serpentine are identified within alluvial fans in the central uplift and rim of the Ismenius Lacus crater, whereas Stokes crater contains a host of Fe/Mg/Al phyllosilicates. However, excavation origin cannot be precluded. Our work suggests that impact‐induced hydrothermalism was rare in the Amazonian and/or that impact‐induced hydrothermal alteration was not sufficiently pervasive or spatially widespread for detection by CRISM.

Searching for the Source Crater of Nakhlite Meteorites.

We surveyed the Martian surface in order to identify possible source craters of the nakhlite Martian meteorites. We investigated rayed craters that are assumed to be younger than 11Ma, on lava surfaces with a solidification age around 1.2Ga. An area of 17.3 million km2 Amazonian lava plains was surveyed and 53 rayed craters were identified. Although most of them are smaller than the threshold limit that is estimated as minimum of launching fragments to possible Earth crossing trajectories, their observed size frequency distribution agrees with the expected areal density from cratering models characteristic for craters that are less than few tens of Ma old. We identified 6 craters larger than 3km diameter constituting the potentially best source craters for nakhlites. These larger candidates are located mostly on a smooth lava surface, and in some cases, on the earlier fluvial-like channels. In three cases they are associated with fluidized ejecta lobes and rays - although the rays are faint in these craters, thus might be older than the other craters with more obvious rays. More work is therefore required to accurately estimate ages based on ray system for this purpose. A more detailed search should further link remote sensing Martian data with the in-situ laboratory analyses of Martian meteorites, especially in case of high altitude, steep terrains, where the crater rays seems to rarely survive several Ma.

Opal‐A in the Nakhla meteorite: A tracer of ephemeral liquid water in the Amazonian crust of Mars

AbstractThe nakhlite meteorites are clinopyroxenites that are derived from a ~1300 million year old sill or lava flow on Mars. Most members of the group contain veins of iddingsite whose main component is a fine‐grained and hydrous Fe‐ and Mg‐rich silicate. Siderite is present in the majority of veins, where it straddles or cross‐cuts the Fe‐Mg silicate. This carbonate also contains patches of ferric (oxy)hydroxide. Despite 40 years of investigation, the mineralogy and origins of the Fe‐Mg silicate is poorly understood, as is the paragenesis of the iddingsite veins. Nanometer‐scale analysis of Fe‐Mg silicate in the Nakhla meteorite by electron and X‐ray imaging and spectroscopy reveals that its principal constituents are nanoparticles of opal‐A. This hydrous and amorphous phase precipitated from acidic solutions that had become supersaturated with respect to silica by dissolution of olivine. Each opal‐A nanoparticle is enclosed within a ferrihydrite shell that formed by oxidation of iron that had also been liberated from the olivine. Siderite crystallized subsequently and from solutions that were alkaline and reducing, and replaced both the nanoparticles and olivine. The fluids that formed both the opal‐A/ferrihydrite and the siderite were sourced from one or more reservoirs in contact with the Martian atmosphere. The last event recorded by the veins was alteration of the carbonate to a ferric (oxy)hydroxide that probably took place on Mars, although a terrestrial origin remains possible. These results support findings from orbiter‐ and rover‐based spectroscopy that opaline silica was a common product of aqueous alteration of the Martian crust.

Ferric saponite and serpentine in the nakhlite martian meteorites

Transmission electron microscopy and Fe-K X-ray absorption spectroscopy have been used to determine structure and ferric content of the secondary phase mineral assemblages in the nakhlite martian meteorites, NWA 998, Lafayette, Nakhla, GV, Y 000593, Y 000749, MIL 03346, NWA 817, and NWA 5790. The secondary phases are a rapidly cooled, metastable assemblage that has preserved Mg# and Ca fractionation related to distance from the fluid source, for most of the nakhlites, though one, NWA 5790, appears not to have experienced a fluid pathway. All nine nakhlite samples have also been analysed with scanning electron microscopy, electron probe micro analysis, Bright Field high-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction. By measuring the energy position of the Fe-K XANES 1s→3d pre-edge transition centroid we calculate the ferric content of the minerals within the nakhlite meteorites. The crystalline phyllosilicates and amorphous silicate of the hydrothermal deposits filling the olivine fractures are found to have variable Fe3+/ΣFe values ranging from 0.4 to 0.9. In Lafayette, the central silicate gel parts of the veins are more ferric than the phyllosilicates around it, showing that the fluid became increasingly oxidised. The mesostasis of Lafayette and NWA 817 also have phyllosilicate, which have a higher ferric content than the olivine fracture deposits, with Fe3+/ΣFe values of up to 1.0. Further study, via TEM analyses, reveal the Lafayette and NWA 817 olivine phyllosilicates to have 2:1 T–O–T lattice structure with a the d001-spacing of 0.96nm, whereas the Lafayette mesostasis phyllosilicates have 1:1 T–O structure with d001-spacings of 0.7nm. Based on our analyses, the phyllosilicate found within the Lafayette olivine fractures is trioctahedral ferric saponite (Ca0.2K0.1)∑0.3(Mg2.6Fe2+1.3Fe3+1.7Mn0.1)∑5.7[(Si6.7AlIV0.9Fe3+0.4)∑8.0O20](OH)4·nH2O, and that found in the mesostasis fractures is an Fe-serpentine (Ca0.1Mg0.7Fe3+1.0AlVI0.4)∑2.2[Si2O5]OH4, with a ferric gel of similar composition in Lafayette and found as fracture fills throughout the other nakhlites.

CO2 solubility in primitive martian basalts similar to Yamato 980459, the effect of composition on CO2 solubility of basalts, and the evolution of the martian atmosphere

To determine the influence of basalt composition on the CO2 solubility in martian lavas, we investigated experimentally a synthetic melt based on the martian meteorite Yamato 980459 (Y 980459), an olivine-phyric shergottite and a picritic rock (19 wt% MgO) thought to be a near-primary liquid derived from high-temperature (>1540 °C) partial melting of the martian mantle. Experiments were performed in a piston-cylinder apparatus at 1–2 GPa and 1600–1650 °C. CO2 contents in quenched glasses were determined using Fourier transform infrared spectroscopy (FTIR) and range from 0.45–1.26 wt%. Despite large differences in FeO* and MgO contents, the CO2 solubilities in Y 980459 are similar to that in a less primitive synthetic martian basalt based on the Humphrey rock and to a Hawaiian tholeiite. The lack of enhanced solubility in Fe2+- and Mg2+-rich melts is likely owing to the complex structural role of these cations in silicate melts, acting partly as network formers, rather than network modifiers. The small sensitivity of CO2 solubility to compositional variations among martian and tholeiitic basalts means that the experimentally determined solubilities may be applicable to a wide spectrum of martian magmatic products. Using experimentally determined CO2 solubilities of Y 980459 and Humphrey allows the calibration of the thermodynamic parameters governing dissolution of CO2 vapor as carbonate in martian basalts. This relation facilitates calculation of the CO2 dissolved in magmas derived from graphite-saturated martian basalt source regions as a function of P , T , and f O2. The hot conditions in the source of Y 980459, 1540 ± 10 °C, and 1.2 ± 0.5 GPa, are plausible for plume-related magmas forming the giant Tharsis volcanic complex, which accounts for 50% of martian igneous activity since stabilization of the primordial crust. If oxygen fugacity in the sources of hot Tharsis magmatism were equivalent to that at the iron-wustite buffer (IW) or 1 log unit above (IW+1), respectively, then the entire Tharsis event would outgas 30–300 mbars of CO2 to the martian atmosphere, which is far from the 2 bars required to stabilize an equable climate in the late Noachian and early Hesperian epochs. This mismatch could be reconciled if significant martian igneous activity derived from comparatively oxidized mantle sources (i.e., IW+2) similar to those responsible for the nakhlite meteorites.

Martian subsurface fluid pathways and 3D mineralogy of the Nakhla meteorite

The three dimensional structure of the Nakhla meteorite has been investigated in order to provide a detailed picture of the fluid pathways in the volcanic subsurface of Mars. A combination of computed tomography and electron microscopy have been used to identify, characterise and interpret the distribution, size, interconnectivity and secondary mineralisation of fractures through which water flowed. Secondary minerals which formed during aqueous alteration are found as fracture-filling silicates in olivine grains and a range of carbonates, sulfates and halite are found throughout olivine, pyroxene and mesostasis. The fractures which acted as fluid pathways are highly interconnected, branching and reconnecting at multiple locations, leading to a pervasive and homogeneous distribution of secondary minerals throughout the sample. Miniature topographic basins have been identified and provide a unique method of identifying the true orientation of the meteorite while on its host planetary surface. Halite and sulfate are found to be related to one another, likely formed in the same episode of fluid flow, and are found to postdate both carbonate and olivine-hosted silicate-alteration products. Later episodes of fluid flow may have interacted with, and potentially eroded, earlier generations of secondary minerals. Nakhla, and by implication the other nakhlite meteorites, therefore preserves a complex record of multiple episodes of fluid flow on Mars in the past billion years.

Melt inclusions in augite from the nakhlite meteorites: A reassessment of nakhlite parental melt and implications for petrogenesis

Abstract– The nakhlites, a subgroup of eight clinopyroxenites thought to come from a single geological unit at the Martian surface, show melt inclusions in augite and olivine. In contrast to olivine‐hosted melt inclusions, augite‐hosted melt inclusions are not surrounded by fractures, and are thus considered preferential candidates for reconstructing parent liquid compositions. Furthermore, two types of augite‐hosted melt inclusion have been defined and characterized in four different nakhlites (Northwest Africa [NWA] 817, Nakhla, Governador Valadares, and NWA 998): Type‐I isolated inclusions in augite cores that contain euhedral to subhedral augite, Ti‐magnetite, and pigeonite plus silica‐rich glass and a gas bubble; Type‐II microinclusions that form trails crosscutting host augite crystals. Fast‐heating experiments were performed on selected pristine primary augite‐hosted melt inclusions from these four samples. Of these, only data from Nakhla were considered robust for reconstruction of a nakhlite parental magma composition (NPM). Based upon careful petrographic selection and consideration of iron‐magnesium ratios, our data are used to propose an NPM, which is basaltic (49.1 wt% SiO2), of high Ca/Al (1.95), and K2O‐poor (0.32 wt%). Thermodynamic modeling at an oxygen fugacity one log unit below the QFM buffer using the MELTS and PETROLOG programs implies that Mg‐rich olivine was not a liquidus phase for this composition. Our analysis is used to suggest that olivine megacrysts found in the nakhlites are unlikely to have coprecipitated with augite, and thus may have been introduced during or subsequent to accumulation in the magma chamber, possibly from more evolved portions of the same chamber.

Alteration assemblages in the nakhlites: Variation with depth on Mars

Secondary mineral assemblages in the nakhlite meteorites, Lafayette, Governador Valadares (GV), Nakhla, Yamato (Y)-000593 ⁄ Y-000749 have been studied using scanning electron microscopy, transmission electron microscopy, and electron probe micro analysis. The different nakhlites have distinctive secondary assemblages in their olivine grains and mesostases, showing compositional fractionation correlated with their relative depths below the Martian surface. Fracture-filled veins in Lafayette at the bottom of the pile consist of a siderite-phyllosilicate-Fe oxide-hydrated silicate gel assemblage. Corresponding veins in Nakhla and GV further up the pile are predominantly a siderite-gel assemblage, with additional evaporites including gypsum. Y-000593 ⁄ Y-000749 veins are dominated by gel. The gel's Mg ⁄ (Mg + Fe) ratio decreases from Lafayette (0.37) to GV (0.32), Nakhla (0.24), and Y-000593 (0.15). We suggest that hydrothermal fluid flowed up this depth profile, initiated by melting of buried H2O-CO2 ice. Our results show a complex mix of Fe-rich phyllosilicate within the veins and mesostasis of Lafayette with d-spacings of 0.7-1.1 nm suggesting a mixture of smectite and serpentine. The phyllosilicate formed at close to neutral pH, £150 � C. We also suggest that water rock ratios (W ⁄ R) of 1-10 occurred in Lafayette with smaller values for the other nakhlites. This is reflected in the volume of alteration minerals: 10% of olivine in Lafayette to 3% in Nakhla. Textural evidence of rapid cooling, together with the W ⁄ R and likely fluid velocities, suggest that the secondary assemblages formed quickly, e.g., within months. A model is proposed in which the secondary assemblages formed in an impact-induced hydrothermal system terminated by precipitation of the gel and evaporation of soluble salts.

Early martian mantle overturn inferred from isotopic composition of nakhlite meteorites

Following the crystallization of a magma ocean, the martian mantle probably underwent an overturning event, but its initiation, timing and geochemical consequences are poorly constrained. Isotopic data for martian meteorites and numerical simulations provide strong evidence for early overturning in the martian mantle.

Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: The case of pyroxene phenocrysts from nakhlite meteorites

Ion-microprobe was used to measure Li abundances and isotopic compositions in pyroxenes from three Martian meteorites belonging to the nakhlite family. The profiles performed across augite crystals from Northwest Africa 817 show a large isotopic zoning from crystal cores ( δ 7Li ∼ 0‰) to rims ( δ 7Li ∼ +20‰) while Li abundances are almost constant (∼9.2 μg/g). Unlike NWA 817, the pyroxene studied in the Miller Range 03346 nakhlite shows a zoning in Li abundance, with concentrations increasing from ∼2.5 μg/g in the core to ∼9 μg/g in the rim. The augite rim ( δ 7Li = +7‰) is slightly enriched in 7Li with regard to the core ( δ 7Li = +4‰), but most of the isotopic variations observed occur at an intermediate position along the profile, where δ 7Li falls down to ∼−11‰. In the case of Nakhla, Li concentrations in augite increase from cores (∼3.5 μg/g) to rims (∼6.5 μg/g), while the δ 7Li variation is restricted (i.e., between δ 7Li = +6.0 and +12.6‰). For the three meteorites the Li abundances were also measured in the groundmass, which was found to be enriched in lithium (∼10 μg/g). Conventional magmatic and post-magmatic processes such as alteration and fractional crystallization, fail to explain the dataset obtained on nakhlites. Degassing processes, which were previously proposed to explain the Li distribution in shergottite crystals, cannot result in the strong decoupling between Li abundances and isotopic composition observed in nakhlites. We suggest that the original magmatic Li distributions (concentrations and isotopic compositions) in nakhlites have been modified by diffusion of Li from the Li-rich groundmass towards the pyroxene crystals during sub-solidus cooling. Diffusion appears to have been efficient for NWA 817 and MIL 03346 but, apparently, did not produce a significant migration of Li in Nakhla, possibly because of the lower abundance of groundmass in the latter. Diffusion induced Li redistributions may also affect terrestrial porphyric rocks but very specific cooling rates are required to quench the diffusion profiles as observed in two of the present nakhlites.

Light lithophile elements in pyroxenes of Northwest Africa (NWA) 817 and other Martian meteorites: Implications for water in Martian magmas

Zoning patterns of light lithophile elements (the LLE: Li, Be, and B) in pyroxenes of some Martian basaltic meteorites have been used to suggest that the parent basalts were saturated in water and exsolved an aqueous fluid phase. Here, we examine LLE zoning in the augites of a quickly cooled Martian basalt that was not water-saturated—the Northwest Africa (NWA) 817 nakhlite. Analyses for LLE were by secondary ion mass spectrometry (SIMS), supported by EMP analyses of major and minor elements. In NWA 817, zoning of Be and B is consistent with igneous fractionations while Li abundances are effectively constant across wide ranges in abundance of other incompatible elements (Be, B, Ti, and Fe*). The lack of strong zoning in Li can be ascribed to intracrystalline diffusion, despite the rapid cooling of NWA 817. Most other nakhlites, notably Nakhla and Lafayette, cooled more slowly than did NWA 817 [Treiman, A.H., 2005. The nakhlite Martian meteorites: augite-rich igneous rock from Mars. Chem. Erde 65, 203–270]. In them Li abundances are constant across augite, as are abundances of other elements. In Nakhla pyroxenes, all the LLE have effectively constant abundances across significant ranges in Fe* and Ti abundance. Lafayette is more equilibrated still, and shows constant abundances of LLE and nearly constant Fe*. A pyroxene in the NWA480 shergottite has constant Li abundances, and was interpreted to represent mineral fractionation coupled with exsolution of aqueous fluid. A simple quantitative model of this process requires that the partitioning of Li between basalt and aqueous fluid, Li D aq/bas, be 15 times larger than its experimentally determined value. Thus, its seems unlikely that the Li zoning pattern in NWA480 augite represents exsolution of aqueous fluid. Late igneous or sub-solidus diffusion seems more likely as is suggested by Li isotopic studies [Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2005. An ion-microprobe study of lithium isotopes behavior in nakhlites. Meteorit. Planet. Sci. 40, Abstract #5118; Beck, P., Chaussidon, M., Barrat, J.-A., Gillet, Ph., Bohn, M., 2006. Diffusion induced Li isotopic fractionation during the cooling of magmatic rocks: the case of pyroxene phenocrysts from nakhlite meteorites. Geochim. Cosmochim. Acta 70, in press]. Pyroxenes of the Shergotty and Zagami meteorites have nearly constant abundances of B, and Li that decreases core-to-rim. Applying the quantitative model to the constant B in these pyroxenes requires that B D aq/bas be 25 times larger than experimentally constrained values. Li abundances in pigeonite can be fit by the model of crystal fractionation and fluid loss, but only if Li D aq/bas is 30 times the experimentally constrained value. The Li abundance pattern in augite cannot be modeled by simple fractionation, suggesting some strong crystal-composition effects. Thus, Li and B distributions in Shergotty and Zagami pyroxenes cannot be explained by igneous fractionation and exsolution of aqueous vapor. Intracrystalline diffusion, complete for B and incomplete for Li, seems more consistent with the observed zoning patterns.

Clues to Martian brines based on halogens in salts from nakhlites and MER samples

Chlorine and Br abundances in fracture‐filling secondary salts in Nakhla veins determined in this study by Synchrotron X‐ray Microprobe (Br) and Electron Microprobe (Cl) techniques compare well to the halogens determined recently by APXS instruments in soils and rock rinds at the Gusev and Meridiani sites. The salts in these Mars rocks arise from Martian brines that have undergone evaporative or freezing concentration. The halogen abundances in these salts are corrected for “dilution effect” (because of mixing with halogen‐poor phases) to obtain their “true” abundances, which seem to be close to the halogen abundances in terrestrial sea brines. Consistent with the petrographic evidence for evaporative salt deposition sequence of carbonate‐sulfate‐halite in nakhlite meteorites, Nakhla veins yield high Br (∼250 ppm) and low Cl/Br ratios (∼10–50), suggesting possible salt deposition from concentrated brines, whereas Lafayette iddingsite, with low Br (11 ppm) and high Cl/Br ratios (∼250–300), indicates salt deposition from dilute brines on Mars. The low Cl/Br ratios (∼20 to 80) in salts from Gusev and Meridiani rock rinds indicate that they presumably originate from concentrated subsurface Martian brines. The high Cl/Br ratio (∼270) in salts deposited by dilute solutions in Lafayette and Adirondack is similar to the chondritic Cl/Br ratio, which seems to characterize the dilute brines on Mars (prior to halite precipitation) including “Early Mars Waters” (Noachian or earlier). Our results seem to be consistent with the Burt‐Knauth model involving density stratification during evaporation/freezing of brine solutions in Martian regolith.