Amazonian-age Martian meteorites contain products of indigenous aqueous alteration; yet, establishing when this alteration occurred, and therefore when liquid water was available in the planet's crust, has proven challenging. New Ar-40/Ar-39 dates for iddingsite within the Martian meteorite Lafayette show these minerals precipitated from liquid water at 742 +/- 15 Ma (2 sigma). This age is the most precise constraint to date on water-rock interaction on Mars, and postdates formation of the host igneous rock by similar to 580 Myr. We infer that magmatic activity most likely induced melting of local permafrost and led to alteration of the nakhlites, suggesting that activation of localised hydrological cycles on Amazonian Mars by magmatism was infrequent and transient, but not unusual.

Mars hosts the solar system’s largest volcanoes. Although their size and impact crater density indicate continued activity over billions of years, their formation rates are poorly understood. Here we quantify the growth rate of a Martian volcano by 40 Ar/ 39 Ar and cosmogenic exposure dating of six nakhlites, meteorites that were ejected from Mars by a single impact event at 10.7 ± 0.8 Ma (2 σ ). We find that the nakhlites sample a layered volcanic sequence with at least four discrete eruptive events spanning 93 ± 12 Ma (1416 ± 7 Ma to 1322 ± 10 Ma (2 σ )). A non-radiogenic trapped 40 Ar/ 36 Ar value of 1511 ± 74 (2 σ ) provides a precise and robust constraint for the mid-Amazonian Martian atmosphere. Our data show that the nakhlite-source volcano grew at a rate of ca. 0.4–0.7 m Ma −1 —three orders of magnitude slower than comparable volcanoes on Earth, and necessitating that Mars was far more volcanically active earlier in its history.

On Earth, carbon sequestration in geologic units plays an important role in the carbon cycle, scrubbing CO2 from the atmosphere for long-term storage. While carbonate is identified in low abundances within the dust and soils of Mars, at < 1 wt% in select meteorites, and in limited outcrops, no massive carbonate rock reservoir on Mars has been identified to date. Here, we investigate the largest exposed carbonate-bearing rock unit, the Nili Fossae plains, combining spectral, thermophysical, and morphological analyses to evaluate the timing and carbon sequestration potential of rocks on Mars. We find that the olivine-enriched (similar to 20%-25%) basalts have been altered, by low-temperature in situ carbonation processes, to at most similar to 20% Fe-Mg carbonate, thus limiting carbon sequestration in the Nili Fossae region to similar to 0.25-12 mbar of CO2 during the late Noachian-early Hesperian, before or concurrent with valley network formation. While this is large compared to modern-day CO2 reservoirs, the lack of additional, comparably sized post-late Noachian carbonate-bearing deposits on Mars indicates ineffective carbon sequestration in rock units over the past similar to 3.7 b.y. This implies a thin atmosphere (less than or similar to 500 mbar) during valley network formation, extensive post-Noachian atmospheric loss to space, or diffuse, deep sequestration by a yet-to-be understood process. In stark contrast to Earth's biologically mediated crust: atmosphere carbon reservoir ratio of similar to 10(4)-10(5), Mars' ratio is a mere similar to 10-10(3), even if buried pre-Noachian crust holds multiple bars.

All meteorites contain variable amounts of cosmogenic 38Ar and 36Ar produced during extraterrestrial exposure, and in order to calculate reliable 40Ar/39Ar ages this cosmogenic Ar must be removed from the total Ar budget. The amount of cosmogenic Ar has usually been calculated from the step-wise 38Ar/36Ar, minimum 36Ar/37Ar, or average 38Arcosmogenic/37Ar from the irradiated meteorite fragment. However, if Cl is present in the meteorite, then these values will be disturbed by Ar produced during laboratory neutron irradiation of Cl. Chlorine is likely to be a particular issue for the Nakhlite group of Martian meteorites, which can contain over 1000 ppm Cl [1]. An alternative method for the cosmogenic Ar correction uses the meteorites exposure age as calculated from an un-irradiated fragment and step-wise production rates based on the measured Ca/K [2]. This calculation is independent of the Cl concentration. We applied this correction method to seven Nakhlites, analyzed in duplicate or triplicate. Selected samples were analyzed at both Lawrence Livermore National Laboratory and SUERC to ensure inter-laboratory reproducibility. We find that the cosmogenic argon correction of [2] has a significant influence on the ages calculated for individual steps, particularly for those at lower temperatures (i.e., differences of several tens of million years for some steps). The lower-temperature steps are moreinfluenced by the alternate cosmogenic correction method of [2], as these analyses yielded higher concentrations of Cl-derived 38Ar. As a result, the Nakhlite data corrected using [2] yields step-heating spectra that are flat or nearly so across >70% of the release spectra (in contrast to downward-stepping spectra often reported for Nakhlite samples), allowing for the calculation of precise emplacement ages for these meteorites.

The nakhlite meteorites are samples of a ~1300 million year old martian clinopyroxenite lava flow or sill [1, 2]. These rocks contain secondary minerals including hydrous silicates, carbonates, sulphates and Fe-(hydr)oxides that formed by watermediated alteration of the igneous body [3, 4]. A prerequisite for understanding the nature of the aqueous system from which these minerals formed, including water/rock ratio, the provenance of solutes and its longevity, is knowing whether the secondary minerals formed by replacement of primary igneous components (minerals and glasses), or by cementation of pores that were opened by fracturing. A replacive origin would suggest low water/rock ratios with solutions being close to saturation with respect to secondary minerals, and does not require a pre-existing network of pores for fluids to gain access to mineral grain interiors. An origin by cementation would suggest that solutes had been sourced by dissolution of other parts of the nakhlite parent rock or the martian crust and were introduced by fluid flow under relatively high water/rock ratio conditions; a means of fracturing the rock is also required. Here we have sought to answer the question of whether olivine-hosted veins in the nakhlites formed by cementation or replacement by comparing the microstructures of veins in the nakhlite Lafayette with veins in olivine grains from type I chondrules in Murchison (CM2 carbonaceous chondrite). We also draw on previously published work on ‘iddingsite’ veins in olivine from terrestrial basalts.

The Lafayette meteorite is an olivine clinopyroxenite that crystallized on Mars ∼1300million years ago within a lava flow or shallow sill. Liquid water entered this igneous rock ∼700million years later to produce a suite of secondary minerals, collectively called ‘iddingsite’, that occur as veins within grains of augite and olivine. The deuterium/hydrogen ratio of water within these secondary minerals shows that the aqueous solutions were sourced from one or more near-surface reservoirs. Several petrographically distinct types of veins can be recognised by differences in their width, shape, and crystallographic orientation. Augite and olivine both contain veins of a very fine grained hydrous Fe- and Mg-rich silicate that are ∼1–2μm in width and lack any preferred crystallographic orientation. These narrow veins formed by cementation of pore spaces that had been opened by fracturing and probably in response to shock. The subset of olivine-hosted veins whose axes lie parallel to (001) have serrated walls, and formed by widening of the narrow veins by interface coupled dissolution–precipitation. Widening started by replacement of the walls of the narrow precursor veins by Fe–Mg silicate, and a crystallographic control on the trajectory of the dissolution–precipitation front created micrometre-scale {111} serrations. The walls of many of the finely serrated veins were subsequently replaced by siderite, and the solutions responsible for carbonation of olivine also partially recrystallized the Fe–Mg silicate. Smectite was the last mineral to form and grew by replacement of siderite. This mineralization sequence shows that Lafayette was exposed to two discrete pulses of aqueous solutions, the first of which formed the Fe–Mg silicate, and the second mediated replacement of vein walls by siderite and smectite. The similarity in size, shape and crystallographic orientation of iddingsite veins in the Lafayette meteorite and in terrestrial basalts demonstrates a common microstructural control on water–mineral interaction between Mars and Earth, and indicates that prior shock deformation was not a prerequisite for aqueous alteration of the martian crust.

The nakhlites are a group of mafic igneous rocks that crystallized on Mars at ca. 1.3-1.4 Ga [1-5]. They are amongst the least shocked Martian meteorites, with cumulate igneous textures (Fig. 1) and thus provide a crucial record of igneous activity and fluid-rock interaction on the red planet. Crystallization of the nakhlites. Understanding the original structure of the nakhlite source is crucial for using these stones to explore Martian igneous processes. In particular, are the different nakhlites from a single thick and differentiated lava flow/sill [6; 7], or do they instead represent magmatically related – but distinct – flows/intrusions? If the various meteorites are derived from separate units, then there will be differences in crystallization ages within the nakhlite suite – which may be identified if these differences are sufficiently large relative to the attainable precision of radioisotopic dating techniques. Some studies [e.g., 5] appear to resolve age differences between different stones, and we aim to test the single vs. multiple unit hypotheses via application of detailed 40Ar/39Ar stepheating of six nakhlites. Alteration of the nakhlites, and the timing of waterrock interaction. In addition to primary magmatic minerals and glasses, the nakhlites contain secondary minerals including clays and carbonates that were precipitated by Martian aqueous fluids prior to impact ejection (Fig. 2) [8-10]. When did this alteration occur? As the clays contain potassium, they are amenable to K-Ar and 40Ar/39Ar dating. K-Ar data from Lafayette suggests the alteration phases formed between 0 to 670 Ma [11]. We consider further the timing of alteration using our 40Ar/39Ar data.

The putative occurrence of methane in the Martian atmosphere has had a major influence on the exploration of Mars, especially by the implication of active biology. The occurrence has not been borne out by measurements of atmosphere by the MSL rover Curiosity but, as on Earth, methane on Mars is most likely in the subsurface of the crust. Serpentinization of olivine-bearing rocks, to yield hydrogen that may further react with carbon-bearing species, has been widely invoked as a source of methane on Mars, but this possibility has not hitherto been tested. Here we show that some Martian meteorites, representing basic igneous rocks, liberate a methane-rich volatile component on crushing. The occurrence of methane in Martian rock samples adds strong weight to models whereby any life on Mars is/was likely to be resident in a subsurface habitat, where methane could be a source of energy and carbon for microbial activity.

The 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.

Northwest Africa (NWA) 5790 is the most recently discovered member of the nakhlite group. Its mineralogy differs from the other nakhlites with a high abundance mesostasis (38.1 ± 3.6 vol%) and scarcity of olivine (4.0 ± 2.2 vol%). Furthermore, zoning of augite phenocrysts, and other petrographic and chemical characteristics suggest that NWA 5790 samples the chilled margin of its parent lava flow/sill. NWA 5790 contains calcite and rare clay minerals that are evidence for its exposure to liquid water. The calcite forms a cement to coatings of dust on the outer surface of the find and extends into the interior of the meteorite within veins. The presence of microbial remains within the coating confirms that the dust and its carbonate cement are terrestrial in origin, consistent with the carbon and oxygen isotope composition of the calcite. The clay minerals are finely crystalline and comprise ~0.003 vol% of the meteorite. δD values of the clay minerals range from −212 ± 109‰ to −96 ± 132‰, and cannot be used to distinguish between a terrestrial or Martian origin. As petrographic results are also not definitive, we conclude that secondary minerals produced by Martian groundwaters are at best very rare within NWA 5790. The meteorite has therefore sampled a region of the lava flow/sill with little or no exposure to the aqueous solutions that altered other nakhlites. This isolation could relate to the scarcity of olivine in NWA 5790 because dissolution of olivine in other nakhlites by Martian groundwaters enhanced their porosity and permeability, and provided solutes for secondary minerals.

Petrographic analysis of eight CM carbonaceous chondrites (EET 96029, LAP 031166, LON 94101, MET 01072, Murchison, Murray, SCO 06043, QUE 93005) by electron imaging and diffraction, and X-ray computed tomography, reveals that six of them have a petrofabric defined by shock flattened chondrules. With the exception of Murchison, those CMs that have a strong petrofabric also contain open or mineralized fractures, indicating that tensional stresses accompanying the impacts were sufficient to locally exceed the yield strength of the meteorite matrix. The CMs studied span a wide range of petrologic subtypes, and in common with Rubin (2012) we find that the strength of their petrofabrics increases with their degree of aqueous alteration. This correspondence suggests that impacts were responsible for enhancing alteration, probably because the fracture networks they formed tapped fluid reservoirs elsewhere in the parent body. Two meteorites that do not fit this pattern are MET 01072 and Murchison; both have a strong petrofabric but are relatively unaltered. In the case of MET 01072, impact deformation is likely to have postdated parent body aqueous activity. The same may also be true for Murchison, but as this meteorite also lacks fractures and veins, its chondrules were most likely flattened by multiple low intensity impacts. Multiphase deformation of Murchison is also revealed by the microstructures of calcite grains, and chondrule-defined petrofabrics as revealed by X-ray computed tomography. The contradiction between the commonplace evidence for impact-deformation of CMs and their low shock stages (most belong to S1) can be explained by most if not all having been exposed to multiple low intensity (i.e., <5GPa) shock events. Aqueous alteration was enhanced by those impacts that were of sufficient intensity to open high permeability fracture networks that could connect to fluid reservoirs.

IDDINGSITE VEINS: IMPLICATIONS FOR WATERROCK INTERACTION WITHIN THE MARTIAN CRUST. M. R. Lee, I. MacLaren, A. Kovacs, T. Tomkinson, D. F. Mark, L. J. Hallis & C. L. Smith. School of Geographical & Earth Sciences, University of Glasgow, G12 8QQ, UK Martin.Lee@Glasgow.ac.uk. School of Physics & Astronomy, University of Glasgow, G12 8QQ, UK Ernst Ruska-Centrum für Mikroskopie und Spektroskopie mit Elektronen, Forschungszentrum Jülich GmbH, 52425 Jülich, Germany. Scottish Universities Environmental Research Center, East Kilbride, UK Natural History Museum, London, SW7 5BD, UK