Nicholas J. Tosca

An integrated view of the chemistry and mineralogy of martian soils

The mineralogical and elemental compositions of the martian soil are indicators of chemical and physical weathering processes. Using data from the Mars Exploration Rovers, we show that bright dust deposits on opposite sides of the planet are part of a global unit and not dominated by the composition of local rocks. Dark soil deposits at both sites have similar basaltic mineralogies, and could reflect either a global component or the general similarity in the compositions of the rocks from which they were derived. Increased levels of bromine are consistent with mobilization of soluble salts by thin films of liquid water, but the presence of olivine in analysed soil samples indicates that the extent of aqueous alteration of soils has been limited. Nickel abundances are enhanced at the immediate surface and indicate that the upper few millimetres of soil could contain up to one per cent meteoritic material.

Water alteration of rocks and soils on Mars at the Spirit rover site in Gusev crater.

Gusev crater was selected as the landing site for the Spirit rover because of the possibility that it once held a lake. Thus one of the rovers tasks was to search for evidence of lake sediments. However, the plains at the landing site were found to be covered by a regolith composed of olivine-rich basaltic rock and windblown ‘global’ dust. The analyses of three rock interiors exposed by the rock abrasion tool showed that they are similar to one another, consistent with having originated from a common lava flow. Here we report the investigation of soils, rock coatings and rock interiors by the Spirit rover from sol (martian day) 1 to sol 156, from its landing site to the base of the Columbia hills. The physical and chemical characteristics of the materials analysed provide evidence for limited but unequivocal interaction between water and the volcanic rocks of the Gusev plains. This evidence includes the softness of rock interiors that contain anomalously high concentrations of sulphur, chlorine and bromine relative to terrestrial basalts and martian meteorites; sulphur, chlorine and ferric iron enrichments in multilayer coatings on the light-toned rock Mazatzal; high bromine concentration in filled vugs and veins within the plains basalts; positive correlations between magnesium, sulphur and other salt components in trench soils; and decoupling of sulphur, chlorine and bromine concentrations in trench soils compared to Gusev surface soils, indicating chemical mobility and separation.

Acid‐sulfate weathering of synthetic Martian basalt: The acid fog model revisited

The acid fog model has received considerable attention as a model of soil formation on Mars. Previous evaluations of this model have focused on experimental weathering of terrestrial basalt samples. However, these samples differ significantly from what now is thought to be typical of Martian basalt. The acid fog model is tested here using synthetic basaltic analogs derived from Mars Pathfinder soil and rock compositions. Reaction of synthetic basalt with various acidic solutions and subsequent evaporation has led to the formation of several putative secondary mineral phases. Many of these phases were not produced in prior experimental studies aimed at aqueous interactions on Mars. Of these alteration phases, Mg, Fe, Ca, and Al sulfates were identified. In addition, secondary ferric oxide phases formed via rapid Fe oxidation under relatively high pH levels buffered by basalt dissolution. Amorphous silica is a ubiquitous product in these experiments and has formed by precipitation from solution and by the dissolution of minerals and glasses leaving behind leached surface layers composed of residual silica. The secondary products formed in these experiments demonstrate the importance of primary mineralogy when testing models of aqueous interactions on Mars. New constraints are placed on both the reactivity of primary basalt and the secondary mineralogy present at the Martian surface. Copyright 2004 by the American Geophysical Union.

Overview of the Spirit Mars Exploration Rover Mission to Gusev Crater: Landing site to Backstay Rock in the Columbia Hills

Spirit landed on the floor of Gusev Crater and conducted initial operations on soil-covered, rock-strewn cratered plains underlain by olivine-bearing basalts. Plains surface rocks are covered by wind-blown dust and show evidence for surface enrichment of soluble species as vein and void-filling materials and coatings. The surface enrichment is the result of a minor amount of transport and deposition by aqueous processes. Layered granular deposits were discovered in the Columbia Hills, with outcrops that tend to dip conformably with the topography. The granular rocks are interpreted to be volcanic ash and/or impact ejecta deposits that have been modified by aqueous fluids during and/or after emplacement. Soils consist of basaltic deposits that are weakly cohesive, relatively poorly sorted, and covered by a veneer of wind-blown dust. The soils have been homogenized by wind transport over at least the several kilometer length scale traversed by the rover. Mobilization of soluble species has occurred within at least two soil deposits examined. The presence of monolayers of coarse sand on wind-blown bedforms, together with even spacing of granule-sized surface clasts, suggests that some of the soil surfaces encountered by Spirit have not been modified by wind for some time. On the other hand, dust deposits on the surface and rover deck have changed during the course of the mission. Detection of dust devils, monitoring of the dust opacity and lower boundary layer, and coordinated experiments with orbiters provided new insights into atmosphere-surface dynamics.

Water Activity and the Challenge for Life on Early Mars

In situ and orbital exploration of the martian surface has shown that acidic, saline liquid water was intermittently available on ancient Mars. The habitability of these waters depends critically on water activity (\batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(a_{\mathrm{H}_{2}\mathrm{O}}\) \end{document}), a thermodynamic measure of salinity, which, for terrestrial organisms, has sharply defined limits. Using constraints on fluid chemistry and saline mineralogy based on martian data, we calculated the maximum \batchmode \documentclass[fleqn,10pt,legalpaper]{article} \usepackage{amssymb} \usepackage{amsfonts} \usepackage{amsmath} \pagestyle{empty} \begin{document} \(a_{\mathrm{H}_{2}\mathrm{O}}\) \end{document} for Meridiani Planum and other environments where salts precipitated from martian brines. Our calculations indicate that the salinity of well-documented surface waters often exceeded levels tolerated by known terrestrial organisms.

In situ and experimental evidence for acidic weathering of rocks and soils on Mars

Experimental data for alteration of synthetic Martian basalts at pH = 0-1 indicate that chemical fractionations at low pH are vastly different from those observed during terrestrial weathering. Rock surface analyses from Gusev crater are well described by the relationships apparent from low-pH experimental alteration data. A model for rock surface alteration is developed, which indicates that a leached alteration zone is present on rock surfaces at Gusev. This zone is not chemically fractionated to a large degree from the underlying rock interior, indicating that the rock surface alteration process has occurred at low water to rock ratio. The geochemistry of natural rock surfaces analyzed by APXS is consistent with a mixture between adhering soil/dust and the leached alteration zone. The chemistry of rock surfaces analyzed after brushing with the RAT is largely representative of the leached alteration zone. The chemistry of rock surfaces analyzed after grinding with the RAT is largely representative of the interior of the rock, relatively unaffected by the alteration process occurring at the rock surface. Elemental measurements from the Spirit, Opportunity, Pathfinder, and Viking 1 landing sites indicate that soil chemistry from widely separated locations is consistent with the low-pH, low water to rock ratio alteration relationships developed for Gusev rocks. Soils are affected principally by mobility of Fe and Mg, consistent with alteration of olivine-bearing basalt and subsequent precipitation of Fe- and Mg-bearing secondary minerals as the primary control on soil geochemistry. Copyright 2006 by the American Geophysical Union.

Two Years at Meridiani Planum: Results from the Opportunity Rover

The Mars Exploration Rover Opportunity has spent more than 2 years exploring Meridiani Planum, traveling ∼8 kilometers and detecting features that reveal ancient environmental conditions. These include well-developed festoon (trough) cross-lamination formed in flowing liquid water, strata with smaller and more abundant hematite-rich concretions than those seen previously, possible relict “hopper crystals” that might reflect the formation of halite, thick weathering rinds on rock surfaces, resistant fracture fills, and networks of polygonal fractures likely caused by dehydration of sulfate salts. Chemical variations with depth show that the siliciclastic fraction of outcrop rock has undergone substantial chemical alteration from a precursor basaltic composition. Observations from microscopic to orbital scales indicate that ancient Meridiani once had abundant acidic groundwater, arid and oxidizing surface conditions, and occasional liquid flow on the surface.

Sulfate deposition in subsurface regolith in Gusev crater, Mars

Excavating into the shallow Martian subsurface has the potential to expose stratigraphic layers and mature regolith, which may hold a record of more ancient aqueous interactions than those expected under current Martian surface conditions. During the Spirit rovers exploration of Gusev crater, rover wheels were used to dig three trenches into the subsurface regolith down to 6-11 cm depth: Road Cut, the Big Hole, and The Boroughs. A high oxidation state of Fe and high concentrations of Mg, S, Cl, and Br were found in the subsurface regolith within the two trenches on the plains, between the Bonneville crater and the foot of Columbia Hills. Data analyses on the basis of geochemistry and mineralogy observations suggest the deposition of sulfate minerals within the subsurface regolith, mainly Mg-sulfates accompanied by minor Ca-sulfates and perhaps Fe-sulfates. An increase of Fe2O3, an excess of SiO2, and a minor decrease in the olivine proportion relative to surface materials are also inferred. Three hypotheses are proposed to explain the geochemical trends observed in trenches: (1) multiple episodes of acidic fluid infiltration, accompanied by in situ interaction with igneous minerals and salt deposition; (2) an open hydrologic system characterized by ion transportation in the fluid, subsequent evaporation of the fluid, and salt deposition; and (3) emplacement and mixing of impact ejecta of variable composition. While all three may have plausibly contributed to the current state of the subsurface regolith, the geochemical data are most consistent with ion transportation by fluids and salt deposition as a result of open-system hydrologic behavior. Although sulfates make up >20 wt.% of the regolith in the wall of The Boroughs trench, a higher hydrated sulfate than kieserite within The Boroughs or a greater abundance of sulfates elsewhere than is seen in The Boroughs wall regolith would be needed to hold the structural water indicated by the water-equivalent hydrogen concentration observed by the Gamma-Ray Spectrometer on Odyssey in the Gusev region. Copyright 2006 by the American Geophysical Union.

Fe oxidation processes at Meridiani Planum and implications for secondary Fe mineralogy on Mars

Fe oxidation processes may have occurred during groundwater-mediated diagenesis in Meridiani Planum sediments. To address this question, melanterite oxidation experiments were conducted at epsomite saturation as a function of pH. Results show that schwertmannite is initially formed from acidic Fe oxidation and that its formation and aging to mixtures of jarosite and nanocrystalline goethite is strongly controlled by pH over the range b <2.0-4.0. The pH is controlled in turn by Fe oxidation and Fe3+ hydrolysis. In one 77-d oxidation experiment, nanocrystalline hematite was tentatively identified by MC6ssbauer spectroscopy. Accordingly, aging experiments with synthetic nanocrystalline goethite were conducted (1) to further resolve the formation mechanisms of Fe-phases identified from oxidation experiments and (2) to test whether low water activity (aw) controls the thermodynamically favored goethite to hematite transition at low temperature. MC6ssbauer spectroscopy and total X-ray scattering show no observable changes after 4 months of aging, and instead, these results point to a jarosite precursor for the tentatively identified hematite. On the basis of these results, we suggest that the oxidation and maturation of initially formed Fe2+-bearing saline minerals may account in large part for the distribution of secondary Fe minerals at the Martian surface, contributing to the association of Fe oxides and Mg/Ca sulfates observed from orbital surface analyses. We hypothesize that oxidation of Fe2+ sulfates at low temperature could account for sustained diagenetic acidity in addition to much of the observed Fe mineralogy in Meridiani Planum outcrop rocks. The origin of the gray crystalline hematite at Meridiani, however, is deserving of further experimental work to test this mechanism. Copyright 2008 by the American Geophysical Union.

Veneers, rinds, and fracture fills: Relatively late alteration of sedimentary rocks at Meridiani Planum, Mars

Veneers and thicker rinds that coat outcrop surfaces and partially cemented fracture fills formed perpendicular to bedding document relatively late stage alteration of ancient sedimentary rocks at Meridiani Planum, Mars. The chemistry of submillimeter thick, buff-colored veneers reflects multiple processes at work since the establishment of the current plains surface. Veneer composition is dominated by the mixing of silicate-rich dust and sulfate-rich outcrop surface, but it has also been influenced by mineral precipitation, including NaCl, and possibly by limited physical or chemical weathering of sulfate minerals. Competing processes of chemical alteration (perhaps mediated by thin films of water or water vapor beneath blanketing soils) and sandblasting of exposed outcrop surfaces determine the current distribution of veneers. Dark-toned rinds several millimeters thick reflect more extensive surface alteration but also indicate combined dust admixture, halite precipitation, and possible minor sulfate removal. Cemented fracture fills that are differentially resistant to erosion occur along the margins of linear fracture systems possibly related to impact. These appear to reflect limited groundwater activity along the margins of fractures, cementing mechanically introduced fill derived principally from outcrop rocks. The limited thickness and spatial distribution of these three features suggest that aqueous activity has been rare and transient or has operated at exceedingly low rates during the protracted interval since outcropping Meridiani strata were exposed on the plains surface.