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The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover has detected oxychlorine compounds such as perchlorate or chlorate in Gale Crater samples. Two potential pathways for oxychlorine formation on Mars are UV-induced interaction between chlorine and metal oxides or atmospheric oxygen and radiolysis of Cl-containing surface materials by galactic cosmic rays, with the chlorine being volcanically derived in both cases. Oxychlorine compounds are identified by a diagnostic release of O2 at temperatures <600 °C and an HCl release from ~350-850 °C during sample pyrolysis. Of the 16 samples analyzed by SAM as of July 2018, 12 have contained oxychlorine compounds, including all four scooped samples and 8 of the 12 drilled samples.

In Gale crater, the Curiosity Mars rover has climbed over 300 meters of the Murray formation from the base of the Pahrump Hills to the crest of Vera Rubin Ridge. We discuss the possibility that fine-grained mudstone of the Murray formation is a diagenetic product of sediments with a chemical and mineralogical composition similar to present-day martian soil. Typical (low Ca-sulfate) Murray samples have Na2O, Al2O3, SiO2, SO3, TiO2 and FeOT concentrations within 10% (relative) of average martian soil. These oxides constitute ~85% of each sample. The Al/Si and Ti/Si ratios of Murray samples are comparable to average martian soil but distinct from other martian geologic units. Percentage difference in P2O5, Cl, K2O, Cr2O3, MnO, Ni, Zn, Br, and Ge between soil and Murray samples generally exceed 10%, but these elements and oxides amount to less than 4% of the samples. These constituents are highly variable in Murray mudstone and may reflect mobility in fluid interactions. Large discrepancies in MgO and CaO with ~50% lower concentrations in the Murray samples (~2% absolute differences) are indicative of open-system alteration if the Murray mudstone originated from soil-like material. Mineralogically, martian soil is dominated by plagioclase feldspar, pyroxenes, and olivine with minor hematite, magnetite, and Ca-sulfate. In comparison, Murray samples generally have less feldspar and pyroxene, little to no olivine, more iron oxides and Ca-sulfates, and Fe-containing phyllosilicates. If Murray mudstone originated from a Mars soil composition, aqueous alteration could have converted olivine and pyroxenes to iron oxides and phyllosilicates. Intermixed or zoned plagioclase feldspars could have lost a larger portion of calcic constituents, consistent with susceptibility to weathering, resulting in a change from ~An55 (soil) to ~An40 (Murray). This alteration could be consistent with the major element chemistry, including the small decrease in MgO and CaO. A subsequent influx of minor/trace elements and Ca-sulfate, e.g. from groundwater, would be required. In this diagenetic scenario, the bulk of the alteration would have been nearly isochemical, suggesting limited mineral segregation and aqueous alteration during transport from the drainage basin or a significant direct aeolian contribution to the Murray sediments.

Of 15 samples analyzed to date, the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) has detected oxychlorine compounds (perchlorate or chlorate) in 12 samples. The presence of oxychlorine species is inferred from the release of oxygen at temperatures less than 600degC and HCl between 350-850degC when a sample is heated to 850degC. The O2 release temperature varies with sample, likely caused by different cations, grain size differences, or catalytic effects of other minerals. In the oxychlorine-containing samples, perchlorate abundances range from 0.06 +/- 0.03 to 1.15 +/- 0.5 wt% Cl2O7 equivalent. Comparing these results to the elemental Cl concentration measured by the Alpha Particle X-ray Spectrometer (APXS) instrument, oxychlorine species account for 5-40% of the total Cl present. The variation in oxychlorine abundance has implications for their production and preservation over time. For example, the John Klein (JK) and Cumberland (CB) samples were acquired within a few meters of each other and CB contained approximately1.2 wt% Cl2O7 equivalent while JK had approximately 0.1 wt%. One difference between the two samples is that JK has a large number of veins visible in the drill hole wall, indicating more post-deposition alteration and removal. Finally, despite Cl concentrations similar to previous samples, the last three Murray formation samples (Oudam, Marimba, and Quela) had no detectable oxygen released during pyrolysis. This could be a result of oxygen reacting with other species in the sample during pyrolysis. Lab work has shown this is likely to have occurred in SAM but it is unlikely to have consumed all the O2 released. Another explanation is that the Cl is present as chlorides, which is consistent with data from the ChemCam (Chemical Camera) and CheMin (Chemistry and Mineralogy) instruments on MSL. For example, the Quela sample has approximately1 wt% elemental Cl detected by APXS, had no detectable O2 released, and halite (NaCl) has been tentatively identified in CheMin X-ray diffraction data. These data show that oxychlorines are likely globally distributed on Mars but the distribution is heterogenous depending on the perchlorate formation mechanism (production rate), burial, and subsequent diagenesis

In-situ identification of sulfates at the martian surface by the Mars Exploration Rovers and the Mars Science Laboratory have included calcium sulfates with various states of hydration (gypsum, bassanite, anhydrite), iron sulfates of likely fumarolic origin, massive deposits of iron hydroxysulfates indicative of an acidic history, and minor occurrences of magnesium sulfates. Recent measurements by the Opportunity and Curiosity Alpha Particle X-ray Spectrometers (APXS) have indicated the presence of Ni-substituted Mg-sulfates at the Meridiani Planum and Gale Crater landing sites. The Opportunity rover has traversed nearly 43 km and is currently exploring the impact breccias of the rim of Endeavour crater, near a location where signatures of aqueous alteration have been established from orbit. APXS analyses of subsurface materials excavated by a rover wheel show clear evidence for a Mg(Ni)-sulfate with Mg:Ni (is) approximately 100:1 (molar). On the other side of the planet, Curiosity is continuing its climb up Mount Sharp after driving (is) approximately 13 km since landing. Over the last 4 km of the traverse, there have been multiple chemical analyses of erosionally-resistant nodules and dendritic features in a finely laminated mudstone unit which also indicate Mg(Ni)-sulfate (Mg:Ni (is) approximately 30:1, molar). The geologic settings for the Endeavour rim and the Mount Sharp mudstones are clearly different, but similar formation conditions for these sulfates may be possible. Ni(2+) readily substitutes for Mg(2+) in a variety of geochemical processes due to their comparable ionic radii. The availability of soluble Ni at the time of Mg-sulfate precipitation suggests acidic solutions. The fluids responsible for alteration in the Endeavour rim and for the formation of nodules in Gale mudstones may have had similar chemical characteristics at the time the Mg-sulfates were formed.

Evidence of oxychlorine species such as perchlorates or chlorates have been detected in nearly every acquired sample analyzed on the surface of Mars. Perchlorates were first discovered by the Wet Chemistry Laboratory (WCL) instrument on the Phoenix lander in 2008. The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) has analyzed twelve samples from Gale Crater (as of July 2016), nine drilled samples and three scooped samples. After delivery to SAM, samples are heated to approximately 850 C and evolved gases are measured by a quadrupole mass spectrometer.

Mars Exploration Rover Opportunity is exploring the rim of 22 km diameter, Noachian-aged Endeavour crater. Marathon Valley cuts through the central region of the western rim providing a window into the local lower rim stratigraphic record. Spectra from the Compact Reconnaissance Imaging Spectrometer for Mars show evidence for the occurrence of Fe-Mg smectite in this valley, indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. The Alpha Particle X-ray Spectrometer has determined the compositions of 59 outcrop targets on untreated, brushed and abraded surfaces. Rocks in the Marathon Valley region are soft breccias composed of mm- to cm-sized darker clasts set in a lighter-toned, finegrained matrix. They are basaltic in non-volatile-element composition and compositionally similar to breccias investigated elsewhere on the rim. Alteration styles recorded in the rocks include: (1) Enrichments in Si, Al, Ti and Cr in more reddish-colored rock, consistent with leaching of more soluble cations and/or precipitation of Si +/- Al, Ti, Cr from fluids. Coprecipitation of Ge-rich phases with Si occurred in the western area only; high water:rock is indicated. Pancam multispectral observations indicate higher nanophase ferric oxide contents, but the rocks have lower Fe contents. The highly localized nature of the red zones indicate they cannot be the source of the widespread smectite signature observed from orbit. (2) Outcrops separated by approximately 65 m show common compositional changes between brushed and abraded (approximately 1 mm deep) targets: increases in S and Mg; decreases in Al, Cl and Ca. These changes are likely due to relatively recent, surface-related alteration of valley rocks and formation of surface coatings under low water:rock. (3) One target, from the center of a region of strong CRISM smectite signature, shows modest differences in composition (higher Si, K; lower Mn) compared to most Marathon Valley rocks, while another target approximately 40 cm away on the same outcrop does not; a change towards smectite bulk compositions is not observed. The smectite signature likely resulted from alteration under low water:rock such that primary minerals were partially altered to phyllosilicates, but wholesale leaching of cations by fluids did not occur.

The alpha particle x-ray spectrometer (APXS) on all four Mars Rovers returned geochemical data from about 1000 rocks and soils along the combined traverses of over 50 kilometers. Here we discuss rocks likely of igneous origin, which might represent source materials for the soils and sediments identified along the traverses. Adirondack-type basalts, abundant in the plains of Gusev Crater, are primitive, olivine bearing basalts. They resemble in composition the basaltic soils encountered at all landing sites, except the ubiquitous elevated S, Cl and Zn in soils. They have been postulated to represent closely the average Martian crust composition. The recently identified new Martian meteorite Black Beauty has similar overall geochemical composition, very distinct from the earlier established SNC meteorites. The rim of the Noachian crater Endeavour, predating the sulfate-bearing Burns formation at Meridiani Planum, also resembles closely the composition of Adirondack basalts. At Gale Crater, the MSL Curiosity rover identified a felsic rock type exemplified by the mugearitic float rock JakeM, which is widespread along the traverse at Gale. While a surprise at that time, possibly related more evolved, alkaline rocks had been previously identified on Mars. Spirit encountered the Wishstone rocks in the Columbia Hills with approx. 6% Na2O+K2O, 15 % Al2O3 and low 12% FeO. Pathfinder rocks with elevated K and Na and >50% SiO2 were postulated to be andesitic. Recently Opportunity encountered the rock JeanBaptisteCharbonneau with >15% Al2O3, >50% SiO2 and approx. 10% FeO. A common characteristic all these rocks is the very low abundance of Cr, Ni and Zn, and an Fe/Mn ratio of about 50, indicating an unaltered Fe mineralogy. Beside these likely igneous rock types, which occurred always in several rocks, a few unique rocks were encountered, e.g. Bounce Rock, a pyroxene-bearing ejecta rock fragment resembling the Shergottite EETA 79001B meteorite. The APXS data can be used to relate the findings of all 4 landing sites, constrain the water to rock ratio of sediments or imply source rock provenance. Beyond that the capability to quantify important volatile elements like P, S, Cl, and Br have provided new insights into the chemistry and the environment present during the formation of the sediments.

Mineralogical and geochemical data returned by orbiters and landers over the past 15 years have substantially enhanced our understanding of the history of aqueous alteration on Mars. Here, we summarize aqueous processes that have been implied from data collected by landed missions. Mars is a basaltic planet. The geochemistry of most materials has not been “extensively” altered by open-system aqueous processes and have average Mars crustal compositions. There are few examples of open-system alteration, such as Gale crater’s Pahrump Hills mudstone. Types of aqueous alteration include (1) acid-sulfate and (2) hydrolytic (circum-neutral/alkaline pH) with varying water-to-rock ratios. Several hypotheses have been suggested for acid-sulfate alteration including (1) oxidative weathering of ultramafic igneous rocks containing sulfides; (2) sulfuric acid weathering of basaltic materials; (3) acid fog weathering of basaltic materials; and (4) near-neutral pH subsurface solutions rich in Fe (sup 2 plus) that rapidly oxidized to Fe (sup 3 plus) producing excess acidity. Meridiani Planum’s sulfate-rich sedimentary deposit containing jarosite is the most “famous” acid-sulfate environment visited on Mars, although ferric sulfate-rich soils are common in Gusev crater’s Columbia Hills and jarosite was recently discovered in the Pahrump Hills. An example of aqueous alteration under circum-neutral pH conditions is the formation of Fe-saponite with magnetite in situ via aqueous alteration of olivine in Gale crater’s Sheepbed mudstone. Circum-neutral pH, hydrothermal conditions were likely required for the formation of Mg-Fe carbonate in the Columbia Hills. Diagenetic features (e.g., spherules, fracture filled veins) indicate multiple episodes of aqueous alteration/diagenesis in most sedimentary deposits. However, low water-to-rock ratios are prominent at most sites visited by landed missions (e.g., limited water for reaction to form crystalline phases possibly resulting in large amounts of short-range ordered materials and little physical separation of primary and secondary materials). Most of the aqueous alteration appears to have occurred early in the planet’s history; however, minor aqueous alteration may be occurring at the surface today (e.g., thin films of water forming carbonates akin to those discovered by Phoenix).

Mars Exploration Rover Opportunity has been exploring Meridiani Planum for 11+ years, and is presently investigating the geology of rim segments of 22 km diameter, Noachian-aged Endeavour crater. The Alpha Particle X-ray Spectrometer has determined the compositions of a pre-impact lithology and impact breccias representing ejecta from the crater. Opportunity is now investigating the head (higher elevation, western end) of Marathon Valley. This valley cuts eastward through the central portion of the Cape Tribulation rim segment and provides a window into the lower stratigraphic record of the rim. At the head of Marathon Valley is a shallow (few 10s of cm), ovoid depression approximately 27×36 m in size, named Spirit of Saint Louis, that is surrounded by approximately 20-30 cm wide zone of more reddish rocks (red zone). Opportunity has just entered a region of Marathon Valley that shows evidence for Fe-Mg smectite in Compact Reconnaissance Imaging Spectrometer for Mars spectra indicating areally extensive and distinct lithologic units and/or styles of aqueous alteration. Rocks at the head of Marathon Valley and within Spirit of Saint Louis are breccias (valley-head rocks). In some areas, layering inside Spirit of Saint Louis appears continuous with the rocks outside. The valley-head rocks are of similar, generally basaltic composition. The continuity in composition, texture and layering suggest the valley-head rocks are coeval breccias, likely from the Endeavour impact. These local breccias are similar in non-volatile-element composition to breccias investigated elsewhere on the rim. Rocks within the red zone are like those on either side in texture, but have higher Al, Si and Ge, and lower S, Mn, Fe, Ni and Zn as compared to rocks on either side. The valley-head rocks have higher S than most Endeavour rim breccias, while red zone rocks are like those latter breccias in S. Patches within the rocks outside Spirit of Saint Louis have higher Al, Si and Ge indicating red-zone-style alteration extended beyond the narrow red zone. Rocks on either side of the red zone and patches within it have the multispectral signature (determined by Panoramic Camera) of red hematite indicating an oxidizing environment. The red zone appears to be a thin alteration zone marking the border of Spirit of Saint Louis, but the origin of this morphologic feature remains obscure.

Three years into exploration of sediments in Gale crater on Mars, the Mars Science Laboratory rover Curiosity has provided data on several modes and episodes of diagenetic mineral formation. Curiosity determines mineralogy principally by X-ray diffraction (XRD), but with supporting data from thermal-release profiles of volatiles, bulk chemistry, passive spectroscopy, and laser-induced breakdown spectra of targeted spots. Mudstones at Yellowknife Bay, within the landing ellipse, contain approximately 20% phyllosilicate that we interpret as authigenic smectite formed by basalt weathering in relatively dilute water, with associated formation of authigenic magnetite as in experiments by Tosca and Hurowitz [Goldschmidt 2014]. Varied interlayer spacing of the smectite, collapsed at approximately 10 A or expanded at approximately 13.2 A, is evidence of localized diagenesis that may include partial intercalation of metal-hydroxyl groups in the approximately 13.2 A material. Subsequent sampling of stratigraphically higher Windjana sandstone revealed sediment with multiple sources, possible concentration of detrital magnetite, and minimal abundance of diagenetic minerals. Most recent sampling has been of lower strata at Mount Sharp, where diagenesis is widespread and varied. Here XRD shows that hematite first becomes abundant and products of diagenesis include jarosite and cristobalite. In addition, bulk chemistry identifies Mg-sulfate concretions that may be amorphous or crystalline. Throughout Curiosity's traverse, later diagenetic fractures (and rarer nodules) of mm to dm scale are common and surprisingly constant and simple in Ca-sulfate composition. Other sulfates (Mg,Fe) appear to be absent in this later diagenetic cycle, and circumneutral solutions are indicated. Equally surprising is the rarity of gypsum and common occurrence of bassanite and anhydrite. Bassanite, rare on Earth, plays a major role at this location on Mars. Dehydration of gypsum to bassanite in the dry atmosphere of Mars has been proposed but considered unlikely based on lab studies of dehydration kinetics in powdered samples. Dehydration is even less likely for bulk vein samples, as lab data show dehydration rates one to two orders of magnitude slower in bulk samples than in powders. On Mars, exposure ages of 100 Ma or more may be a significant factor in dehydration of hydrous phases.

Phosphorus is an essential element in terrestrial organisms and thus characterizing the occurrences of phosphate phases at the martian surface is crucial in the assessment of habitability. The Alpha Particle X-Ray Spectrometers onboard Spirit, Opportunity and Curiosity discovered a variety of primary and secondary phosphate phases allowing direct comparisons across the three landing sites. The Spirit rover at Gusev Crater encountered the "Wishstone/Watchtower" class of P-rich (up to 5.2 wt% P2O5) rocks interpreted to be alkaline volcanic rocks with a physical admixture of approximately 10 to 20% merrillite [Usui et al 2008]. These rocks are characterized by elevated Ti and Y and anomalously low Cr and Ni, which could largely reflect the nature of the protoliths: Evolved magmatic rocks. Many of these chemical signatures are also found in pyroclastic deposits at nearby "Home Plate" and in phosphate precipitates derived from fluid interactions with these rocks ("Paso Robles" soils). The Opportunity rover at Meridiani Planum recently analyzed approximately 4 cm clast in a fine-grained matrix, one of numerous rocks of similar appearance at the rim of Endeavour Crater. This clast, "Sarcobatus," has minor enrichments in Ca and P relative to the matrix, and like the P-rich rocks at Gusev, Sarcobatus also shows elevated Al and Ti. On the same segment of the Endeavour rim, subsurface samples were found with exceptional levels of Mn (approximately 3.5 wt% MnO). These secondary and likely aqueous deposits contain strong evidence for associated Mg-sulfate and Ca-phosphate phases. Finally, the Curiosity traverse at Gale crater encountered P-rich rocks compositionally comparable to Wishstone at Gusev, including elevated Y. Phosphorous-rich rocks with similar chemical characteristics are prevalent on Mars, and the trace and minor element signatures provide constraints on whether these are primary deposits, secondary products of physical weathering or secondary products of chemical weathering.

Mars Exploration Rover Opportunity is exploring Noachian age rocks of the rim of 22 km diameter Endeavour crater. Overlying the pre-impact lithologies and rim breccias is a thin apron of fine-grained sediments, the Grasberg fm, forming annuli on the lower slopes of rim segments. Hesperian Burns fm sandstones overly the Grasberg fm. Grasberg rocks have major element compositions that are distinct from Burns fm sandstones, especially when comparing interior compositions exposed by the Rock Abrasion Tool. Grasberg rocks are also different from Endeavour rim breccias, but have general compositional similarities to them. Grasberg sediments are plausibly fine-grained materials derived from the impact breccias. Veins of CaSO4 transect Grasberg fm rocks demonstrating post-formation aqueous alteration. Minor/trace elements show variations consistent with mobilization by aqueous fluids. Grasberg fm rocks have low Mn and high Fe/Mn ratios compared to the other lithologies. Manganese likely was mobilized and removed from the Grasberg host rock by redox reactions. We posit that Fe2+ from acidic solutions associated with formation of the Burns sulfate-rich sandstones acted as an electron donor to reduce more oxidized Mn to Mn2+. The Fe contents of Grasberg rocks are slightly higher than in other rocks suggesting precipitation of Fe phases in Grasberg materials. Pancam spectra show that Grasberg rocks have a higher fraction of ferric oxide minerals than other Endeavour rim rocks. Solutions transported Mn2+ into the Endeavour rim materials and oxidized and/or precipitated it in them. Grasberg has higher contents of the mobile elements K, Zn, Cl, and Br compared to the rim materials. Similar enrichments of mobile elements were measured by the Spirit APXS on West Spur and around Home Plate in Gusev crater. Enhancements in these elements are attributed to interactions of hydrothermal acidic fluids with the host rocks. Interactions of fluids with the Grasberg fm postdate the genesis of the Endeavour rim phyllosilicates. The aqueous alteration history of Endeavour rim rocks is complicated by different styles of alteration that have spanned the Noachian and Hesperian. Late stage acidic aqueous alteration of Grasberg fm materials is likely penecontemporaneous with the diagenesis of the sulfate-rich sediments of Meridiani Planum.

Drill fines of mudstone (targets John Klein and Cumberland) from the Sheepbed unit at Yel-lowknife Bay were analyzed by MSL payload elements including the Chemistry and Mineralogy (CheMin), APXS (Alpha Particle X-Ray Spectrometer), and Sample Analysis at Mars (SAM) instruments. CheMin XRD results show a variety of crystalline phases including feldspar, pyroxene, olivine, oxides, oxyhydroxides, sulfates, sulfides, a tri-octahedral smectite, and XRD amorphous material. The drill fines are distinctly different from corresponding analyses of the global soil (target Rocknest) in that the mudstone samples contained detectable phyllosilicate. Here we focus on John Klein and combine CheMin and APXS data to calculate the chemical composition and concentration of the amorphous component. The chemical composition of the amorphous plus smectite component for John Klein was calculated by subtracting the abundance-weighted chemical composition of the individual XRD crystalline components from the bulk composition of John Kline as measured by APXS. The chemical composition of individual crystalline components was determined either by stoichiometry (e.g., hematite and magnetite) or from their unit cell parameters (e.g., feldspar, olivine, and pyroxene). The chemical composition of the amorphous + smectite component (approx 71 wt.% of bulk sample) and bulk chemical composition are similar. In order to calculate the chemical composition of the amorphous component, a chemical composition for the tri-octahedral smectite must be assumed. We selected two tri-octahedral smectites with very different MgO/(FeO + Fe2O3) ratios (34 and 1.3 for SapCa1 and Griffithite, respectively). Relative to bulk sample, the concentration of amorphous and smectite components are 40 and 29 wt.% for SapCa1 and 33 and 36 wt.% for Griffithite. The amount of smectite was calculated by requiring the MgO concentration to be approx 0 wt.% in the amorphous component. Griffithite is the preferred smectite because the position of its 021 diffraction peak is similar to that reported for John Klein. In both cases, the amorphous component has low SiO2 and MgO and high FeO + Fe2O3, P2O5, and SO3 concentrations relative to bulk sample. The chemical composition of the bulk drill fines and XRD crystalline, smectite, and amorphous components implies alteration of an initially basaltic material under near neutral conditions (not acid sulfate), with the sulfate incorporated later as veins of CaSO4 injected into the mudstone.

The chemical composition, global abundance, distribution, and formation pathways of carbonates are central to understanding aqueous processes, climate, and habitability of early Mars. The Mars Exploration Rover (MER) Spirit analyzed a series of olivine-rich outcrops while descending from the summit region of Husband Hill into the Inner Basin of the Columbia Hills of Gusev Crater to the eastern edge of the El Dorado ripple field in late 2005. Reanalysis of Spirit s mineralogical data from the Moessbauer Spectrometer (MB) and the Miniature Thermal Emission Spectrometer (Mini-TES) and chemical data from the Alpha Particle X-Ray Spectrometer (APXS) in 2010, coupled with new laboratory data for carbonate-bearing samples, lead to identification of carbonate in one of the outcrops (Comanche) [Morris, R.V., et al., Science, 329, 421-424]. The carbonate is rich in magnesium and iron (Mc62Sd25Cc11Rh2, assuming all Ca and Mn is associated with the carbonate) and is a major component of the Comanche outcrops (16 to 34 wt.%). The mineralogical, chemical, and abundance data are constrained in multiple, mutually consistent ways by the MER analyses. For example, a low-Ca carbonate is required by the MB and APXS data and is consistent with Mini-TES data. Three spectral features attributable to fundamental infrared vibrational modes of low-Ca carbonate are present in the Mini-TES spectra of Comanche outcrops. The average composition of Comanche carbonate approximates the average composition of the carbonate globules in Martian meteorite ALH 84001. Analogy with ALH 84001, terrestrial, and synthetic carbonate globules suggests that Comanche carbonate precipitated from aqueous solutions under hydrothermal conditions at near neutral pH in association with volcanic activity during the Noachian era. Comanche outcrop morphology suggests they are remnants of a larger carbonate-bearing formation that evolved in ultramafic rock and then preferentially eroded by a combination of aeolian abrasion and chemical decomposition by exposure to acid-sulfate vapors/solutions. The high carbonate concentration in the Comanche outcrops supports climate models involving a CO2 greenhouse gas on a wet and warm early Mars and subsequent sequestering of at least part of that atmosphere in carbonate minerals.

The Mars Exploration Rover Opportunity has been operating at the surface of Mars for over 2100 sols and has driven a distance of approximately 20 km. Throughout the traverse, outcrop rocks with margins and fracture fill resistant to erosion have been imaged and analyzed in detail by the Moessbauer (MB) spectrometer and the Alpha Particle X-ray Spectrometer (APXS). A recent APXS analysis of an outcrop block excavated by a young impact crater shows a coating with the highest concentration of iron measured by either rover, not including the iron-nickel meteorites. Texturally, this sample (referred to as "Chocolate Hills -Aloya") appears as a cemented collection of partially fragmented \blueberries." With the exception of an elevated sulfur content, the elemental chemistry of this particular sample is entirely consistent with other analyses of hematite spherules at Merdiani Planum. As a result, it is difficult to determine whether this coating, which may have been filling a fracture in outcrop rocks prior to disruption by the impact, was simply an agglomeration of spherules or a result of a more complicated aqueous process. In contrast, a number of other fracture-filling exposures and erosion-resistant rinds have been analyzed by the APXS and MB instruments showing significant concentrations of iron in the form of hematite without the texture of spherule fragments. In one of these samples, a broken piece of fracture fill within Victoria crater referred to as "Dorsal," showed over 50% of the iron in hematite, the highest Mn concentration of any sample measured by the rovers, and elevated levels of Cl and Br. While the Fe:Mn ratio of the Dorsal analyses are comparable to that of Gusev and Meridiani basalts, it is clear that chemistry of this sample cannot be completely explained by a simple mixing of outcrop and blueberry compositions

The Mars Exploration Rover Spirit has traversed over 7.5 km in 1470 sols of operations at the Gusev Crater landing site. Chemical and mineralogical evidence from approximately 200 in-situ samples indicate various degrees of exposure to liquid water, from wet and saturated to dry and unaltered. (1) Six samples with concentrations of amorphous silica between 60 and 95 wt% were discovered in a small valley less than 50 meters in length. Associated enrichments in titanium oxide, relatively insoluble at low pH, suggest that these silica deposits formed as a result of acidic leaching processes. Liquid water interactions with these surface materials were necessary to remove cations solubilized in the low pH environment or to concentrate silica in solution prior to precipitation. (2) Hydrated ferric sulfates are found in subsurface deposits which have the unmistakable chemical signatures of nearby rocks. The movement of hydrothermal fluids and/or fumarolic vapors through local rocks prior to precipitation of these materials is suggested by these observations. (3) Goethite (alpha-FeOOH), a mineral phase which requires water to form, represents 20% to 35% of the iron in numerous rock samples (Clovis Class) on the West Spur of the Columbia Hills. Alteration of iron under aqueous conditions is clearly indicated by this presence of goethite. (4) Nearly isochemical signatures are found in elemental analyses of over ten distinct samples (Wishstone/Watchtower class rocks), yet the ratio of ferric iron to total iron varies from 0.4 to 0.95. Small quantities of water, insufficient to flush cations from the samples, were likely responsible for this weathering. (5) Bromine, a trace element readily mobilized by water, is found in high concentrations in certain rock interiors and is enhanced in subsurface soils, consistent with transport to localized cold traps by water thin-films. (6) Also relevant to the characterizing the role of liquid water is the discovery of an areally extensive ultramafic sequence of rocks where over 70% of the iron is in unaltered olivine and the ferric to total iron ratio is 0.1. This result indicates that certain materials at the martian surface have been protected from aqueous alteration.