Acid drainage generation and associated Ca-Fe-SO4 minerals in a periglacial environment, Eagle Plains, Northern Yukon, Canada: A potential analogue for low-temperature sulfate formation on Mars

Near Eagle Plains, northern Yukon, Canada, acidic Ca-Fe-Mg sulfate waters are discharging year-long from disturbed permafrosted sandstone bedrock overlying pyritiferous black shales. These acidic waters are precipitating gypsum with minor amounts of jarosite-K (Na), schwertmannite and hematite. This mineral assemblage is similar to that observed at Meridiani Planum (and other location on Mars), making this site a valuable analogue for low-temperature sulfate geochemistry and mineral formation on Mars. Stable O-S isotope analysis of the acidic waters near Eagle Plains revealed that the oxygen in the dissolved sulfate is mostly derived from water (ca. 70%), suggesting that the sulfide oxidation process could be in part biomediated (i.e., accelerated by acidophilic Fe-oxidizing bacteria). However, unlike the dissolved sulfate in the waters, the formation of the Ca-Fe-SO₄ minerals appears to be purely abiotic. The stable O-S isotope composition of the sulfate minerals is well within the predicted equilibrium range at low temperature, suggesting that they formed through physico-chemical processes (i.e., evaporation or freezing). Low-temperature geochemical modeling with FREZCHEM and PHREEQC suggests that the mineral assemblage at Eagle Plains precipitated mainly through the freezing of Ca-Fe-Mg-SO₄ acidic waters, rather than through evaporation during the dry summer season, although the latter is still possible. This suggests that the sulfate mineral assemblage observed on Mars could have also formed under a periglacial-type climate. Considering that the active layer in the zone affected by acid drainage does not freeze-over during winter, the residual talik offers a localized niche environment to support acidophilic microorganisms. Overall, the fact that acid drainage is presently active near Eagle Plains allows the direct observation of the low-temperature geochemical processes responsible for generating acid drainage conditions and precipitation of gypsum, schwertmannite, jarosite-K, jarosite-Na, goethite and hematite.     

A formation mechanism for hematite-rich spherules on Mars

Gray crystalline hematite on Mars has been detected in three regions, Sinus Meridiani, Aram Chaos, and Valles Marineris, first by the Thermal Emission Spectrometer (TES) onboard the Mars Global Surveyor (MGS) orbiter, and then confirmed by other instruments. The hematite-rich spherules were also detected by the Mars Exploration Rover (MER) Opportunity at Meridiani Planum (Sinus Meridiani). Formation mechanisms of the hematite-rich spherules have been discussed widely since then. Here, we argue for an alternative formation mechanism, that is, the spherules originally formed at Valles Marineris due to the interaction of volcanic deposits and acidic hydrothermal fluids, and then were transported to and deposited at Meridiani Planum and Aram Chaos as alluvial/fluvial sedimentary deposits with other materials such as sulfates and rock fragments during the wash-out flows from Valles Marineris to Meridiani Planum and Aram Chaos. Diagenesis of the hematite-rich spherules may have also been a possible mechanism following sediment transport and emplacement. The hypothesis is consistent with available relevant information to date and provides an insight into the understanding of Martian surficial processes.     

New insights into the mineralogy and weathering of the Meridiani Planum meteorite,Mars

Meridiani Planum is the first officially recognized meteorite find on the surface of Mars. It was discovered at and named after the landing site of the Mars Exploration Rover Opportunity. Based on its composition, it was classified as a IAB complex iron meteorite. Mössbauer spectra obtained by Opportunity are dominated by kamacite (α‐Fe‐Ni) and exhibit a small contribution of ferric oxide. Several small features in the spectra have been neglected to date. To shed more light on these features, five iron meteorite specimens were investigated as analogs to Meridiani Planum with a laboratory Mössbauer setup. Measurements were performed on (1) their metallic bulk, (2) troilite (FeS) inclusions, (3) cohenite ((Fe,Ni,Co)₃C) and schreibersite ((Fe,Ni)₃P), and (4) corroded rims. In addition to these room‐temperature measurements, a specimen from the Mundrabilla IAB‐ungrouped meteorite was measured at Mars‐equivalent temperatures. Based on these measurements, the features in Meridiani Planum spectra can be explained with the presence of small amounts of schreibersite and/or cohenite and iron oxides. The iron oxides can be attributed to a previously reported coating on Meridiani Planum. Their presence indicates weathering through the interaction of the meteorite with small amounts of water.     

Diagenetic haematite and sulfate assemblages in Valles Marineris

Previous orbital mapping of crystalline gray haematite, ferric oxides, and sulfates has shown an association of this mineralogy with light-toned, layered deposits on the floor of Valles Marineris, in chaos terrains in the canyon’s outflow channels, and in Meridiani Planum. The exact nature of the relationship between ferric oxides and sulfates within Valles Marineris is uncertain. The Observatoire pour la Mineralogie, l’Eau, les Glaces et l’Activite (OMEGA) spectrometer initially identified sulfate and ferric oxides in the layered deposits of Valles Marineris. The Thermal Emission Spectrometer (TES) has also mapped coarse (gray) haematite in or at the base of these deposits. We use Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) spectra and Context Camera (CTX) and High Resolution Imaging Science Experiment (HiRISE) imagery from the Mars Reconnaissance Orbiter (MRO) to explore the mineralogy and morphology of the large layered deposit in central Capri Chasma, part of the Valles Marineris canyon system that has large, clear exposures of sulfate and haematite. We find kieserite (MgSO₄·H₂O) and ferric oxide (often crystalline red haematite) in the lower bedrock exposures and a polyhydrated sulfate without ferric oxides in the upper bedrock. This stratigraphy is duplicated in many other basinal chasmata, suggesting a common genesis. We propose the haematite and monohydrated sulfate formed by diagenetic alteration of a sulfate-rich sedimentary deposit, where the upper polyhydrated sulfate-rich, haematite-poor layers either were not buried sufficiently to convert to a monohydrated sulfate or were part of a later depositional phase. Based on the similarities between the Valles Marineris assemblages and the sulfate and haematite-rich deposits of Meridiani Planum, we hypothesize a common evaporite and diagenetic formation process for the Meridiani Planum sediments and the sulfate-bearing basinal Interior Layered Deposits.     

Does martian soil release reactive halogens to the atmosphere?

Detailed statistical examination of Cl, Br, and S distributions, in martian soil profiles at Gusev Crater and Meridiani Planum, indicates decreasing Br abundance and weakening Br–S association towards the surface. All three elements decrease towards the surface in the order Cl < S < Br. Furthermore, Br variability decouples from potential cations such as Mg at the surface relative to the subsurface. These observations support a relative loss of surficial Br compared to S and Cl, all highly mobile elements in aqueous environments. We propose that Br may have converted preferentially to gas phases (e.g., BrO), driven either by UV photolysis or by chemical oxidants. Such volatilization pathways may in turn impart a global signature on Mars by acting as controls on oxidants such as ozone and perchlorates. S/Cl mass ratios vary with depth (∼4–5 in the subsurface; 1.8–3.6 on the surface) as well, with a strong correlation of S and Cl near the surface but more variable at depth, consistent with differential vertical mobility, but not volatilization of Cl. Elevated S/Cl in subsurface soil also suggests that the ratio may be higher in bulk soil – a key repository of martian geologic and climatic records – than previously thought.     

Evidence for Amazonian acidic liquid water on Mars—A reinterpretation of MER mission results

The Mars Exploration Rover (MER) missions have confirmed aqueous activity on Mars. Here we review the analyses of the field-based MER data, and conclude that some weathering processes in Meridiani Planum and Gusev crater are better explained by late diagenetic water-rock interactions than by early diagenesis only. At Meridiani, the discovery of jarosite by MER-1 Opportunity indicates acidic aqueous activity, evaporation, and desiccation of rock materials. MER-based information, placed into the context of published data, point to local and limited aqueous activity during geologically recent times in Meridiani. Pre-Amazonian environmental changes (including important variations in the near-surface groundwater reservoirs, impact cratering, and global dust storms and other pervasive wind-related erosion) are too extreme for pulverulent jarosite to survive over extended time periods, and therefore we argue instead that jarosite deposits must have formed in a climatically more stable period. Any deposits of pre-existent concretionary jarosite surviving up to the Amazonian would not have reached completion in the highly saline and acidic brines occurring at Meridiani. MER-2 Spirit has also revealed evidence for local and limited Amazonian aqueous environmental conditions in Gusev crater, including chemical weathering leading to goethite and hematite precipitation, rock layering, and chemical enhancement of Cl, S, Br, and oxidized iron in rocks and soils. The estimated relative age of the impact crater materials in Gusev indicates that these processes have taken place during the last 2 billion years. We conclude that minor amounts of shallow acidic liquid water have been present on the surface of Mars at local scales during the Amazonian Period.     

Meridiani Planum hematite deposit and the search for evidence of life on Mars—iron mineralization of microorganisms in rock varnish

The extensive hematite deposit in Meridiani Planum was selected as the landing site for the Mars Exploration Rover Opportunity because the site may have been favorable to the preservation of evidence of possible prebiotic or biotic processes. One of the proposed mechanisms for formation of this deposit involves surface weathering and coatings, exemplified on Earth by rock varnish. Microbial life, including microcolonial fungi and bacteria, is documented in rock varnish matrices from the southwestern United States and Australia. Limited evidence of this life is preserved as cells and cell molds mineralized by iron oxides and hydroxides, as well as by manganese oxides. Such mineralization of microbial cells has previously been demonstrated experimentally and documented in banded iron formations, hot spring deposits, and ferricrete soils. These types of deposits are examples of the four “water-rock interaction” scenarios proposed for formation of the hematite deposit on Mars. The instrument suite on Opportunity has the capability to distinguish among these proposed formation scenarios and, possibly, to detect traces that are suggestive of preserved martian microbiota. However, the confirmation of microfossils or preserved biosignatures will likely require the return of samples to terrestrial laboratories.     

Mineralogy of Terra Meridiani and western Arabia Terra from OMEGA/MEx and implications for their formation

Analyses of Mars Express OMEGA hyperspectral data (0.4-2.7 μm) for Terra Meridiani and western Arabia Terra show that the northern mantled cratered terrains are covered by dust that is spectrally dominated by nanophase ferric oxides. Dark aeolian dunes inside craters and dark streaks extending from the dunes into the intercrater areas in mantled cratered terrains in western Arabia Terra have similar pyroxene-rich signatures demonstrating that the dunes supply dark basaltic material to create dark streaks. The dissected cratered terrains to the south of the mantled terrains are dominated spectrally by both low-calcium and high-calcium pyroxenes with abundances of 20-30% each retrieved from nonlinear radiative transfer modeling. Spectra over the hematite-bearing plains in Meridiani Planum are characterized by very weak but unique spectral features attributed to a mixture of a dark and featureless component (possibly gray hematite) and minor olivine in some locations. Hydrated minerals (likely hydrous ferric sulfates and/or hydrous hydroxides) associated with poorly ferric crystalline phases are found in the etched terrains to the north and east of the hematite-bearing plains where erosion has exposed ∼1 km of section of layered outcrops with high thermal inertias. These materials are also found in numerous craters in the northern Terra Meridiani and may represent outliers of the etched terrain materials. A few localized spots within the etched terrain also exhibit the spectral signature of Fe-rich phyllosilicates. The ensemble of observations show that the evidence for aqueous processes detected by the Opportunity Rover in Meridiani Planum is widespread and confirms the extended presence of surface or near-surface water over this large region of Mars. The scenarios of formation of Terra Meridiani (“dirty” acidic evaporite, impact surge or weathering of volcanic ash) cannot satisfactorily explain the mineralogy derived from the OMEGA observations. The formation of the etched terrains is consistent with leaching of iron sulfides and formation of sulfates and hydrated iron oxides, either in-place or via transport and evaporation of aqueous fluids and under aqueous conditions less acidic than inferred from rocks examined by Opportunity.     

Mössbauer study of Meridiani Planum,the first iron‐nickel meteorite found on the surface of Mars by the MER Opportunity

Abstract— –Meridiani Planum is the first iron meteorite found on Mars. It was discovered in 2005 by the Mars Exploration Rover Opportunity (MER‐B). Mössbauer spectra (MS) of the unbrushed and brushed meteorite species were acquired in 10 degrees temperature windows in the range of 210–260 K. Earlier examinations of these MS have led to the conclusion that the meteorite, which contains ～～7 wt% Ni, belongs to the IAB meteorite group. Here, making use of a recently developed calibration/folding procedure for MER MS, we report the results of the MS analyses for the single temperature windows m5 (210–220 K), m6 (220–230 K), m7 (230–240 K), and m89 (240–260 K). All spectra consist of a sextet and a ferric doublet. The hyperfine field of the sextet, extrapolated to room temperature, is ～～34.5 T, which is, based on Mössbauer studies of meteorites found on Earth, indeed consistent with the presence of kamacite. The fractional spectral area of the sextet is ～～0.96 of the total spectrum. The ferric doublet has an average quadrupole splitting of 0.70 mm/s and is not diagnostic of any specific Fe mineral.     

Bounce Rock—A shergottite‐like basalt encountered at Meridiani Planum,Mars

Abstract– The Opportunity rover of the Mars Exploration Rover mission encountered an isolated rock fragment with textural, mineralogical, and chemical properties similar to basaltic shergottites. This finding was confirmed by all rover instruments, and a comprehensive study of these results is reported here. Spectra from the miniature thermal emission spectrometer and the Panoramic Camera reveal a pyroxene‐rich mineralogy, which is also evident in Mössbauer spectra and in normative mineralogy derived from bulk chemistry measured by the alpha particle X‐ray spectrometer. The correspondence of Bounce Rock’s chemical composition with the composition of certain basaltic shergottites, especially Elephant Moraine (EET) 79001 lithology B and Queen Alexandra Range (QUE) 94201, is very close, with only Cl, Fe, and Ti exhibiting deviations. Chemical analyses further demonstrate characteristics typical of Mars such as the Fe/Mn ratio and P concentrations. Possible shock features support the idea that Bounce Rock was ejected from an impact crater, most likely in the Meridiani Planum region. Bopolu crater, 19.3 km in diameter, located 75 km to the southwest could be the source crater. To date, no other rocks of this composition have been encountered by any of the rovers on Mars. The finding of Bounce Rock by the Opportunity rover provides further direct evidence for an origin of basaltic shergottite meteorites from Mars.     

Mars: Evidence for dynamic processes from mariners 6 and 7

Mariners 6 and 7 photographs of the equatorial region of Mars document a three-stage evolution of that part of the Martian surface: (1) High- and intermediate-albedo cratered terrains in Meridiani Sinus, Margaritifer Sinus-Thymiamata, Deucalionis Regio-Sabaeus Sinus, and Hellespontus; (2) low-albedo moderately cratered terrain and dark crater fill in Meridiani Sinus, Thymiamata, and Deucalionis Regio-Sabaeus Sinus and possible volcanism in the Hellas-Hellespontus border; and (3) high-albedo surficial deposits, banked-up crater fill, a possible bright-ray crater in Meridiani Sinus, chaotic terrain on the edge of the Margaritifer Sinus mesa, featureless terrain in Hellas and Edom, sinuous channel-like reentrants on scarps at the Hellas-Hellespontus boundary. Regional faulting seems to have occurred following formation of the old cratered plains and prior to formation of low-albedo plains in Meridiani Sinus and also prior to formation of canyon-like reentrants and featureless terrain along the Hellas-Hellespontus boundary.Mars has had a complex history of dynamic evolution, possibly analogous to the more stable regions of Earth. Its geochemical differentiation and thermal regime should account for long-term postaccretional tectonic and volcano-tectonic processes as well as for fluid media on its surface sufficient to cause erosion, including the cutting of large canyons.     

Modeling hot spring chemistries with applications to martian silica formation

Many recent studies have implicated hydrothermal systems as the origin of martian minerals across a wide range of martian sites. Particular support for hydrothermal systems include silica (SiO₂) deposits, in some cases >90% silica, in the Gusev Crater region, especially in the Columbia Hills and at Home Plate. We have developed a model called CHEMCHAU that can be used up to 100 °C to simulate hot springs associated with hydrothermal systems. The model was partially derived from FREZCHEM, which is a colder temperature model parameterized for broad ranges of temperature (<−70 to 25 °C), pressure (1-1000 bars), and chemical composition. We demonstrate the validity of Pitzer parameters, volumetric parameters, and equilibrium constants in the CHEMCHAU model for the Na-K-Mg-Ca-H-Cl-ClO₄-SO₄-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system up to 100 °C and apply the model to hot springs and silica deposits.A theoretical simulation of silica and calcite equilibrium shows how calcite is least soluble with high pH and high temperatures, while silica behaves oppositely. Such influences imply that differences in temperature and pH on Mars could lead to very distinct mineral assemblages. Using measured solution chemistries of Yellowstone hot springs and Icelandic hot springs, we simulate salts formed during the evaporation of two low pH cases (high and low temperatures) and a high temperature, alkaline (high pH) sodic water. Simulation of an acid-sulfate case leads to precipitation of Fe and Al minerals along with silica. Consistency with martian mineral assemblages suggests that hot, acidic sulfate solutions are plausibility progenitors of minerals in the past on Mars. In the alkaline pH (8.45) simulation, formation of silica at high temperatures (355 K) led to precipitation of anhydrous minerals (CaSO₄, Na₂SO₄) that was also the case for the high temperature (353 K) low pH case where anhydrous minerals (NaCl, CaSO₄) also precipitated. Thus we predict that secondary minerals associated with massive silica deposits are plausible indicators on Mars of precipitation environments and aqueous chemistry. Theoretical model calculations are in reasonable agreement with independent experimental silica concentrations, which strengthens the validity of the new CHEMCHAU model.     

Modeling aqueous perchlorate chemistries with applications to Mars

NASA’s Phoenix lander identified perchlorate and carbonate salts on Mars. Perchlorates are rare on Earth, and carbonates have largely been ignored on Mars following the discovery by NASA’s Mars Exploration Rovers of acidic precipitated minerals such as jarosite. In light of the Phoenix results, we updated the aqueous thermodynamic model FREZCHEM to include perchlorate chemistry. FREZCHEM models the Na-K-Mg-Ca-Fe(II)-Fe(III)-Al-H-Cl-Br-SO₄-NO₃-OH-HCO₃-CO₃-CO₂-O₂-CH₄-Si-H₂O system, with 95 solid phases. We added six perchlorate salts: NaClO₄·H₂O, NaClO₄·2H₂O, KClO₄, Mg(ClO₄)₂·6H₂O, Mg(ClO₄)₂·8H₂O, and Ca(ClO₄)₂·6H₂O. Modeled eutectic temperatures for Na, Mg, and Ca perchlorates ranged from 199 K (−74 °C) to 239 K (−34 °C) in agreement with experimental data.We applied FREZCHEM to the average solution chemistry measured by the Wet Chemistry Laboratory (WCL) experiment at the Phoenix site when soil was added to water. FREZCHEM was used to estimate and alkalinity concentrations that were missing from the WCL data. The amount of is low compared to estimates from elemental abundance made by other studies on Mars. In the charge-balanced solution, the dominant cations were Mg²⁺ and Na⁺ and the dominant anions were , and alkalinity. The abundance of calcite measured at the Phoenix site has been used to infer that the soil may have been subject to liquid water in the past, albeit not necessarily locally; so we used FREZCHEM to evaporate (at 280.65 K) and freeze (from 280.65 to 213.15 K) the WCL-measured solution to provide insight into salts that may have been in the soil. Salts that precipitated under both evaporation and freezing were calcite, hydromagnesite, gypsum, KClO₄, and Mg(ClO₄)₂·8H₂O. Epsomite (MgSO₄·7H₂O) and NaClO₄·H₂O were favored by evaporation at temperatures >0 °C, while meridianite (MgSO₄·11H₂O), MgCl₂·12H₂O, and NaClO₄·2H₂O were favored at subzero temperatures. Incongruent melting of such highly hydrated salts could be responsible for vug formation elsewhere on Mars.All K⁺ precipitated as insoluble KClO₄ during both evaporation and freezing simulations, accounting for 15.8% of the total perchlorates. During evaporation, 35.8% of perchlorates precipitated with Na⁺ and 48.4% with Mg²⁺. During freezing, 58.4% precipitated with Na⁺ and 24.8% with Mg²⁺. Given its low eutectic temperature, the existence of Mg(ClO₄)₂ in either case allows for the possibility of liquid brines on Mars today. FREZCHEM also showed that Ca(ClO₄)₂ would likely not have precipitated at the Phoenix landing site due to the strong competing sinks for Ca as calcite and gypsum. Overall, these results help constrain the salt mineralogy of the soil. Differences between evaporites and cryogenites suggest ways to discriminate between evaporation and freezing during salt formation. Future efforts, such as sample return or in situ X-ray diffraction, may make such a determination possible.     

Fresnel modeling of hematite crystal surfaces and application to martian hematite spherules

The gray crystalline hematite at Meridiani Planum first discovered by the Mars Global Surveyor Thermal Emission Spectrometer (MGS-TES) instrument occurs as spherules that have been interpreted as concretions. Analysis of the TES and mini-TES spectra shows that no 390 cm⁻¹ feature is present in the characteristic martian hematite spectrum. Here, we incorporate the mid-IR optical constants of hematite into a simple Fresnel reflectance model to understand the effect of emission angle and crystal morphology on the presence or absence of the 390 cm⁻¹ feature in an IR hematite spectrum. Based on the results we offer two models for the internal structure of the martian hematite spherules.     

Geological features indicative of processes related to the hematite formation in Meridiani Planum and Aram Chaos, Mars: a comparison with diagenetic hematite deposits in southern Utah, USA

In order to understand the formation of the few but large, hematite deposits on Mars, comparisons are often made with terrestrial hematite occurrences. In southern Utah, hematite concretions have formed within continental sandstones and are exposed as extensive weathered-out beds. The hematite deposits are linked to geological and geomorphological features such as knobs, buttes, bleached beds, fractures and rings. These terrestrial features are visible in aerial and satellite images, which enables a comparison with similar features occurring extensively in the martian hematite-rich areas. The combination of processes involved in the movement and precipitation of iron in southern Utah can provide new insights in the context of the hematite formation on Mars. Here we present a mapping of the analogue geological and geomorphological features in parts of Meridiani Planum and Aram Chaos. Based on mapping comparisons with the Utah occurrences, we present models for the formation of the martian analogues, as well as a model for iron transport and precipitation on Mars. Following the Utah model, high albedo layers and rings in the mapped area on Mars are due to removal or lack of iron, and precipitation of secondary diagenetic minerals as fluids moved up along fractures and permeable materials. Hematite was precipitated intraformationally where the fluid transporting the reduced iron met oxidizing conditions. Our study shows that certain geological/geomorphological features can be linked to the hematite formation on Mars and that pH differences could suffice for the transport of the iron from an orthopyroxene volcanoclastic source rock. The presence of organic compounds can enhance the iron mobilization and precipitation processes. Continued studies will focus on possible influence of biological activity and/or methane in the formation of the hematite concretions in Utah and on Mars.     

Volatiles on Earth and Mars: A comparison

Based on our new and previous determinations of halogens in SNC meteorites, the bulk concentrations of halogens in the SPB, which is thought to be Mars, are estimated. The two-component model for the formation of terrestrial planets as proposed byA. E. Ringwood (Geochem. J. 11, 111–135 (1977) andOn the Origin of the Earth and Moon, Springer-Verlag, New York, 1979) andH. Wa¨nke (Philos. Trans. Roy. Soc. London, Ser. A 303, 287–302 (1981) is further substantiated. It is argued that almost all of the H₂O added to Mars during its homogeneous accretion was converted on reaction with metallic Fe to H₂, which escaped. By comparing the solubilities of H₂O and HCl in molten silicates, the amount of H₂O left in the mantle of Mars at the end of accretion can be related to the abundance of Cl. In this way an H₂O content in the Martian mantle of 36 ppm is obtained, corresponding to an ocean covering the whole planet to a depth of about 130 m.The huge quantities of H₂ produced by the reaction of H₂O with metallic iron should also have removed other volatile species by hydrodynamic escape. Thus it is postulated that the present atmospheres of Venus, Earth, and Mars were formed by degassing the interiors of the planets, after the production of H₂ had ceased, i.e., after metallic iron was no longer available. It is also postulated that the large differences in the amounts of primordial rare gases in the atmospheres of Venus, Earth, and Mars are due mainly to different loss factors.Except for gaseous species, Mars is found to be richer in volatile (halogens) and moderately volatile elements than the Earth. The resulting low release factor of⁴⁰Ar for Mars is attributed to a low degree of fractionation, leading to a relatively small crustal enrichment of even the most incompatible elements like K.     

Chemical weathering on Mars thermodynamic stabilities of primary minerals (and their alteration products) from mafic igneous rocks

Chemical weathering on Mars is examined theoretically from the standpoint of heterogeneous equilibrium between solid mineral phases and gaseous O₂, H₂O, and CO₂ in the Martian atmosphere. Thermochemical calculations are performed in order to identify important gas-solid decomposition reactions involving the major mineral constituents of mafic igneous rocks. Where unavailable in the thermochemical literature, Gibbs free energy and enthalpy of formation are estimated for certain minerals and details of these estimation procedures are given. Partial pressure stability diagrams are presented to show pertinent mineral reaction boundaries at 298 and at 240°K. In the present Martian environment, the thermodynamically stable products of gas-solid weathering of individual minerals at 240°K should be Fe₂O₃, as hematite or maghemite (from fayalite, magnetite, and Fe-bearing pyroxenes), quartz (from all silicates), calcite (from Ca-bearing pyroxenes and plagioclase), magnesite (from forsterite and Mg-bearing pyroxenes), corundum (from all Al-bearing silicates), Ca-beidellite (from anorthite), and szomolnokite, FeSO₄ or FeSO₄·H₂O (from iron sulfides). Albite, microcline, and apatite should be stable with respect to gas-solid decomposition, suggesting that gas-solid weathering products on Mars may be depleted in Na, K, and P (and, possibly, Cl and F). Certain montmorillonite-type clay minerals are thermodynamically favorable intermediate gas-solid decomposition products of Al-bearing pyroxenes and may be metastable intermediate products of special mineral surface reaction mechanisms. However, the predicted high thermodynamic susceptibility of these clay minerals to subsequent gas-solid decomposition implies that they should ultimately decompose in the present Martian surface environment. Kaolinite is apparently the only clay mineral which should be thermodynamically stable over all ranges of temperature and water vapor abundance in the present environment at the Martian surface. Considering thermodynamic criteria, including possible gas-solid decomposition reactions, it is doubtful that significant amounts of goethite and clay minerals can be currently forming on Mars by mechanisms known to operate to Earth. If major amounts of goethite and clay minerals occur on Mars, they probably owe their existence to formation in an environment characterized by the presence of liquid water or by mechanism possibly unique to Mars. In any case, any goethite or montmorillonite-type clay mineral on Mars must ultimately decompose.     

Inflated flows on Daedalia Planum (Mars)? Clues from a comparative analysis with the Payen volcanic complex (Argentina)

Inflation is an emplacement process of lava flows, where a thin visco-elastic layer, produced at an early stage, is later inflated by an underlying fluid core. The core remains hot and fluid for extended period of time due to the thermal-shield effect of the surface visco-elastic crust. Plentiful and widespread morphological fingerprints of inflation like tumuli and lava rises are found on the Payen volcanic complex (Argentina), where pahoehoe lava flows extend over the relatively flat surface of the Pampean foreland and reach at least 180 km in length.The morphology of the Argentinean Payen flows were compared with lava flows on Daedalia Planum (Mars), using Thermal Emission Imaging System (THEMIS), Mars Orbiter Laser Altimeter (MOLA), Mars Orbiter Camera (MOC), Mars Reconnaissance Orbiter (MRO)/High-Resolution Imaging Science Experiment (HiRISE). THEMIS images were used to map the main geological units of Daedalia Planum and determine their stratigraphic relationships. MOLA data were used to investigate the topographic surface over which the flows propagated and assess the thickness of lava flows. Finally, MOC and MRO/HIRISE images were used to identify inflations fingerprints and assess the cratering age of the Daedalia Planum’ s youngest flow unit which were found to predate the caldera formation on top of the Arsia Mons. The identification of similar inflation features between the Daedalia Planum and the Payen lava fields suggests that moderate and long lasting effusion rates coupled with very efficient spreading processes could have cyclically occurred in the Arsia Mons volcano during its eruptive history. Consequently the effusion rates and rheological proprieties of Daedalia lava flows, which do not take into account the inflation process, can be overestimated. These findings raise some doubts about the effusion rates and lava rheological properties calculated on Martian flows and recommends that these should be used with caution if applied on flows not checked with high-resolution images and potentially affected by inflation. Further HiRISE data acquisition will permit additional analysis of the flow surfaces and will allow more accurate estimates of effusion rates and rheological properties of the lava flows on Mars particularly if this data is acquired under a favourable illumination.     

North polar region of Mars: Advances in stratigraphy, structure, and erosional modification

We have remapped the geology of the north polar plateau on Mars, Planum Boreum, and the surrounding plains of Vastitas Borealis using altimetry and image data along with thematic maps resulting from observations made by the Mars Global Surveyor, Mars Odyssey, Mars Express, and Mars Reconnaissance Orbiter spacecraft. New and revised geographic and geologic terminologies assist with effectively discussing the various features of this region. We identify 7 geologic units making up Planum Boreum and at least 3 for the circumpolar plains, which collectively span the entire Amazonian Period. The Planum Boreum units resolve at least 6 distinct depositional and 5 erosional episodes. The first major stage of activity includes the Early Amazonian (∼3 to 1 Ga) deposition (and subsequent erosion) of the thick (locally exceeding 1000 m) and evenly-layered Rupes Tenuis unit (Abrt), which ultimately formed approximately half of the base of Planum Boreum. As previously suggested, this unit may be sourced by materials derived from the nearby Scandia region, and we interpret that it may correlate with the deposits that regionally underlie pedestal craters in the surrounding lowland plains. The second major episode of activity during the Middle to Late Amazonian (1 Ga) began with a section of dark, sand-rich and light-toned ice-rich irregularly-bedded sequences (Planum Boreum cavi unit, Abb_c) along with deposition of evenly-bedded light-toned ice- and moderate-toned dust-rich layers (Planum Boreum 1 unit, Abb₁). These units have transgressive and gradational stratigraphic relationships. Materials in Olympia Planum underlying the dunes of Olympia Undae are interpreted to consist mostly of the Planum Boreum cavi unit (Abb_c). Planum Boreum materials were then deeply eroded to form spiral troughs, Chasma Boreale, and marginal scarps that define the major aspects of the polar plateau's current regional topography. Locally- to regionally-extensive (though vertically minor) episodes of deposition of evenly-bedded, light- and dark-toned layered materials and subsequent erosion of these materials persisted throughout the Late Amazonian. Sand saltation, including dune migration, is likely to account for much of the erosion of Planum Boreum, particularly at its margin, alluding to the lengthy sedimentological history of the circum-polar dune fields. Such erosion has been controlled largely by topographic effects on wind patterns and the variable resistance to erosion of materials (fresh and altered) and physiographic features. Some present-day dune fields may be hundreds of kilometers removed from possible sources along the margins of Planum Boreum, and dark materials, comprised of sand sheets, extend even farther downwind. These deposits also attest to the lengthy period of erosion following emplacement of the Planum Boreum 1 unit. We find no evidence for extensive glacial flow, topographic relaxation, or basal melting of Planum Boreum materials. However, minor development of normal faults and wrinkle ridges may suggest differential compaction of materials across buried scarps. Timing relations are poorly-defined mostly because resurfacing and other uncertainties prohibit precise determinations of surface impact crater densities. The majority of the stratigraphic record may predate the recent (<20 Ma) part of the orbitally-driven climate record that can be reliably calculated. Given the strong stratigraphic but loose temporal constraints of the north polar geologic record, a comparison of north and south polar stratigraphy permits a speculative scenario in which major Amazonian depositional and erosional episodes driven by global climate activity is plausible.     

Beta-carotene—A possible biomarker in the Martian evaporitic environment: Raman micro-spectroscopic study

Due to the discovery of the evaporitic environment on the Martian surface, there is a reasonable possibility that evaporites served (or still serve) as habitats for microbial life if ever present on Mars. At the very least, if no signatures of extant life exist within these rocks, it may sustain molecular remnants as evidence for living organisms in the past. β-Carotene, among other carotenoids, could be such a suitable biomarker. In this study, Raman micro-spectroscopy was tested as a nondestructive method of determining the presence of β-carotene in experimentally prepared evaporitic matrices. Samples prepared by mixing β-carotene with powdered gypsum (CaSO₄·2H₂O), halite (NaCl) and epsomite (MgSO₄·7H₂O) were analyzed using a 785 nm excitation source. Various concentrations of β-carotene in the matrices were investigated to determine the lowest β-carotene content detectable by Raman micro-spectroscopy. Mixtures were also measured with a laser beam permeating the crystals of gypsum and epsomite in order to evaluate the possibility of identifying β-carotene inside the mineral matrix.We were able to obtain a clear β-carotene signal at the 10 mg kg⁻¹ concentration level—the number of registered β-carotene Raman bands differed depending on the particular mineral matrix. Spectral signatures of β-carotene were detected even when analyzing samples containing 1 mg kg⁻¹ of this molecule. The 10-100 mg kg⁻¹ of β-carotene in mineral matrices (halite, epsomite) was detected when analyzed through the monocrystal of gypsum and epsomite, respectively. These results will aid both in-situ analyses on Mars and sample analyses on Earth.