Experimental Evidence for Weathering and Martian Sulfate Formation Under Extremely Cold Weather-Limited Environments

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being wide-spread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars [1, 2]. The mechanism for sulfate formation on Mars has been frequently attributed to playa-like evaporative environments under prolonged warm conditions [3]. However, there are several problems with the presence of prolonged surface temperatures on Mars above 273 K during the Noachian including the faint young Sun [4] and the presence of suitable greenhouse gases [5]. The geomorphic evidence for early warm conditions may instead be explained by periodic episodes of warming rather than long term prolonged warm temperatures [6]. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history [6]. This view is more consistent with the climate models, but has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryo-concentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars [7, 8]. This study seeks to test whether sulfate formation may be possible at temperatures well below 0 C in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars

Olivine Weathering aud Sulfate Formation Under Cryogenic Conditions

High resolution photography and spectroscopy of the martian surface (MOC, HiRISE) from orbit has revolutionized our view of Mars with one of the most important discoveries being widespread layered sedimentary deposits associated with sulfate minerals across the low to mid latitude regions of Mars. The mechanism for sulfate formation on Mars has been frequently attributed to playalike evaporative environments under prolonged warm conditions. An alternate view of the ancient martian climate contends that prolonged warm temperatures were never present and that the atmosphere and climate has been similar to modern conditions throughout most of its history. This view has had a difficult time explaining the sedimentary history of Mars and in particular the presence of sulfate minerals which seemingly need more water. We suggest here that mixtures of atmospheric aerosols, ice, and dust have the potential for creating small films of cryoconcentrated acidic solutions that may represent an important unexamined environment for understanding weathering processes on Mars. This study seeks to test whether sulfate formation may be possible at temperatures well below 0degC in water limited environments removing the need for prolonged warm periods to form sulfates on early Mars. To test this idea we performed laboratory experiments to simulate weathering of mafic minerals under Marslike conditions. The weathering rates measured in this study suggest that fine grained olivine on Mars would weather into sulfate minerals in short time periods if they are exposed to H2SO4 aerosols at temperatures at or above 40degC. In this system, the strength of the acidic solution is maximized through eutectic freezing in an environment where the silicate minerals are extremely fine grained and have high surface areas. This provides an ideal environment despite the very low temperatures. On Mars the presence of large deposits of mixed ice and dust is undisputed. The presence of substantial sulfurrich volcanism, and sulfurrich surface deposits also makes it very likely that sulfate aerosols have also been an important component of the martian atmosphere. Thus mixtures of ice, dust, and sulfate aerosols are likely to have been common on the martian surface. Given the fact that it is not difficult to achieve surface temperatures above 40degC on Mars throughout its history, it seems likely that sulfate formation on Mars is controlled by the availability of sulfate aerosols and not by the martian climate. The current polar regions of Mars and Earth provide interesting analogs. Large regions of sulfaterich material have been detected on and around the modern north polar region of Mars. The prevalence of icedust mixtures in this region and the existence of sulfates within the ice cap itself are strong evidence for the origin of the sulfates from inside the ice deposits. In addition sulfates have been found in ice deposits in Greenland and Mount Fuji on Earth that have been attributed to forming within the ice deposit. These sulfates can form either through interaction with dust particles in the atmosphere or through weathering inside the ice itself

A high resolution, hard x-ray photoemission investigation of La_(2-2x)Sr_(1+2x)Mn_2O_7 (0.30<x<0.50): on microscopic phase separation and the surface electronic structure of a bilayered CMR manganite

Photoemission data taken with hard x-ray radiation on cleaved single crystals of the bilayered, colossal magnetoresistant manganite La_(2-2x)Sr_(1+2x)Mn_2O_7 (LSMO) with 0.30<x<0.50 are presented. Making use of the increased bulk-sensitivity upon hard x-ray excitation it is shown that the core level footprint of the electronic structure of the LSMO cleavage surface is identical to that of the bulk. Furthermore, by comparing the core level shift of the different elements as a function of doping level x, it is shown that microscopic phase separation is unlikely to occur for this particular manganite well above the Curie temperature.Comment: 7 pages, 5 figure

Angle-resolved and core-level photoemission study of interfacing the topological insulator Bi1.5Sb0.5Te1.7Se1.3 with Ag, Nb and Fe

Interfaces between a bulk-insulating topological insulator (TI) and metallic adatoms have been studied using high-resolution, angle-resolved and core-level photoemission. Fe, Nb and Ag were evaporated onto Bi1.5Sb0.5Te1.7Se1.3 (BSTS) surfaces both at room temperature and 38K. The coverage- and temperature-dependence of the adsorption and interfacial formation process have been investigated, highlighting the effects of the overlayer growth on the occupied electronic structure of the TI. For all coverages at room temperature and for those equivalent to less than 0.1 monolayer at low temperature all three metals lead to a downward shift of the TI's bands with respect to the Fermi level. At room temperature Ag appears to intercalate efficiently into the van der Waals gap of BSTS, accompanied by low-level substitution of the Te/Se atoms of the termination layer of the crystal. This Te/Se substitution with silver increases significantly for low temperature adsorption, and can even dominate the electrostatic environment of the Bi/Sb atoms in the BSTS near-surface region. On the other hand, Fe and Nb evaporants remain close to the termination layer of the crystal. On room temperature deposition, they initially substitute isoelectronically for Bi as a function of coverage, before substituting for Te/Se atoms. For low temperature deposition, Fe and Nb are too immobile for substitution processes and show a behaviour consistent with clustering on the surface. For both Ag and Fe/Nb, these differing adsorption pathways leads to the qualitatively similar and remarkable behavior for low temperature deposition that the chemical potential first moves upward (n-type dopant behavior) and then downward (p-type behavior) on increasing coverage.Comment: 10 pages, 4 figures. In our Phys. Rev. B manuscript an error was made in formulating the last sentence of the abstract that, unfortunately, was missed in the page proofs. Version 2 on arxiv has the correct formulation of this sentenc

Calcium Sulfate in Atacama Desert Basalt: A Possible Analog for Bright Material in Adirondack Basalt, Gusev Crater

The Atacama Desert in northern Chile is one of the driest deserts on Earth (< 2mm/y). The hyper-arid conditions allow extraordinary accumulations of sulfates, chlorides, and nitrates in Atacama soils. Examining salt accumulations in the Atacama may assist understanding salt accumulations on Mars. Recent work examining sulfate soils on basalt parent material observed white material in the interior vesicles of surface basalt. This is strikingly similar to the bright-white material present in veins and vesicles of the Adirondack basalt rocks at Gusev Crater which are presumed to consist of S, Cl, and/or Br. The abundance of soil gypsum/anhydrite in the area of the Atacama basalt suggested that the white material consisted of calcium sulfate (Ca-SO4) which was later confirmed by SEM/EDS analysis. This work examines the Ca-SO4 of Atacama basalt in an effort to provide insight into the possible nature of the bright material in the Adirondack basalt of Gusev Crater. The objectives of this work are to (i) discuss variations in Ca-SO4 crystal morphology in the vesicles and (ii) examine the Ca-SO4 interaction(s) with the basalt interior

The Alteration History of Clovis Class Rocks in Gusev Crater as Determined by Ti-Normalzed Mass Balance Analysis

The West Spur Clovis class rocks in Gusev Crater are some of the most altered rocks in Gusev Crater and likely contain a mixed sulfate and phyllosilicate mineralogy [1,2]. The high S and Cl content of the Clovis rocks suggests that acidic vapors or fluids of H2SO4 and HCl reacted with the Clovis parent rock to form Ca, Mg,- sulfates, iron-oxyhydroxides and secondary aluminosilicates (approx.60 wt.%) of a poorly crystalline nature (e.g., allophane) [1]. Up to 14-17 wt.% phyllosilicates (e.g., kaolinite, chlorite, serpentine) are hypothesized to exist in the Clovis materials suggesting that Clovis parent materials while possibly exposed to acidic pHs were likely neutralized by basalt dissolution which resulted in mildly acidic pHs (4-6) [1, 2]. This work proposes that subsequent to the alteration of the Clovis rocks, alteration fluids became concentrated in ions resulting in the addition of silicate and salts. The objective of this work is to utilize Ti-normalized mass balance analysis to evaluate (1) mineral gains and losses and (2) elemental gains and losses in the Clovis rocks. Results of this work will be used evaluate the nature of geochemical conditions that affect phyllosilicate and sulfate formation at Gusev crater

The Formation of Fe/Mg Smectite Under Mildly Acidic Conditions on Early Mars

The detection of Fe/Mg smectites and carbonate in Noachian and early Hesperian terrain of Mars has been used to suggest that neutral to mildly alkaline conditions prevailed during the early history of Mars. However, if early Mars was neutral to moderately alkaline with a denser CO2 atmosphere than today, then large carbonates deposits should be more widely detected in Noachian terrain. The critical question is: Why have so few carbonate deposits been detected compared to Fe/Mg smectites? We suggest that Fe/Mg smectites on early Mars formed under mildly acidic conditions, which would inhibit the extensive formation of carbonate deposits. The goal of this work is to evaluate the formation of Fe/Mg smectites under mildly acidic conditions. The stability of smectites under mildly acidic conditions is attributed to elevated Fe/Mg activities that inhibit smectite dissolution. Beidelite and saponite have been shown to form from hydrothermal alteration of basaltic glass at pH 3.5-4.0 in seawater solutions. Nontronite is also known to be stable in mildly acidic systems associated with mafic and ultramafic rock. Nontronite was shown to form in acid sulfate soils in the Bangkok Plain, Thailand due to oxidation of Fe-sulfides that transformed saponite to nontronite. Smectite is known to transform to kaolinite in naturally acid soils due to selective leaching of Mg. However, if Mg removal is limited, then based on equilibrium relationships, the dissolution of smectite should be minimized. If Fe and Mg solution activities are sufficiently high, such as might be found in a low water/rock ratio system that is poorly drained, smectite could form and remain stable under mildly acidic conditions on Mars. The sources of mild acidity on early Mars includes elevated atmospheric CO2 levels, Fe-hydrolysis reactions, and the presence of volcanic SO2 aerosols. Equilibrium calculations dictate that water equilibrated with an early Mars CO2 atmosphere at 1 to 4 bar yields a pH of 3.6 to 3.9. Fe hydrolysis reactions on Mars is another source of protons that would have contributed to acidity. The presence of SO2 from volcanic processes could also have contributed to geochemical acidification. These sources of acidity competed with base-forming cations that resulted in mildly acidic solutions that were not favorable for carbonate formation but may have allowed for Fe/Mg smectite formation. Noachian to early Hesperian Mars could have been mildly acidic, allowing Fe/Mg smectite formation but preventing widespread carbonate deposition. This paradigm shift from an early Mars that was neutral-alkaline to mildly acidic may possibly explain why there is a disparity between the occurrence of carbonate and Fe/Mg smectites. Potential microbiological activity would not be eliminated under a mildly acidic Mars; however, there could be tighter constraints as to the type and species of microbiology that could exist

Absolute rigidity spectrum of protons and helium nuclei above 10 GV/c

Proton and helium nuclei differential spectra were gathered with a balloon borne magnet spectrometer. The data were fitted to the assumption that the differential flux can be represented by a power law in rigidity. In the rigidity range 10 to 25 GV/c the spectral indices were found to be -(2.74 plus or minus 0.04) for protons and -(2.71 plus or minus 0.05) for helium nuclei. A brief discussion is given by systematic errors

Transition in the Fractal Geometry of Arctic Melt Ponds

During the Arctic melt season, the sea ice surface undergoes a remarkable transformation from vast expanses of snow covered ice to complex mosaics of ice and melt ponds. Sea ice albedo, a key parameter in climate modeling, is determined by the complex evolution of melt pond configurations. In fact, ice–albedo feedback has played a major role in the recent declines of the summer Arctic sea ice pack. However, understanding melt pond evolution remains a significant challenge to improving climate projections. By analyzing area–perimeter data from hundreds of thousands of melt ponds, we find here an unexpected separation of scales, where pond fractal dimension D transitions from 1 to 2 around a critical length scale of 100 m2 in area. Pond complexity increases rapidly through the transition as smaller ponds coalesce to form large connected regions, and reaches a maximum for ponds larger than 1000 m2, whose boundaries resemble space-filling curves, with D ≈ 2. These universal features of Arctic melt pond evolution are similar to phase transitions in statistical physics. The results impact sea ice albedo, the transmitted radiation fields under melting sea ice, the heat balance of sea ice and the upper ocean, and biological productivity such as under ice phytoplankton blooms