Carbon and oxygen isotope composition of carbonates from an L6 chondrite: Evidence for terrestrial weathering from the Holbrook meteorite

Terrestrial weathering in meteorites is an important process which alters pristine elemental and isotopic abundances. The Holbrook L6 chondrite fell in 1912. Material was recovered at the time of the fall, in 1931, and 1968. The weathering processes operating on the freshly fallen meteorite in a semi-arid region of northeastern Arizona have been studied after a ground residence of 19 and 56 years. It has been shown that a large portion of the carbonate material in 7 Antarctic ordinary chondrites either underwent extensive isotopic exchange with atmospheric CO2, or formed recently in the Antarctic environment. In fact it has been demonstrated that hydrated Mg-carbonates, nesquehonite and hydromagnesite, formed in less than 40 years on LEW 85320. In order to help further constrain the effects of terrestrial weathering in meteorites, the carbon and oxygen isotopes extracted from carbonates of three different samples of Holbrook L6: a fresh sample at the time of the fall in 1912, a specimen collected in 1931, and a third specimen collected at the same site in 1968

Carbon Isotope Systematics in Mineral-Catalyzed Hydrothermal Organic Synthesis Processes at High Temperature and Pressures

Observation of methane in the Martian atmosphere has been reported by different detection techniques. Reduction of CO2 and/or CO during serpentization by mineral surface catalyzed Fischer-Tropsch Type (FTT) synthesis may be one possible process responsible for methane generation on Mars. With the evidence a recent study has discovered for serpentinization in deeply buried carbon rich sediments, and more showing extensive water-rock interaction in Martian history, it seems likely that abiotic methane generation via serpentinization reactions may have been common on Mars. Experiments involving mineral-catalyzed hydrothermal organic synthesis processes were conducted at 750 C and 5.5 Kbars. Alkanes, alcohols and carboxylic acids were identified as organic compounds. No "isotopic reversal" of delta C-13 values was observed for alkanes or carboxylic acids, suggesting a different reaction pathway than polymerization. Alcohols were proposed as intermediaries formed on mineral surfaces at experimental conditions. Carbon isotope data were used in this study to unravel the reaction pathways of abiotic formation of organic compounds in hydrothermal systems at high temperatures and pressures. They are instrumental in constraining the origin and evolution history of organic compounds on Mars and other planets

A New Method for Evaluating the Carbon Isotope Characteristics of Carbonate Formed Under Cryogenic Conditions Analogous to Mars

The two upcoming robotic missions to Mars, Phoenix and MSL, will both have the capability of measuring the carbon isotopic composition of CO2 in the martian atmosphere, as well as possible CO2 trapped in carbonate minerals in the Martian soil. Results from orbital and landed missions now clearly indicate that no large scale deposits of carbonate materials exist at the surface. However, some results from orbital remote sensing have been interpreted to indicate that carbonate minerals are present as fine particles interspersed at low concentrations (approx. 2%) in the martian dust. One likely mechanism for the production of these carbonates is during the freezing of transient water near the surface. Large deposits of near surface ice and photographic evidence for flowing water on the surface suggest that transient melting and refreezing of H2O is an active process on Mars. Any exposure of these fluids to the CO2 rich atmosphere should al-low the production of HCO3- solutions. Carbonates are likely precipitates from these solutions during freezing as extensive CO2 degassing, driven by the fluid s decreasing volume, drives CO2 out. This rapid CO2 degassing increases the pH of the solution and drives carbonate precipitation. It has been shown in previous studies that this rapid CO2 degassing also results in a kinetic isotopic fractionation where the CO2 gas has a much lighter isotopic composition causing a large isotope enrichment of C-13 in the precipitated carbonate. This kinetic isotope enrichment may be very common in the current martian environment, and may be a very important factor in understanding the very high deltaC-13 values of carbonates found in the martian meteorites. However, while previous studies have succeeded in generally quantifying the magnitude of this effect, detailed studies of the consistency of this effect, and the freezing rates needed to produce it are needed to understand any carbon isotope analyses from carbonate minerals in the martian soil or dust. This study demonstrates an innovative new method for measuring the isotopic composition of gas evolved from the freezing of carbonate solutions in real time, which allows for a much clearer view of the chemical processes involved. This method now sets the stage for detailed analysis of the chemical and isotopic mechanisms that produce cryogenic carbonates

Zeolite Formation and Weathering Processes in Dry Valleys of Antartica: Martian Analogs

Terrestrial weathering processes in cold-desert climates such as the Dry Valleys of Antarctica may provide an excellent analog to chemical weathering and diagenesis of soils on Mars. Detailed studies of soil development and the chemical and mineralogical alterations occurring within soil columns in Wright Valley, Antarctica show incredible complexity in the upper meter of soil. Previous workers noted the ice-free Dry Valleys are the best terrestrial approximations to contemporary Mars. Images returned from the Pathfinder and Spirit landers show similarities to surfaces observed within the Dry Valleys. Similarities to Mars that exist in these valleys are: mean temperatures always below freezing (-20 C), no rainfall, sparse snowfall-rapidly removed by sublimation, desiccating winds, diurnal freeze-thaw cycles (even during daylight hours), low humidity, oxidative environment, relatively high solar radiation and low magnetic fields . The Dry Valley soils contain irregular distributions and low abundances of soil microorganisms that are somewhat unusual on Earth. Physical processes-such as sand abrasion-are dominant mechanisms of rock weathering in Antarctica. However, chemical weathering is also an important process even in such extreme climates. For example, ionic migration occurs even in frozen soils along liquid films on individual soil particles. It has also been shown that water with liquid-like properties is present in soils at temperatures on the order of approx.-80 C and it has been observed that the percentage of oxidized iron increases with increasing soil age and enrichments in oxidized iron occurs toward the surface. The presence of evaporates is evident and appear similar to "evaporite sites" within the Pathfinder and Spirit sites. Evaporites indicate ionic migration and chemical activity even in the permanently frozen zone. The presence of evaporates indicates that chemical weathering of rocks and possibly soils has been active. Authogenic zeolites have been identified within the soil columns because they are fragile; i.e. they are euhedral, unabraded, and unfractured, strongly suggesting in situ formation. Their presence in Antarctic samples is another indication that diagenic processes are active in cold-desert environments. The presence of zeolites, and other clays along with halites, sulfates, carbonates, and hydrates are to be expected within the soil columns on Mars at the Gusev and Isidis Planitia regions. The presence of such water-bearing minerals beneath the surface supplies one of the requirements to support biological activity on Mars

Antarctic weathering of the CK chondrites EET90004, 90007, and 90022: Nickel and sulfur mobility

CK chondrites are a relatively new class of carbonaceous chondrite that have been described in the literature. Most meteorites that comprise the CK group are restricted to Antarctic finds; therefore terrestrial weathering processes can influence the geochemical records contained within these chondrites. The paired CK chondrites EET90004, 90007, and 90022 share not only a common heritage but similar weathering histories since all three meteorites were found on Antarctic ice covered with thick evaporative coatings. Additional material has grown on these samples during curation at the Antarctic Meteorite Lab at JSC, NASA. At present, efflorescence up to a millimeter thick coats the surface of EET90004 and 90022, with less material coating EET90007. The chemistry, mineralogy, and isotopic composition of efflorescence on EET90004 and 90022, described here, provide valuable information regarding the fate of meteoritic components in the Antarctic environment

Mars Sample Return: The Value of Depth Profiles

Sample return from Mars offers the promise of data from Martian materials that have previously only been available from meteorites. Return of carefully selected samples may yield more information about the history of water and possible habitability through Martian history. Here we propose that samples collected from Mars should include depth profiles of material across the interface between weathered material on the surface of Mars into unweathered parent rock material. Such profiles have the potential to yield chemical kinetic data that can be used to estimate the duration of water and information about potential habitats on Mars

Source water, phenology and growth of two tropical dry forest tree species growing on shallow karst soils

Seasonally dry tropical forests are dominated by deciduous and evergreen tree species with a wide range of leaf phenology. We hypothesized that Piscidia piscipula is able to extend leaf senescence until later in the dry season due to deeper and more reliable water sources than Gymnopodium floribundum, which loses leaves earlier in the dry season. Physiological performance was assessed as timing of leaf production and loss, growth, leaf water potential, depth of water uptake determined by stable isotopes, and leaf stable isotopic composition of carbon (δ¹³C) and oxygen (δ¹⁸O). P. piscipula took water primarily from shallow sources, whereas G. floribundum took water from shallow and deep sources. The greatest variation in water sources occurred during the onset of the dry season, when G. floribundum was shedding old leaves and growing new leaves, but P. piscipula maintained its leaves from the previous wet season. P. piscipula showed greater relative growth rate, greater leaf expansion rates, and more negative predawn and midday water potentials than G. floribundum. P. piscipula also exhibited greater leaf organic δ¹³C and lower δ¹⁸O values, indicating that the decrease in photosynthetic carbon isotope discrimination was associated with greater stomatal conductance and greater photosynthesis. Our results indicate that the contrasting early and late dry season leaf loss phenology of these two species is not simply determined by rooting depth, but rather a more complicated suite of characteristics based on opportunistic use of dynamic water sources, maximizing carbon gain, and maintenance of water potential during the dry season

Experimental Study of Abiotic Organic Synthesis at High Temperature and Pressure Conditions: Carbon Isotope and Mineral Surface Characterizations

Abiotic organic synthesis processes have been proposed as potential mechanisms for methane generation in subseafloor hydrothermal systems on Earth, and on other planets. To better understand the detailed reaction pathways and carbon isotope fractionations in this process under a wide range of physical and chemical conditions, hydrothermal experiments at high temperature (750 C) and pressure (0.55 GPa) were performed using piston cylinder apparatus. Formic acid was used as the source of CO2 and H2, and magnetite was the mineral catalyst. The chemical and carbon isotopic compositions of dissolved organic products were determined by GC-C-MS-IRMS, while organic intermediaries on the mineral catalyst were characterized by Pyrolysis-GC-MS. Among experimental products, dissolved CO2 was the dominant carbon species with a relative abundance of 88 mol%. Dissolved CH4 and C2H6 were also identified with a mole ratio of CH4 over C2H6 of 15:1. No dissolved CO was detected in the experiment, which might be attributable to the loss of H2 through the Au capsule used in the experiments at high temperature and pressure conditions and corresponding conversion of CO to CO2 by the water-gas shift reaction. Carbon isotope results showed that the 13C values of CH4 and C2H6 were -50.3% and -39.3% (V-PDB), respectively. CO2 derived from decarboxylation of formic acid had a (sigma)C-13 value of -19.2%, which was 3.2% heavier than its source, formic acid. The (sigma)C-13 difference between CO2 and CH4 was 31.1%, which was higher than the value of 9.4% calculated from theoretical isotopic equilibrium predictions at experimental conditions, suggesting the presence of a kinetic isotope effect. This number was also higher than the values (4.6 to 27.1%) observed in similar experiments previously performed at 400 C and 50 MPa with longer reaction times. CH4 is 11.0% less enriched in C-13 than C2H6. Alcohols were observed as carbon compounds on magnetite surfaces by Pyrolysis-GC-MS, which confirms the hypothesis regarding the reaction pathways of hydrothermal abiotic organic synthesis proposed by Fu et al. (2007, 2008). In this proposed pathway, hydroxymethylene (-CHOH) groups serve as organic intermediaries on mineral surfaces while dissolved H2 serves as a chain terminator/breaker to generate short chain hydrocarbons and oxygenated compounds. This pathway is different from the carbide polymerization theory of Fischer- Tropsch-type (FTT) synthesis in a gas phase. The observed increase of (sigma)C-13 values of C1 and C2 alkanes with carbon number in our hydrothermal experiments can be readily interpreted by hydroxymethylene pathway, and might be used to differentiate between hydroxymethylene and carbide polymerization pathways. Carbon isotope analysis of alcohols on mineral catalyst surfaces is under way to provide further constraints on formation of organic compounds by FTT in hydrothermal systems

Lost cold Antarctic deserts inferred from unusual sulfate formation and isotope signatures

The Antarctic ice cap significantly affects global ocean circulation and climate. Continental glaciogenic sedimentary deposits provide direct physical evidence of the glacial history of the Antarctic interior, but these data are sparse. Here we investigate a new indicator of ice sheet evolution: sulfates within the glaciogenic deposits from the Lewis Cliff Ice Tongue of the central Transantarctic Mountains. The sulfates exhibit unique isotope signatures, including I 34 S up to +50‰ for mirabilite evaporites, I " 17 O up to +2.3‰ for dissolved sulfate within contemporary melt-water ponds, and extremely negative I 18 O as low as a '22.2‰. The isotopic data imply that the sulfates formed under environmental conditions similar to todaya € s McMurdo Dry Valleys, suggesting that ice-free cold deserts may have existed between the South Pole and the Transantarctic Mountains since the Miocene during periods when the ice sheet size was smaller than today, but with an overall similar to modern global hydrological cycle