A First Look at Carbon and Oxygen Stable Isotope Measurements of Martian Atmospheric C02 by the Phoenix Lander

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. The isotopic composition of the martian atmosphere has been measured using a number of different methods (Table 1), however a precise value (<1%) has yet to be achieved. Given the elevated 13C values measured in carbonates in martian meteorites it has been supposed that the martian atmosphere was enriched in delta(sup 13)C. This was supported by measurements of trapped CO2 gas in EETA 79001[2] which showed elevated delta(sup 13)C values (Table 1). More recently, Earth-based spectroscopic measurements of the martian atmosphere have measured the martian CO2 to be depleted in delta(sup 13)C relative to CO2 in the terrestrial atmosphere. The spectroscopic measurements performed by Krasnopolsky et al. were reported with approx.2% uncertainties which are much smaller than the Viking measurements, but still remain very large in comparison to the magnitude of carbon and oxygen isotope fractionations under martian surface conditions. The Thermal Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander included a magnetic sector mass spectrometer (EGA) which had the goal of measuring the isotopic composition of martian atmospheric CO2 to within 0.5%. The mass spectrometer is a miniature magnetic sector instrument intended to measure both the martian atmosphere as well as gases evolved from heating martian soils. Ions produced in the ion source are drawn out by a high voltage and focused by a magnetic field onto a set of collector slits. Four specific trajectories are selected to cover the mass ranges, 0.7 - 4, 7 - 35, 14 - 70, and 28 - 140 Da. Using four channels reduces the magnitude of the mass scan and provides simultaneous coverage of the mass ranges. Channel electron multiplier (CEM) detectors that operate in the pulse counting mode detect the ion beams

Thermal and Evolved Gas Behavior of Calcite Under Mars Phoenix TEGA Operating Conditions

The Mars Phoenix Scout Mission with its diverse instrument suite successfully examined several soils on the Northern plains of Mars. The Thermal and Evolved Gas Analyzer (TEGA) was employed to detect organic and inorganic materials by coupling a differential scanning calorimeter (DSC) with a magnetic-sector mass spectrometer (MS). Martian soil was heated up to 1000 C in the DSC ovens and evolved gases from mineral decomposition products were examined with the MS. TEGA s DSC has the capability to detect endothermic and exothermic reactions during heating that are characteristic of minerals present in the Martian soil. Initial TEGA results indicated the presence of endothermic peaks with onset temperatures that ranged from 675 C to 750 C with corresponding CO2 release. This result suggests the presence of calcite (CaCO3. CaO + CO2). Organic combustion to CO2 is not likely since this mostly occurs at temperatures below 550 C. Fe-carbonate and Mg-carbonate are not likely because their decomposition temperatures are less than 600 C. TEGA enthalpy determinations suggest that calcite, may occur in the Martian soil in concentrations of approx.1 to 5 wt. %. The detection of calcite could be questioned based on previous results that suggest Mars soils are mostly acidic. However, the Phoenix landing site soil pH was measured at pH 8.3 0.5, which is typical of terrestrial soils where pH is controlled by calcite solubility. The range of onset temperatures and calcite concentration as calculated by TEGA is poorly con-strained in part because of limited thermal data of cal-cite at reduced pressures. TEGA operates at <30 mbar while most calcite literature thermal data was obtained at 1000 mbar or higher pressures

Thermal and Evolved Gas Analysis of Magnesium Perchlorate: Implications for Perchlorates in Soils at the Mars Phoenix Landing Site

Perchlorate salts were discovered in the soils around the Phoenix landing site on the northern plains of Mars [1]. Perchlorate was detected by an ion selective electrode that is part of the MECA Wet Chemistry Laboratory (WCL). The discovery of a mass 32 fragment (likely 02) by the Thermal and Evolved-Gas Analyzer (TEGA) provided additional confirmation of a strong oxidizer in the soils around the landing site. The purpose of this paper is to evaluate the thermal and evolved gas behavior of perchlorate salts using TEGA-like laboratory testbed instruments. TEGA ovens were fabricated from high purity Ni. Hence, an additional objective of this paper is to determine the effects that Ni might have on the evolved gas behavior of perchlorate salts

Combustion of Organic Molecules by the Thermal Decomposition of Perchlorate Salts: Implications for Organics at the Mars Phoenix Scout Landing Site

The Mars 2007 Phoenix Scout Mission successfully landed on May 25, 2008 and operated on the northern plains of Mars for 150 sols. The primary mission objective was to study the history of water and evaluate the potential for past and present habitability in Martian arctic ice-rich soil [1]. Phoenix landed near 68 N latitude on polygonal terrain created by ice layers that are a few centimeters under loose soil materials. The Phoenix Mission is assessing the potential for habitability by searching for organic molecules in the ice or icy soils at the landing site. Organic molecules are necessary building blocks for life, although their presence in the ice or soil does not indicate life itself. Phoenix searched for organic molecules by heating soil/ice samples in the Thermal and Evolved-Gas Analyzer (TEGA, [2]). TEGA consists of 8 differential scanning calorimeter (DSC) ovens integrated with a magnetic-sector mass spectrometer with a mass range of 2-140 daltons [2]. Endothermic and exothermic reactions are recorded by the TEGA DSC as samples are heated from ambient to ~1000 C. Evolved gases, including any organic molecules and their fragments, are simultaneously measured by the mass spectrometer during heating. Phoenix TEGA data are still under analysis; however, no organic fragments have been identified to date in the evolved gas analysis (EGA). The MECA Wet Chemistry Lab (WCL) discovered a perchlorate salt in the Phoenix soils and a mass 32 peak evolved between 325 and 625 C for one surface sample dubbed Baby Bear [3]. The mass 32 peak is attributed to evolved O2 generated during the thermal decomposition of the perchlorate salt. Perchlorates are very strong oxidizers when heated, so it is possible that organic fragments evolved in the temperature range of 300-600 C were combusted by the O2 released during the thermal decomposition of the perchlorate salt. The byproduct of the combustion of organic molecules is CO2. There is a prominent release of CO2 between 200-600 C for several of the Phoenix soils analyzed by TEGA. This low temperature release of CO2 might be any combination of 1) desorption of adsorbed CO2, 2) thermal decomposition of Fe- and Mg-carbonates, and 3) combustion of organic molecules [2]

Sulfur Mineralogy at the Mars Phoenix Landing Site

The Mars Phoenix Scout mission landed at the northernmost location (approx.68deg N) of any lander or rover on the martian surface. This paper compares the S mineralogy at the Phoenix landing site with S mineralogy of soils studied by previous Mars landers. S-bearing phases were not directly detected by the payload onboard the Phoenix spacecraft. Our objective is to derive the possible mineralogy of S-bearing phases at the Phoenix landing site based upon Phoenix measurements in combination with orbital measurements, terrestrial analog and Martian meteorite studies, and telescopic observations