John H. Hoffman

Detection of Perchlorate and the Soluble Chemistry of Martian Soil at the Phoenix Lander Site

Phoenix Ascending The Phoenix mission landed on Mars in March 2008 with the goal of studying the ice-rich soil of the planets northern arctic region. Phoenix included a robotic arm, with a camera attached to it, with the capacity to excavate through the soil to the ice layer beneath it, scoop up soil and water ice samples, and deliver them to a combination of other instruments—including a wet chemistry lab and a high-temperature oven combined with a mass spectrometer—for chemical and geological analysis. Using this setup, Smith et al. (p. 58) found a layer of ice at depths of 5 to 15 centimeters, Boynton et al. (p. 61) found evidence for the presence of calcium carbonate in the soil, and Hecht et al. (p. 64) found that most of the soluble chlorine at the surface is in the form of perchlorate. Together these results suggest that the soil at the Phoenix landing site must have suffered alteration through the action of liquid water in geologically the recent past. The analysis revealed an alkaline environment, in contrast to that found by the Mars Exploration Rovers, indicating that many different environments have existed on Mars. Phoenix also carried a lidar, an instrument that sends laser light upward into the atmosphere and detects the light scattered back by clouds and dust. An analysis of the data by Whiteway et al. (p. 68) showed that clouds of ice crystals that precipitated back to the surface formed on a daily basis, providing a mechanism to place ice at the surface. Most of the chlorine at the Phoenix landing site is in the form of perchlorate, a salt that is highly soluble in water. The Wet Chemistry Laboratory on the Phoenix Mars Lander performed aqueous chemical analyses of martian soil from the polygon-patterned northern plains of the Vastitas Borealis. The solutions contained ~10 mM of dissolved salts with 0.4 to 0.6% perchlorate (ClO4) by mass leached from each sample. The remaining anions included small concentrations of chloride, bicarbonate, and possibly sulfate. Cations were dominated by Mg2+ and Na+, with small contributions from K+ and Ca2+. A moderately alkaline pH of 7.7 ± 0.5 was measured, consistent with a carbonate-buffered solution. Samples analyzed from the surface and the excavated boundary of the ~5-centimeter-deep ice table showed no significant difference in soluble chemistry.

H2O at the Phoenix Landing Site

Phoenix Ascending The Phoenix mission landed on Mars in March 2008 with the goal of studying the ice-rich soil of the planets northern arctic region. Phoenix included a robotic arm, with a camera attached to it, with the capacity to excavate through the soil to the ice layer beneath it, scoop up soil and water ice samples, and deliver them to a combination of other instruments—including a wet chemistry lab and a high-temperature oven combined with a mass spectrometer—for chemical and geological analysis. Using this setup, Smith et al. (p. 58) found a layer of ice at depths of 5 to 15 centimeters, Boynton et al. (p. 61) found evidence for the presence of calcium carbonate in the soil, and Hecht et al. (p. 64) found that most of the soluble chlorine at the surface is in the form of perchlorate. Together these results suggest that the soil at the Phoenix landing site must have suffered alteration through the action of liquid water in geologically the recent past. The analysis revealed an alkaline environment, in contrast to that found by the Mars Exploration Rovers, indicating that many different environments have existed on Mars. Phoenix also carried a lidar, an instrument that sends laser light upward into the atmosphere and detects the light scattered back by clouds and dust. An analysis of the data by Whiteway et al. (p. 68) showed that clouds of ice crystals that precipitated back to the surface formed on a daily basis, providing a mechanism to place ice at the surface. A water ice layer was found 5 to 15 centimeters beneath the soil of the north polar region of Mars. The Phoenix mission investigated patterned ground and weather in the northern arctic region of Mars for 5 months starting 25 May 2008 (solar longitude between 76.5° and 148°). A shallow ice table was uncovered by the robotic arm in the center and edge of a nearby polygon at depths of 5 to 18 centimeters. In late summer, snowfall and frost blanketed the surface at night; H2O ice and vapor constantly interacted with the soil. The soil was alkaline (pH = 7.7) and contained CaCO3, aqueous minerals, and salts up to several weight percent in the indurated surface soil. Their formation likely required the presence of water.

Evidence for Calcium Carbonate at the Mars Phoenix Landing Site

Phoenix Ascending The Phoenix mission landed on Mars in March 2008 with the goal of studying the ice-rich soil of the planets northern arctic region. Phoenix included a robotic arm, with a camera attached to it, with the capacity to excavate through the soil to the ice layer beneath it, scoop up soil and water ice samples, and deliver them to a combination of other instruments—including a wet chemistry lab and a high-temperature oven combined with a mass spectrometer—for chemical and geological analysis. Using this setup, Smith et al. (p. 58) found a layer of ice at depths of 5 to 15 centimeters, Boynton et al. (p. 61) found evidence for the presence of calcium carbonate in the soil, and Hecht et al. (p. 64) found that most of the soluble chlorine at the surface is in the form of perchlorate. Together these results suggest that the soil at the Phoenix landing site must have suffered alteration through the action of liquid water in geologically the recent past. The analysis revealed an alkaline environment, in contrast to that found by the Mars Exploration Rovers, indicating that many different environments have existed on Mars. Phoenix also carried a lidar, an instrument that sends laser light upward into the atmosphere and detects the light scattered back by clouds and dust. An analysis of the data by Whiteway et al. (p. 68) showed that clouds of ice crystals that precipitated back to the surface formed on a daily basis, providing a mechanism to place ice at the surface. The action of liquid water may have helped to form the calcium carbonate found in the soils around the Phoenix landing site. Carbonates are generally products of aqueous processes and may hold important clues about the history of liquid water on the surface of Mars. Calcium carbonate (approximately 3 to 5 weight percent) has been identified in the soils around the Phoenix landing site by scanning calorimetry showing an endothermic transition beginning around 725°C accompanied by evolution of carbon dioxide and by the ability of the soil to buffer pH against acid addition. Based on empirical kinetics, the amount of calcium carbonate is most consistent with formation in the past by the interaction of atmospheric carbon dioxide with liquid water films on particle surfaces.

Composition and Structure of the Venus Atmosphere: Results from Pioneer Venus

Results from the Pioneer Venus sounder probe neutral mass spectrometer indicate that there is no difference in the isotopic ratios of carbon and oxygen between Venus and Earth to within � 5 percent. The mixing ratio of nitrogen is 3.5+3-2 percent with an isotopic ratio within 20 percent of that of Earth. The ratio of argon-36 to argon-40 is 85 percent, and the ratio of argon-38 to argon-36 is 20 percent. The mixing ratios of argon-36 and argon-40 are approximately 40 and 50 parts per million, respectively, with an error of about a factor of 2 (mainly toward a lesser amount) resulting from uncertainty in the response of the ion pump to rare gases. Hydrogen chloride cannot account for more than a few percent of the 36 mass peak, and therefore the large excess of primordial argon is a reasonable conclusion. The ratio of neon-20 to argon-36 of 0.5 � 0.3 is definitely terrestrial in character rather than solar. These results indicate that there is a large excess of all primordial noble gases on Venus relative to Earth. There appears to be a considerably higher abundance of sulfur compounds below 20 kilometers than in or above the main cloud layer. The 32 and 60 mass peaks show a sharp increase below 22 kilometers, indicating the possible production of sulfur and carbon oxysulfide (COS) at the expense of sulfur dioxide.

Studies of the composition of the ionosphere with a magnetic deflection mass spectrometer

Abstract Small magnetic sector-field mass spectrometers have been flown on the Explorer XXXI Satellite and on several rockets to study the composition of the earths ionosphere. When calibrated in-flight these instruments measure absolute ion concentrations. Data at 500 km (Explorer XXXI perigee) show 10 different ion species in the 1 to 20 amu mass range with O + dominant. At 3000 km (apogee) H + is dominant and O + is not observed at mid to low latitudes. However in the polar regions, O + may become dominant and H + ions are found to be streaming outward with velocities of 10 to 15 km/sec. These ions constitute the polar wind.

Phoenix mars mission—The thermal evolved gas analyzer

The Phoenix spacecraft that was launched to Mars in August 2007 landed safely on the Martian northern arctic region on May 25, 2008. It carried six experiments to study the history of water on the planet and search for organic molecules in the icy subsurface Martian soil. The spacecraft is a lander with an arm and scoop designed to dig a trench though the top soil to reach an expected ice layer near the surface. One of the instruments on board is the thermal evolved gas analyzer (TEGA), which consists of two components, a set of eight very small ovens that will heat samples of the ice soil mixtures from the trench to release imbedded gases and mineral decomposition products, and a mass spectrometer that serves as the analysis tool for the evolved gases, and also for measurements of the composition and isotopic ratios of the gases that comprise the atmosphere of Mars. The mass spectrometer is a miniature magnetic sector instrument controlled by microprocessor-driven power supplies. One feature is the gas enrichment cell that will increase the partial pressures of the noble gases in an atmosphere sample by removing all the active gases, carbon dioxide, and nitrogen, to improve the accuracy of their isotopic ratio measurements.

Stable Isotope Measurements of Martian Atmospheric CO2 at the Phoenix Landing Site

Martian Carbon Dioxide As a primary component of the martian atmosphere and as the primary greenhouse gas for Mars, carbon dioxide has played a role in climate and geological processes during martian history. Niles et al. (p. 1334) present high-precision measurements of the isotopic composition of the martian atmospheric CO2, made in situ by the Mars Phoenix Lander. Atmospheric CO2 on Mars was not enriched in 13C, which implies that volcanic degassing and carbonate formation have been important in the recent past, but it was enriched in 18O, which suggests that low-temperature water-rock interactions have been dominant on Mars. Combined with previous work on martian meteorites, the results suggest that carbonate formation has been active on Mars for the past 200 million years. Mass spectrometric measurements constrain the history of water, volcanism, and climate evolution on Mars. Carbon dioxide is a primary component of the martian atmosphere and reacts readily with water and silicate rocks. Thus, the stable isotopic composition of CO2 can reveal much about the history of volatiles on the planet. The Mars Phoenix spacecraft measurements of carbon isotopes [referenced to the Vienna Pee Dee belemnite (VPDB)] [δ13CVPDB = –2.5 ± 4.3 per mil (‰)] and oxygen isotopes [referenced to the Vienna standard mean ocean water (VSMOW)] (δ18OVSMOW = 31.0 ± 5.7‰), reported here, indicate that CO2 is heavily influenced by modern volcanic degassing and equilibration with liquid water. When combined with data from the martian meteorites, a general model can be constructed that constrains the history of water, volcanism, atmospheric evolution, and weathering on Mars. This suggests that low-temperature water-rock interaction has been dominant throughout martian history, carbonate formation is active and ongoing, and recent volcanic degassing has played a substantial role in the composition of the modern atmosphere.

Venus Lower Atmospheric Composition: Preliminary Results from Pioneer Venus

Initial examination of data from the neutral mass spectrometer on the Pioneer Venus sounder probe indicates that the abundances of argon-36, argon-38, and neon-20 in the Venus atmosphere are much higher than those of the corresponding gases in Earths atmosphere, although the abundance of radiogenic argon-40 is apparently similar for both planets. The lower atmosphere of Venus includes significant concentrations of various gaseous sulfur compounds. The inlet leak to the mass spectrometer was temporarily blocked by an apparently liquid component of the Venus clouds during passage through the dense cloud layer. Analysis of gases released during the evaporation of the droplets shows the presence of water vapor to some compound or compounds of sulfur.

atmospheric helium isotopic ratio

A recent study of the isotopic ratio of helium (3He/4He) in the terrestrial atmosphere led the individuals who made the investigation to suggest that this ratio is decreasing with time, probably due to anthropogenic release of low isotopic ratio crustal helium from oil and gas wells. The measurements made over an 11 year period from 1977 to 1988 led to the prediction that the rate of decrease was of the order of 1 × 10−9/yr. Several absolute isotopic ratio measurements made between 1969 and the present time also have been reported. These show a slight decrease in the helium isotopic ratio (much less than the 11 year data set shows). In the present paper, we report an unpublished, absolute helium isotopic ratio measurement the authors made in 1956. This value, when combined with the previously reported results, extends the time over which such measurements were made to a 32 year period and does not confirm that there is any decrease in the helium isotopic ratio in the atmosphere over this time.

TESSX: A Mission for Space Exploration with Tethers

Tethers offer significant potential for substantially increasing payload mass fraction, increasing spacecraft lifetime, enhancing long-term space travel, and enabling the understanding and development of gravity-dependant technologies required for Moon and Mars exploration. The development of the Tether Electrodynamic Spin-up and Survivability Experiment (TESSX) will support applications relevant to NASAOs new exploration initiative, including: artificial gravity generation, formation flying, electrodynamic propulsion, momentum exchange, and multi-amp current collection and emission. Under the broad term TESSX, we are currently evaluating several different tether system configurations and operational modes. The initial results of this work are presented, including hardware development, orbital dynamics simulations, and electrodynamics design and analysis.