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A model for studying the composition and chemical effects of stratospheric aerosols

We developed polynomial expressions for the temperature dependence of the mean binary and water activity coefficients for H2SO4 and HNO3 solutions. These activities were used in an equilibrium model to predict the composition of stratospheric aerosols under a wide range of environmental conditions. For typical concentrations of H2O, H2SO4, HNO3, HCl, HBr, HF, and HOCl in the lower stratosphere, the aerosol composition is estimated as a function of the local temperature and the ambient relative humidity. For temperatures below 200 K, our results indicate that (1) HNO3 contributes a significant mass fraction to stratospheric aerosols, and (2) HCl solubility is considerably affected by HNO3 dissolution into sulfate aerosols. We also show that, in volcanically disturbed periods, changes in stratospheric aerosol composition can significantly alter the microphysics that leads to the formation of polar stratospheric clouds. The effects caused by HNO3 dissolution on the physical and chemical properties of stratospheric aerosols are discussed.

Tabazadeh, Azadeh↗

Supersaturated Electrolyte Solutions: Theory and Experiment

Highly supersaturated electrolyte solutions can be prepared and studied employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. In the approach suggested the metastable state for electrolyte solutions is described in terms of the conserved order parameter omega(r,t) associated with fluctuations of the mean solute concentration n(sub 0). Parameters of the corresponding Ginzburg-Landau free energy functional which defines the dynamics of metastable state relaxation are determined and expressed through the experimentally measured quantities. A correspondence of 96-99 % between theory and experiment for all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin), and its calculation for various electrolyte solutions at 298 K. The assumption that subcritical solute clusters consist of the electrically neutral Bjerrum pairs has allowed both analytical and numerical investigation of the number-size N(sub c) of nucleation monomers (aggregates of the Bjerrum pairs) which are elementary units of the solute critical clusters. This has also allowed estimations for the surface tension Alpha, and equilibrium bulk energy Beta per solute molecule in the nucleation monomers. The dependence of these properties on the temperature T and on the solute concentration n(sub 0) through the entire metastable zone (from saturation concentration n(sub sat) to spinodal n(sub spin) is examined. It has been demonstrated that there are the following asymptotics: N(sub c), = I at spinodal concentration and N(sub c) = infinity at saturation.

Izmailov, Alexander F.↗

Thermodynamic Studies of Levitated Microdroplets of Highly Supersaturated Electrolyte Solutions

Highly supersaturated electrolyte solutions are studied by employing an electrodynamic levitator trap (ELT) technique. The ELT technique involves containerless suspension of a microdroplet thus eliminating dust, dirt, and container walls which normally cause heterogeneous nucleation. This allows very high supersaturations to be achieved. A theoretical study of the experimental results obtained for the water activity in microdroplets of various electrolyte solutions is based on the development of the Cahn-Hilliard formalism for electrolyte solutions. A correspondence of 96-99% between the theory and experiment for the all solutions studied was achieved and allowed the determination of an analytical expression for the spinodal concentration n(sub spin) and its calculation for various electrolyte solutions at 298 K.

Myerson, Allan S.↗

A New Parameterization of H2SO4/H2O Aerosol Composition: Atmospheric Implications

Recent results from a thermodynamic model of aqueous sulfuric acid are used to derive a new parameterization for the variation of sulfuric acid aerosol composition with temperature and relative humidity. This formulation is valid for relative humidities above 1 % in the temperature range of 185 to 260 K. An expression for calculating the vapor pressure of supercooled liquid water, consistent with the sulfuric acid model, is also presented. We show that the Steele and Hamill [1981] formulation underestimates the water partial pressure over aqueous H2SOI solutions by up to 12% at low temperatures. This difference results in a corresponding underestimate of the H2SO4 concentration in the aerosol by about 6 % of the weight percent at approximately 190 K. In addition, the relation commonly used for estimating the vapor pressure of H2O over supercooled liquid water differs by up to 10 % from our derived expression. The combined error can result in a 20 % underestimation of water activity over a H2SO4 solution droplet in the stratosphere, which has implications for the parameterization of heterogeneous reaction rates in stratospheric sulfuric acid aerosols. The influence of aerosol composition on the rate of homogeneous ice nucleation from a H2SO4 solution droplet is also discussed. This parameterization can also be used for homogeneous gas phase nucleation calculations of H2SO4 solution droplets under various environmental conditions such as in aircraft exhaust or in volcanic plumes.

Tabazadeh, Azadeh↗

The Hypothesis of Caves on Mars Revisited Through MGS Data; Their Potential as Targets for the Surveyor Program

In a previous publication, we proposed the formation of caves at mega and microscale on Mars and emphasized their potential for the exobiology exploration. The recent MOC images have shown promising indicators that caves are actually existing on Mars. In the first section, we develop the theoretical potential formation of martian caves. Then, we show how MOC is supporting this hypothesis of their formation and the new types of environments it suggests. The existence of caves on Mars from microscale to microscale structures can be predicted according to the Mars geological and climatic history. A first global approach is to consider caves as a result of underground water activity combined with tectonic movement. They can be formed by: (1) diversion of channel courses in underground conduits; (2) fractures of surface drainage patterns; chaotic terrain and collapsed areas in general; (4) seepage face in valley walls and/or headwaters; (5) inactive hydrothermal vents and lava tubes.

Grin, E. A.↗

1999 Marsokhod Field Experiment: A Simulation of a Mars Rover Science Mission

A field experiment to simulate a rover mission to Mars was performed in February 1999. This experiment, the latest in a series of rover field experiments, was designed to demonstrate and validate technologies and investigation strategies for high-science, high-technology performance, and cost-effective planetary rover operations. Objectives: The experiment objectives were to: (1) train scientists in a mission configuration relevant to Surveyor program rover missions at a terrestrial analog field site simulating the criteria of high-priority candidate landing-sites on Mars; (2) develop optimal exploration strategies; (3) evaluate the effectiveness of imaging and spectroscopy in addressing science objectives; (4) assess the value and limitation of descent imaging in supporting rover operations; and (5) evaluate the ability of a science team to correctly interpret the geology of the field site using rover observations. A field site in the California Mojave Desert was chosen for its relevance to the criteria for landing site selection for the Mars Surveyor program. These criteria are: (1) evidence of past water activity; (2) presence of a mechanism to concentrate life; (3) presence of thermal energy sources; (4) evidence of rapid burial; and (5) excavation mechanisms that could expose traces of life.

Stoker, C.↗

Deep Basalt Aquifers in Orcus Patera, Elysium Basin Mars: Perspectives for Exobiology Exploration

Direct indicators of shorelines, spillways, and terraces allowed to determine the extent of the Elysium Paleolake between the contour-lines 1000 and 500 m below the Martian datum. The Elysium Paleolake is bordered north by Orcus Patera (14N/181W), which lies west of the Tartarus Montes and Tartarus Colles. The Orcus Patera displays an ellipse-shaped collapsed caldera of 360-km long and 100-km wide. Viking topographic data show that the bottom of the caldera is located at 2500 below the Martian datum, and surrounded by a steep-walled ram art which crest is located at about 0 m elevation. Considering the localization of Orcus Patera in the Elysium paleolake, its altimetry, and the magmatic origin of this caldera, we propose the existence of a paleolake in Orcus Patera generated (a) by juvenile water from magma during the Noachian period, and (b) by intermittent influx of the Elysium Basin from Hesperian to Amazonian. Results are encouraging to consider this site as a potential high-energy source environment for microbial communities. are circumscribed by a 50-km wide lava field mapped as Noachian material. The structure of Orcus Patera represents the record of material erupted from a magmatic reservoir. The caldera is enclosed by steep inner walls (25% measured from topographic data), values which could be in agreement with the presence of a deep magmatic reservoir, as suggested by the typology of Crumpler et.al. The depth of the caldera might be due to the collapse of the magma reservoir, and the release of gases accompanying the magma thermal evolution. Origins of water for the paleolake(s): The water that generated a paleolake in Orcus Patera may have come from two origins: (1) Juvenile water: Plescia and Crips estimated a magma H20 content by weight between 0.5% and 1.5% using for the first value a comparison with terrestrial basalt, and for the second values from a Martian meteorite. The amount of H20 can be estimated by the volume of erupted lava, and the lava content of the caldera. In this study, we adopt a water content of 1%. The total volume of magma that has been contained in the caldera, and the volume of lava contained in the observed lava field is about 110 x 10(exp 6) cubic km, that gives a total volume of 1.10 x 10(exp 6) cubic km of water. The juvenile water expelled by the overpressure within the magma chamber charged with desolved water-vapor may have moved into the crust. The decrease in overburden pressure led to bubble formation. The ascent of these bubbles generated a pressurization of the magma, which was sufficient to fracture the overlaying magma layer, (2) Water from Elysium paleolake. During the Amazonian, the rise of the Elysium paleolake level generated an overspilling that supplied the caldera with water. The southern portion of the crest shows a deep gap 12-km wide at -1500 m elevation, locating the gap between 500 to 1000 in below the assumed water of Elysium paleolake, thus facilitating the influx of Elysium paleolake water into Orcus Patera. Bathymetric calculations give a floor area of 25,500 sq km at -2000 m elevation, and a water volume of 42,000 cubic km, with a lake-level at -1500 m. A substantial amount of water may have percolated through the fractured lava, and part of the volume may have overspilled the northern crest of Orcus Patera to debouch in the Tartarus Montes region. We envision the formation of a subsurface aqueous environment in basaltic rocks at the contact of the two water-source origins, possibly the percolating surface lake water, and more likely the juvenile water. Similarly to terrestrial calderas, Orcus Patera might be surrounded by ring-fractures caused by the collapse of the magma chamber that followed the release of gases. These ring-fractures may have been covered later by sedimentation in the caldera (lacustrine, aeolian, and volcanic), and by mass wasting. The detumescence of the magma in the caldera, and the vesiculation of the juvenile water may have operated simultaneously. Comparatively to terrestrial melts, Martian iron-rich melts are denser. This greater density implies greater effusion rates (eight-times terrestrial values), and larger fissuration widths (two-times terrestrial ones). With increasing vesiculation of magma, the bubbles interact with one-another because there are of similar pressure. They make a magma froth at the contact with the caldera surface, and on the walls of the fractures. In the saturated magma, froth, where the volume ratio of gases-to-liquid is about 4:1, the bubbles form a huge surface area of interconnected spaces. Bubbles near the caldera surface disrupt the magma, and fragmentation takes place, which moves downward through the magma column. On Earth, the bubbles are likely to grow between 1 and 50 mm in diameter due to the difference between the magma surface tension, and the bubble supersaturation pressure. The Martian low-pressure at surface level is likely to accelerate the expansion of the bubbles, and increase their final diameter and number, creating more voids in the magma. The strong magma froth with enclosed juvenile water bubbles interconnected with exsolved gas bubbles constitute a potential geothermal environment for geochemical energy production from basalt and water that does not require excessive temperatures. This process can start at +20C. Similar types of environments have been shown on Earth as potential energy sources for microbial metabolism, and could have provided deep aqueous basaltic niches for possible Martian microorganisms, even geologically recently. During the Amazonian, combination of volcanism and water activity still existed on Mars. Moreover, this type of potential niches open ways for investigation of possible oases of extinct or extant life, not only on paleolakes, and surface hydrothermalism spring areas, but also all large systems of fossae, which combine hydrologic and volcanic activities, and which provide an energy source, and an underground shelter to prevent surface UV bombardment. Additional information contained in the original.

Grin, E. A.↗

Definitive Mineralogical Analysis of Martian Rocks and Soil Using the CheMin XRD/XRF Instrument and the USDC Sampler

The search for evidence of extant or extinct life on Mars will initially be a search for evidence of present or past conditions supportive of life (e.g., evidence of water), not for life itself. Definitive evidence of past or present water activity lies in the discovery of: * Hydrated minerals: The "rock type" hosting the hydrated minerals could be igneous, metamorphic, or sedimentary, with only a minor hydrated mineral phase. Therefore, the identification of minor phases is important. * Clastic sediments: Clastic sediments are commonly identified by the fact that they contain minerals of disparate origin that could only have come together as a mechanical mixture. Therefore, the identification of all minerals present in a mixture to ascertain mineralogical source regions is important. * Hydrothermal precipitates and chemical sediments: Some chemical precipitates are uniquely identified only by their structure. For example, Opal A, Opal CT, tridymite, crystobalite, high and low Quartz all have the same composition (SiO2) but different crystal structures indicative of different environments - from hydrothermal hydrothermal formation to low temperature precipitation. Other silica types such as stishovite can provide evidence of shock metamorphism. Therefore, identification of crystal structures and structural polymorphs is important. The elucidation of the nature of the Mars soil will require the identification of mineral components that can unravel its history and the history of the Mars atmosphere.

D F Blake↗

Regional Variability in Convection and Rain Retrievals from the TRMM Microwave Imager (TMI)

Precipitation Radar (PR) on board the TRMM satellite shows that the average height of 30 dBz in convective rain areas of the tropics varies significantly from one region to the other. When the convection is weak this height is shallow and when convection is strong this height extends deeper into the troposphere. The brightness temperature (Tb) measured by the microwave radiometer by itself does not reflect this nature of convection satisfactorily. Radiative transfer simulations of Tbs reveal that this could be due to the variations in the vertical distribution of optically active water and ice hydrometeors and their density, shape, and size. These variations are not coupled uniquely to the strength of the convective updrafts, and as a result the Tbs do not reflect properly the convective strength indicated by PR. Because of this deficiency in the Tbs the rain rate deduced from them differs from that of PR. For this reason, to improve the estimation of rain rate we have developed an empirical method. In this method a parameter based on the areal extent of the Tbs that exceed a certain magnitude is included along with the Tbs. Rain rate deduced with this approach is better correlated with that of PR when compared to the current Version 5 operational algorithm. The percentage of rain volume as a function of rain rate, for a given region of 5deg lat. X 5deg long. over a period of three months, deduced from this method, is also in better agreement with that of the PR.

Prabhakara, C.↗

Geochemical and Mineralogical Indicators for Aqueous Processes on the West Spur of the Columbia Hills in Gusev Crater

The primary objective of the MER Spirit and Opportunity Rovers is to identify and investigate rocks, outcrops, and soils that have the highest possible chance of preserving evidence of water activity on Mars. The Athena Science Instrument Payload onboard the two rovers has provided geochemical and mineralogical information that indicates a variety of aqueous processes and various degrees of alteration at the two landing sites.

Ming, D. W.↗

MAPGEN : mixed initiative planning and scheduling for the Mars '03 MER mission

The Mars Exploration Rovers Mars '03 mission is one of NASA's most ambitious science missions to date. The rovers will be launched in the summer of 2003 with each rover carrying instruments to conduct remote and in-situ observation to elucidate the planet's past climate, water activity, and habitability. Science is the primary driver of MER and, as a consequence, making best use of the scientific instruments, within the available resources, is a crucial aspect of the mission. To address this critically, the MER project has selected MAPGEN (Mixed-Initiative Activity Plan GENerator) as an activity planning tool. MAPGEN combines two exiting systems, each with a strong heritage: APGEN the Activity Planning tool from the Jet Propulsion Laboratory and the Europs Planning/Scheduling system from NASA Ames Research Center. This paper discusses the issues arising from combining these tools in the context of this mission.

planning and scheduling↗

An Energetic Concept of Habitability for the Deep Subsurface

Universally, life must be characterized by a characteristic level of order and complexity. In the most general sense, habitability could then be defined as the set of factors required to allow the creation and maintenance of molecular complexity. These factors are: chemical raw materials; energy with which to assemble those materials into complex molecules and sustain the resultant state of complexity; a solvent that allows the interaction of complex molecules, promotes tertiary structure, and permits compartmentalization; and environmental conditions that permit the assembly and maintenance of complex molecules. On Earth, these general requirements correspond to the major biogenic elements C, H, O, N, P, S; chemical or light energy; the solvent water; and specific ranges of temperature, pH, radiation, ionic strength, and so forth, which have thus far been determined on and exclusively empirical basis. Importantly, while the complete absence of any of these factors ensures uninhabitable conditions, the mere presence of all four does not guarantee habitability. In each case - even that of water - it is a question of degree. This question can be couched in quantitative terms by considering the impact of each of these factors on cellular energy balance. More "extreme" conditions (e.g., high temperature, high or low pH, etc.), lower water activity, and low concentrations of nutrients incur or have potential to be addressed by increased investment of energy on the part of the cell. This must be balanced by energy conservation in the cell, noting that biochemical, mass transport, and abiotic chemical limitations intervene between environmental energy availability and biological energy capture. Similarly, lower boundary conditions are emplaced on useful environmental energy yields by the "quantized" nature of biological energy conservation, and upper boundary conditions are emplaced by energy levels or fluxes that are destructive with respect to complexity. This energetic framework, with boundary conditions supplied by the specifics of the biochemistry in question, offers a generalized, yet quantitative means of assessing the habitability of any system with respect to complex life.

Hoehler, Tori M.↗

The MER Mossbauer Spectrometers: 40 Months of Operation on the Martian Surface

The primary MER objectives have been successfully completed. The total integration time of all MB measurements exceeds the duration of the primary 90-sols-mission for Spirit's MB spectrometer, and approaches this value for Opportunity's MB spectrometer. Both MB spectrometers continue to accumulate valuable scientific data after three years of operation (data is available for download [13]) The identification of aqueous minerals such as goethite in Gusev crater and jarosite at Meridiani Planum by the MER Mossbauer spectrometers is strong evidence for past water activity at the two landing sites.

Fleischer, Iris↗

NEXT Ion Propulsion System Configurations and Performance for Saturn System Exploration

The successes of the Cassini/Huygens mission have heightened interest to return to the Saturn system with focused robotic missions. The desire for a sustained presence at Titan, through a dedicated orbiter and in-situ vehicle, either a lander or aerobot, has resulted in definition of a Titan Explorer flagship mission as a high priority in the Solar System Exploration Roadmap. The discovery of active water vapor plumes erupting from the tiger stripes on the moon Enceladus has drawn the attention of the space science community. The NASA's Evolutionary Xenon Thruster (NEXT) ion propulsion system is well suited to future missions to the Saturn system. NEXT is used within the inner solar system, in combination with a Venus or Earth gravity assist, to establish a fast transfer to the Saturn system. The NEXT system elements are accommodated in a separable Solar Electric Propulsion (SEP) module, or are integrated into the main spacecraft bus, depending on the mission architecture and performance requirements. This paper defines a range of NEXT system configurations, from two to four thrusters, and the Saturn system performance capability provided. Delivered mass is assessed parametrically over total trip time to Saturn. Launch vehicle options, gravity assist options, and input power level are addressed to determine performance sensitivities. A simple two-thruster NEXT system, launched on an Atlas 551, can deliver a spacecraft mass of over 2400 kg on a transfer to Saturn. Similarly, a four-thruster system, launched on a Delta 4050 Heavy, delivers more than 4000 kg spacecraft mass. A SEP module conceptual design, for a two thruster string, 17 kW solar array, configuration is characterized.

Benson, Scott W.↗

The Miniaturized Moessbauer Spectrometers MIMOS II on MER: Four Years of Operation - A Summary

The two Miniaturized Moessbauer Spectrometers (MIMOS II) on board the two Mars Exploration Rovers Spirit and Opportunity have now been collecting important scientific data for more than four years. The spectrometers provide information about Fe-bearing mineral phases and determine Fe oxidation states. The total amount of targets analized exceeds 600, the total integration time exceeds 260 days for both rovers. Since landing, more than five half-lives of the Co-57 MB sources have past (intensity at the time of landing approx. 150 mCi). Current integration times are about 50 hours in order to achieve reasonable statistics as opposed to 8 hours at the beginning of the mission. In total, 13 different mineral phases were detected: Olivine, pyroxene, hematite, magnetite and nanophase ferric oxide were detected at both landing sites. At Gusev, ilmenite, goethite, a ferric sulfate phase and a yet unassigned phase (in the rock Fuzzy Smith) were detected. At Meridiani, jarosite, metallic iron in meteoritic samples (kamacite), troilite, and an unassigned ferric phase were detected. Jarosite and goethite are of special interest, as these minerals are indicators for water activity. In this abstract, an overview of Moessbauer results will be given, with a focus on data obtained since the last martian winter. The MER mission has proven that Moessbauer spectroscopy is a valuable tool for the in situ exploration of extraterrestrial bodies and for the study of Febearing samples. The experience gained through the MER mission makes MIMOS II a obvious choice for future missions to Mars and other targets. Currently, MIMOS II is on the scientific payload of two approved future missions: Phobos Grunt (Russian Space Agency; 2009) and ExoMars (European Space Agency; 2013).

Fleischer, I.↗

The Science from Spirit and Opportunity

This slide presentation shows views from the Mars rovers, Spirit and Opportunity. Included are views of the takeoff, and descent on to Mars. The science objective of these missions are to determine the water, climate, and geologic history of two sites on Mars where evidence has been preserved for past and persistent liquid water activity that may have supported biotic or pre-biotic processes. There are also shots of the Athena Science Payload with views of the instrumentation. Also presented are graphs showing Mossbauer Spectra of varions martian rocks.

Spirit↗

Thermal Infrared Emission Spectroscopy of Synthetic Allophane and its Potential Formation on Mars

Allophane is a poorly-crystalline, hydrous aluminosilicate with variable Si/Al ratios approx.0.5-1 and a metastable precursor of clay minerals. On Earth, it forms rapidly by aqueous alteration of volcanic glass under neutral to slightly acidic conditions [1]. Based on in situ chemical measurements and the identification of alteration phases [2-4], the Martian surface is interpreted to have been chemically weathered on local to regional scales. Chemical models of altered surfaces detected by the Mars Exploration Rover Spirit in Gusev crater suggest the presence of an allophane-like alteration product [3]. Thermal infrared (TIR) spectroscopy and spectral deconvolution models are primary tools for determining the mineralogy of the Martian surface [5]. Spectral models of data from the Thermal Emission Spectrometer (TES) indicate a global compositional dichotomy, where high latitudes tend to be enriched in a high-silica material [6,7], interpreted as high-silica, K-rich volcanic glass [6,8]. However, later interpretations proposed that the high-silica material may be an alteration product (such as amorphous silica, clay minerals, or allophane) and that high latitude surfaces are chemically weathered [9-11]. A TIR spectral library of pure minerals is available for the public [12], but it does not contain allophane spectra. The identification of allophane on the Martian surface would indicate high water activity at the time of its formation and would help constrain the aqueous alteration environment [13,14]. The addition of allophane to the spectral library is necessary to address the global compositional dichotomy. In this study, we characterize a synthetic allophane by IR spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy (TEM) to create an IR emission spectrum of pure allophane for the Mars science community to use in Martian spectral models.

Rampe, E. B.↗