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Description
Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are

Chemical and mineralogical data from Mars shows that the surface has been chemically weathered on local to regional scales. Chemical trends and the types of chemical weathering products present on the surface and their abundances can elucidate information about past aqueous processes. Thermal-infrared (TIR) data and their respective models are essential for interpreting Martian mineralogy and geologic history. However, previous studies have shown that chemical weathering and the precipitation of fine-grained secondary silicates can adversely affect the accuracy of TIR spectral models. Furthermore, spectral libraries used to identify minerals on the Martian surface lack some important weathering products, including poorly-crystalline aluminosilicates like allophane, thus eliminating their identification in TIR spectral models. It is essential to accurately interpret TIR spectral data from chemically weathered surfaces to understand the evolution of aqueous processes on Mars. Laboratory experiments were performed to improve interpretations of TIR data from weathered surfaces. To test the accuracy of deriving chemistry of weathered rocks from TIR spectroscopy, chemistry was derived from TIR models of weathered basalts from Baynton, Australia and compared to actual weathering rind chemistry. To determine how specific secondary silicates affect the TIR spectroscopy of weathered basalts, mixtures of basaltic minerals and small amounts of secondary silicates were modeled. Poorly-crystalline aluminosilicates were synthesized and their TIR spectra were added to spectral libraries. Regional Thermal Emission Spectrometer (TES) data were modeled using libraries containing these poorly-crystalline aluminosilicates to test for their presence on the Mars. Chemistry derived from models of weathered Baynton basalts is not accurate, but broad chemical weathering trends can be interpreted from the data. TIR models of mineral mixtures show that small amounts of crystalline and amorphous silicate weathering products (2.5-5 wt.%) can be detected in TIR models and can adversely affect modeled plagioclase abundances. Poorly-crystalline aluminosilicates are identified in Northern Acidalia, Solis Planum, and Meridiani. Previous studies have suggested that acid sulfate weathering was the dominant surface alteration process for the past 3.5 billion years; however, the identification of allophane indicates that alteration at near-neutral pH occurred on regional scales and that acid sulfate weathering is not the only weathering process on Mars.
ContributorsRampe, Elizabeth Barger (Author) / Sharp, Thomas G (Thesis advisor) / Christensen, Phillip (Committee member) / Hervig, Richard (Committee member) / Shock, Everett (Committee member) / Williams, Lynda (Committee member) / Arizona State University (Publisher)
Created2011
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Description
Lunar Reconnaissance Orbiter (LRO) and MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft missions provide new data for investigating the youngest impact craters on Mercury and the Moon, along with lunar volcanic end-members: ancient silicic and young basaltic volcanism. The LRO Wide Angle Camera (WAC) and Narrow Angle Camera

Lunar Reconnaissance Orbiter (LRO) and MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft missions provide new data for investigating the youngest impact craters on Mercury and the Moon, along with lunar volcanic end-members: ancient silicic and young basaltic volcanism. The LRO Wide Angle Camera (WAC) and Narrow Angle Camera (NAC) in-flight absolute radiometric calibration used ground-based Robotic Lunar Observatory and Hubble Space Telescope data as standards. In-flight radiometric calibration is a small aspect of the entire calibration process but an important improvement upon the pre-flight measurements. Calibrated reflectance data are essential for comparing images from LRO to missions like MESSENGER, thus enabling science through engineering. Relative regolith optical maturation rates on Mercury and the Moon are estimated by comparing young impact crater densities and impact ejecta reflectance, thus empirically testing previous models of faster rates for Mercury relative to the Moon. Regolith maturation due to micrometeorite impacts and solar wind sputtering modies UV-VIS-NIR surface spectra, therefore understanding maturation rates is critical for interpreting remote sensing data from airless bodies. Results determined the regolith optical maturation rate on Mercury is 2 to 4 times faster than on the Moon. The Gruithuisen Domes, three lunar silicic volcanoes, represent relatively rare lunar lithologies possibly similar to rock fragments found in the Apollo sample collection. Lunar nonmare silicic volcanism has implications for lunar magmatic evolution. I estimated a rhyolitic composition using morphologic comparisons of the Gruithuisen Domes, measured from NAC 2-meter-per-pixel digital topographic models (DTMs), with terrestrial silicic dome morphologies and laboratory models of viscoplastic dome growth. Small, morphologically sharp irregular mare patches (IMPs) provide evidence for recent lunar volcanism widely distributed across the nearside lunar maria, which has implications for long-lived nearside magmatism. I identified 75 IMPs (100-5000 meters in dimension) in NAC images and DTMs, and determined stratigraphic relationships between units common to all IMPs. Crater counts give model ages from 18-58 Ma, and morphologic comparisons with young lunar features provided an additional age constraint of <100 Ma. The IMPs formed as low-volume basaltic eruptions significantly later than previous evidence of lunar mare basalt volcanism's end (1-1.2 Ga).
ContributorsBraden, Sarah E (Author) / Robinson, Mark S (Thesis advisor) / Bell, James F. (Committee member) / Christensen, Philip R. (Committee member) / Clarke, Amanda B (Committee member) / Lawrence, Samuel J (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size,

Harsh environments have conditions that make collecting scientific data difficult with existing commercial-off-the-shelf technology. Micro Electro Mechanical Systems (MEMS) technology is ideally suited for harsh environment characterization and operation due to the wide range of materials available and an incredible array of different sensing techniques while providing small device size, low power consumption, and robustness. There were two main objectives of the research conducted. The first objective was to design, fabricate, and test novel sensors that measure the amount of exposure to ionizing radiation for a wide range of applications including characterization of harsh environments. Two types of MEMS ionizing radiation dosimeters were developed. The first sensor was a passive radiation-sensitive capacitor-antenna design. The antenna's emitted frequency of peak-intensity changed as exposure time to radiation increased. The second sensor was a film bulk acoustic-wave resonator, whose resonant frequency decreased with increasing ionizing radiation exposure time. The second objective was to develop MEMS sensor systems that could be deployed to gather scientific data and to use that data to address the following research question: do temperature and/or conductivity predict the appearance of photosynthetic organisms in hot springs. To this end, temperature and electrical conductivity sensor arrays were designed and fabricated based on mature MEMS technology. Electronic circuits and the software interface to the electronics were developed for field data collection. The sensor arrays utilized in the hot springs yielded results that support the hypothesis that temperature plays a key role in determining where the photosynthetic organisms occur. Additionally, a cold-film fluidic flow sensor was developed, which is suitable for near-boiling temperature measurement. Future research should focus on (1) developing a MEMS pH sensor array with integrated temperature, conductivity, and flow sensors to provide multi-dimensional data for scientific study and (2) finding solutions to biofouling and self-calibration, which affects sensor performance over long-term deployment.
ContributorsOiler, Jonathon (Author) / Yu, Hongyu (Thesis advisor) / Anbar, Ariel (Committee member) / Hartnett, Hilairy (Committee member) / Scannapieco, Evan (Committee member) / Timmes, Francis (Committee member) / Arizona State University (Publisher)
Created2013
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Description
Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients,

Biological soil crusts (BSCs) are critical components of arid and semiarid environments and provide the primary sources of bioavailable macronutrients and increase micronutrient availability to their surrounding ecosystems. BSCs are composed of a variety of microorganisms that perform a wide range of physiological processes requiring a multitude of bioessential micronutrients, such as iron, copper, and molybdenum. This work investigated the effects of BSC activity on soil solution concentrations of bioessential elements and examined the microbial production of organic chelators, called siderophores. I found that aluminum, vanadium, copper, zinc, and molybdenum were solubilized in the action of crusts, while nickel, zinc, arsenic, and zirconium were immobilized by crust activity. Potassium and manganese displayed behavior consistent with biological removal and mobilization, whereas phosphorus and iron solubility were dominated by abiotic processes. The addition of bioavailable nitrogen altered the effects of BSCs on soil element mobilization. In addition, I found that the biogeochemical activites of BSCs were limited by molybdenum, a fact that likely contributes to co-limitation by nitrogen. I confirmed the presence of siderophore producing microbes in BSCs. Siderophores are low-molecular weight organic compounds that are released by bacteria to increase element solubility and facilitate element uptake; siderophore production is likely the mechanism by which BSCs affect the patterns I observed in soil solution element concentrations. Siderophore producers were distributed across a range of bacterial groups and ecological niches within crusts, suggesting that siderophore production influences the availability of a variety of elements for use in many physiological processes. Four putative siderophore compounds were identified using electrospray ionization mass spectrometry; further attempts to characterize the compounds confirmed two true siderophores. Taken together, the results of my work provide information about micronutrient cycling within crusts that can be applied to BSC conservation and management. Fertilization with certain elements, particularly molybdenum, may prove to be a useful technique to promote BSC growth and development which would help prevent arid land degradation. Furthermore, understanding the effects of BSCs on soil element mobility could be used to develop useful biomarkers for the study of the existence and distribution of crust-like communities on ancient Earth, and perhaps other places, like Mars.
ContributorsNoonan, Kathryn Alexander (Author) / Hartnett, Hilairy (Thesis advisor) / Anbar, Ariel (Committee member) / Garcia-Pichel, Ferran (Committee member) / Shock, Everett (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Early spacecraft missions to Mars, including the Marnier and Viking orbiters and landers revealed a morphologically and compositionally diverse landscape that reshaped widely held views of Mars. More recent spacecraft including Mars Global Surveyor, Mars Odyssey, Mars Express, Mars Reconnaissance Orbiter, and the Mars Exploration Rovers have further refined, enhanced,

Early spacecraft missions to Mars, including the Marnier and Viking orbiters and landers revealed a morphologically and compositionally diverse landscape that reshaped widely held views of Mars. More recent spacecraft including Mars Global Surveyor, Mars Odyssey, Mars Express, Mars Reconnaissance Orbiter, and the Mars Exploration Rovers have further refined, enhanced, and diversified our understanding of Mars. In this dissertation, I take a multiple-path approach to planetary and Mars science including data analysis and instrument development. First, I present several tools necessary to effectively use new, complex datasets by highlighting unique and innovative data processing techniques that allow for the regional to global scale comparison of multiple datasets. Second, I present three studies that characterize several processes on early Mars, where I identify a regional, compositionally distinct, in situ, stratigraphically significant layer in Ganges and Eos Chasmata that formed early in martian history. This layer represents a unique period in martian history where primitive mantle materials were emplaced over large sections of the martian surface. While I originally characterized this layer as an effusive lava flow, based on the newly identified regional or global extent of this layer, I find the only likely scenario for its emplacement is the ejecta deposit of the Borealis Basin forming impact event. I also re-examine high thermal inertia, flat-floored craters identified in Viking data and conclude they are typically more mafic than the surrounding plains and were likely infilled by primitive volcanic materials during, or shortly after the Late Heavy Bombardment. Furthermore, the only plausible source for these magmas is directly related to the impact process, where mantle decompression melting occurs as result of the removal of overlying material by the impactor. Finally, I developed a new laboratory microscopic emission and reflectance spectrometer designed to help improve the interpretation of current remote sensing or in situ data from planetary bodies. I present the design, implementation, calibration, system performance, and preliminary results of this instrument. This instrument is a strong candidate for the next generation in situ rover instruments designed to definitively assess sample mineralogy and petrology while preserving geologic context.
ContributorsEdwards, Christopher (Author) / Christensen, Philip R. (Thesis advisor) / Bell, James (Committee member) / Sharp, Thomas (Committee member) / Clarke, Amanda B (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from

Lithium (Li) is a trace element in kerogen, but the content and isotopic distribution (δ7Li) in kerogen has not previously been quantified. Furthermore, kerogen has been overlooked as a potential source of Li to sedimentary porefluids and buried sediments. Thus, knowing the content and isotopic composition of Li derived from kerogen may have implications for research focused on the Li-isotopes of buried sediments (e.g., evaluating paleoclimate variations using marine carbonates).The objective of this work is to better understand the role of kerogen in the Li geochemical cycle. The research approach consisted of 1) developing reference materials and methodologies to measure the Li-contents and δ7Li of kerogen in-situ by Secondary Ion Mass Spectrometry, 2) surveying the Li-contents and δ7Li of kerogen bearing rocks from different depositional and diagenetic environments and 3) quantifying the Li-content and δ7Li variations in kerogen empirically in a field study and 4) experimentally through hydrous pyrolysis. A survey of δ7Li of coals from depositional basins across the USA showed that thermally immature coals have light δ7Li values (–20 to – 10‰) compared to typical terrestrial materials (> –10‰) and the δ7Li of coal increases with burial temperature suggesting that 6Li is preferentially released from kerogen to porefluids during hydrocarbon generation. A field study was conducted on two Cretaceous coal seams in Colorado (USA) intruded by dikes (mafic and felsic) creating a temperature gradient from the intrusives into the country rock. Results showed that δ7Li values of the unmetamorphosed vitrinite macerals were up to 37‰ lighter than vitrinite macerals and coke within the contact metamorphosed coal. To understand the significance of Li derived from kerogen during burial diagenesis, hydrous pyrolysis experiments of three coals were conducted. Results showed that Li is released from kerogen during hydrocarbon generation and could increase sedimentary porefluid Li-contents up to ~100 mg/L. The δ7Li of coals becomes heavier with increased temperature except where authigenic silicates may compete for the released Li. These results indicate that kerogen is a significant source of isotopically light Li to diagenetic fluids and is an important contributor to the global geochemical cycle.
ContributorsTeichert, Zebadiah (Author) / Williams, Lynda B. (Thesis advisor) / Bose, Maitrayee (Thesis advisor) / Hervig, Richard (Committee member) / Semken, Steven (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2022
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Description
The seasonal deposition of CO2 on the polar caps is one of the most dynamic processes on Mars and is a dominant driver of the global climate. Remote sensing temperature and albedo data were used to estimate the subliming mass of CO2 ice on south polar gullies near Sisyphi Cavi.

The seasonal deposition of CO2 on the polar caps is one of the most dynamic processes on Mars and is a dominant driver of the global climate. Remote sensing temperature and albedo data were used to estimate the subliming mass of CO2 ice on south polar gullies near Sisyphi Cavi. Results showed that column mass abundances range from 400 - 1000 kg.m2 in an area less than 60 km2 in late winter. Complete sublimation of the seasonal caps may occur later than estimated by large-scale studies and is geographically dependent. Seasonal ice depth estimates suggested variations of up to 1.5 m in depth or 75% in porosity at any one time. Interannual variations in these data appeared to correlate with dust activity in the southern hemisphere. Correlation coefficients were used to investigate the relationship between frost-free surface properties and the evolution of the seasonal ice in this region. Ice on high thermal inertia units was found to disappear before any other ice, likely caused by inhibited deposition during fall. Seasonal ice springtime albedo appeared to be predominantly controlled by orientation, with north-facing slopes undergoing brightening initially in spring, then subliming before south-facing slopes. Overall, the state of seasonal ice is far more complex than globally and regionally averaged studies can identify.

The discovery of cryovolcanic features on Charon and the presence of ammonia hydrates on the surfaces of other medium-sized Kuiper Belt Objects suggests that cryovolcanism may be important to their evolution. A two-dimensional, center-point finite difference, thermal hydraulic model was developed to explore the behavior of cryovolcanic conduits on midsized KBOs. Conduits on a Charon-surrogate were shown to maintain flow through over 200 km of crust and mantle down to radii of R = 0.20 m. Radii higher than this became turbulent due to high viscous dissipation and low thermal conductivity. This model was adapted to explore the emplacement of Kubrik Mons. Steady state flow was achieved with a conduit of radius R = 0.02 m for a source chamber at 2.3 km depth. Effusion rates computed from this estimated a 122 - 163 Myr upper limit formation timescale.
ContributorsMount, Christopher (Author) / Christensen, Philip R. (Thesis advisor) / Desch, Steven J (Committee member) / Bell, James F. (Committee member) / Clarke, Amanda B (Committee member) / Whipple, Kelin X (Committee member) / Arizona State University (Publisher)
Created2019
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Description
Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand

Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog.

This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes.

An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM.
ContributorsNapolitano, Denise (Author) / Herckes, Pierre (Thesis advisor) / Fraser, Matthew (Committee member) / Shock, Everett (Committee member) / Arizona State University (Publisher)
Created2018
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Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance

Chemical and physical interactions of flowing ice and rock have inexorably shaped planetary surfaces. Weathering in glacial environments is a significant link in biogeochemical cycles – carbon and strontium – on Earth, and may have once played an important role in altering Mars’ surface. Despite growing recognition of the importance of low-temperature chemical weathering, these processes are still not well understood. Debris-coated glaciers are also present on Mars, emphasizing the need to study ice-related processes in the evolution of planetary surfaces. During Earth’s history, subglacial environments are thought to have sheltered communities of microorganisms from extreme climate variations. On Amazonian Mars, glaciers such as lobate debris aprons (LDA) could have hosted chemolithotrophic communities, making Mars’ present glaciers candidates for life preservation. This study characterizes glacial processes on both Earth and Mars.

Chemical weathering at Robertson Glacier, a small alpine glacier in the Canadian Rocky Mountains, is examined with a multidisciplinary approach. The relative proportions of differing dissolution reactions at various stages in the glacial system are empirically determined using aqueous geochemistry. Synthesis of laboratory and orbital thermal infrared spectroscopy allows identification of dissolution rinds on hand samples and characterization of carbonate dissolution signals at orbital scales, while chemical and morphological evidence for thin, discontinuous weathering rinds at microscales are evident from electron microscopy. Subglacial dissolution rates are found to outpace those of the proglacial till plain; biologically-mediated pyrite oxidation drives the bulk of this acidic weathering.

Second, the area-elevation relationship, or hypsometry, of LDA in the midlatitudes of Mars is characterized. These glaciers are believed to have formed ~500 Ma during a climate excursion. Hypsometric measurements of these debris-covered glaciers enable insight into past flow regimes and drive predictions about past climate scenarios. The LDA in this study fall into three major groups, strongly dependent on basal elevation, implying regional and climatic controls on ice formation and flow.

I show that biologically-mediated mineral reactions drive high subglacial dissolution rates, such that variations within the valley can be detected with remote sensing techniques. In future work, these insights can be applied to examining Mars’ glacial regions for signs of chemical alteration and biosignatures.
ContributorsRutledge, Alicia Marie (Author) / Christensen, Philip R. (Thesis advisor) / Shock, Everett (Committee member) / Clarke, Amanda (Committee member) / Sharp, Thomas (Committee member) / Whipple, Kelin (Committee member) / Arizona State University (Publisher)
Created2015
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Description
Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding

Amorphous phases are detected over large regions of the Martian surface from orbit and in more localized deposits by rovers on the surface. Amorphous silicates can be primary or secondary in origin, both having formed through very different processes, so the unambiguous identification of these phases is important for understanding the geologic history of Mars. Secondary amorphous silicates are poorly understood and underrepresented in spectral libraries because they lack the long-range structural order that makes their crystalline counterparts identifiable in most analytical techniques. Fortunately, even amorphous materials have some degree of short-range order so that distinctions can be made with careful characterization.

Two sets of laboratory experiments were used to produce and characterize amorphous weathering products under probable conditions for the Martian surface, and one global spectral analysis using thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) instrument was used to constrain variations in amorphous silicates across the Martian surface. The first set of experiments altered crystalline and glassy basalt samples in an open system under strong (pH 1) and moderate (pH 3) acidic conditions. The second set of experiments simulated a current-day Martian weathering scenario involving transient liquid water where basalt glass weathering solutions, formed in circumneutral (pH ~5.5 and 7) conditions, were rapidly evaporated, precipitating amorphous silicates. The samples were characterized using visible and near-infrared (VNIR) spectroscopy, TIR spectroscopy, scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD).

All experiments formed amorphous silicate phases that are new to spectral libraries. Moderately acidic alteration experiments produced no visible or spectral evidence of alteration products, whereas exposure of basalt glass to strongly acidic fluids produced silica-rich alteration layers that are spectrally consistent with VNIR and TIR spectra from the circum-polar region of Mars, indicating this region has undergone acidic weathering. Circum-netural pH basalt weathering solution precipitates are consistent with amorphous materials measured by rovers in soil and rock surface samples in Gale and Gusev Craters, suggesting transient water interactions over the last 3 billion years. Global spectral analyses determine that alteration conditions have varied across the Martian surface, and that alteration has been long lasting.
ContributorsSmith, Rebecca (Author) / Christensen, Philip R. (Philip Russel) (Thesis advisor) / Shock, Everett (Committee member) / Hartnett, Hilairy (Committee member) / Shim, Sang-Heon (Committee member) / Sharp, Thomas (Committee member) / Arizona State University (Publisher)
Created2016