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All sourcesNASA NTRSDOE OSTI
NASA NTRS2005

Creation and testing of an artificial neural network based carbonate detector for Mars rovers

We have developed an artificial neural network (ANN) based carbonate detector capable of running on current and future rover hardware. The detector can identify calcite in visible/NIR (350-2500 nm) spectra of both laboratory specimens covered by ferric dust and rocks in Mars analogue field environments. The ANN was trained using the Backpropagation algorithm with sigmoid activation neurons. For the training dataset, we chose nine carbonate and eight non-carbonate representative mineral spectra from the USGS spectral library. Using these spectra as seeds, we generated 10,000 variants with up to 2% Gaussian noise in each reflectance measurement. We cross-validated several ANN architectures, training on 9,900 spectra and testing on the remaining 100. The best performing ANN correctly detected, with perfect accuracy, the presence (or absence) of carbonate in spectral data taken on field samples from the Mojave desert and clean, pure marbles from CT. Sensitivity experiments with JSC Mars-1 simulant dust suggest the carbonate detector would perform well in aeolian Martian environments.

neural networks↗
NASA NTRS2006

Remote Pulsed Laser Raman Spectroscopy System for Detecting Qater, Ice, and Hydrous Minerals

For exploration of planetary surfaces, detection of water and ice is of great interest in supporting existence of life on other planets. Therefore, a remote Raman spectroscopy system was demonstrated at NASA Langley Research Center in collaboration with University of Hawaii for detecting ice-water and hydrous minerals on planetary surfaces. In this study, a 532 nm pulsed laser is utilized as an excitation source to allow detection in high background radiation conditions. The Raman scattered signal is collected by a 4-inch telescope positioned in front of a spectrograph. The Raman spectrum is analyzed using a spectrograph equipped with a holographic super notch filter to eliminate Rayleigh scattering, and a holographic transmission grating that simultaneously disperses two spectral tracks onto the detector for higher spectral range. To view the spectrum, the spectrograph is coupled to an intensified charge-coupled device (ICCD), which allows detection of very weak Stokes line. The ICCD is operated in gated mode to further suppress effects from background radiation and long-lived fluorescence. The sample is placed at 5.6 m from the telescope, and the laser is mounted on the telescope in a coaxial geometry to achieve maximum performance. The system was calibrated using the spectral lines of a Neon lamp source. To evaluate the system, Raman standard samples such as calcite, naphthalene, acetone, and isopropyl alcohol were analyzed. The Raman evaluation technique was used to analyze water, ice and other hydrous minerals and results from these species are presented.

Garcia, Christopher S.↗
NASA NTRS2007

Rb-Sr and Sm-Nd Isotopic Studies of Martian Depleted Shergottes SaU 094/005

Sayh al Uhaymir (SaU) 094 and SaU 005 are olivine-phyric shergottites from the Oman desert and are considered as pairs. [e.g., 1]. They are very similar to the Libyan desert shergottite Dar al Gani (DaG) 476 in petrology, chemistry and ejection age [2-6]. This group of shergottites, also recognized as depleted shergottites [e.g. 7] has been strongly shocked and contains very low abundances of light rare earth elements (REE). In addition, terrestrial contaminants are commonly present in meteorites found in desert environments. Age-dating these samples is very challenging, but lower calcite contents in the SaU meteorites suggest that they have been subjected to less severe desert weathering than their DaG counterparts [3-4]. In this report, we present Rb-Sr and Sm-Nd isotopic results for SaU 094 and SaU 005, discuss the correlation of their ages with those of other similar shergottites, and discuss their petrogenesis.

Shih, C.-Y.↗
NASA NTRS2007

Remote Raman Sensor System for Testing of Rocks and Minerals

Recent and future explorations of Mars and lunar surfaces through rovers and landers have spawned great interest in developing an instrument that can perform in-situ analysis of minerals on planetary surfaces. Several research groups have anticipated that for such analysis, Raman spectroscopy is the best suited technique because it can unambiguously provide the composition and structure of a material. A remote pulsed Raman spectroscopy system for analyzing minerals was demonstrated at NASA Langley Research Center in collaboration with the University of Hawaii. This system utilizes a 532 nm pulsed laser as an excitation wavelength, and a telescope with a 4-inch aperture for collecting backscattered radiation. A spectrograph equipped with a super notch filter for attenuating Rayleigh scattering is used to analyze the scattered signal. To form the Raman spectrum, the spectrograph utilizes a holographic transmission grating that simultaneously disperses two spectral tracks on the detector for increased spectral range. The spectrum is recorded on an intensified charge-coupled device (ICCD) camera system, which provides high gain to allow detection of inherently weak Stokes lines. To evaluate the performance of the system, Raman standards such as calcite and naphthalene are analyzed. Several sets of rock and gemstone samples obtained from Ward s Natural Science are tested using the Raman spectroscopy system. In addition, Raman spectra of combustible substances such acetone and isopropanol are also obtained. Results obtained from those samples and combustible substances are presented.

Garcia, Christopher S.↗
NASA NTRS2009

Thermal Decomposition of an Impure (Roxbury) Siderite: Relevance to the Presence of Chemically Pure Magnetite Crystals in ALH84001 Carbonate Disks

The question of the origin of nanophase magnetite in Martian meteorite ALH84001 has been widely debated for nearly a decade. Golden et al. have reported producing nearly chemically pure magnetite from thermal decomposition of chemically impure siderite [(Fe, Mg, Mn)CO3]. This claim is significant for three reasons: first, it has been argued that chemically pure magnetite present in the carbonate disks in Martian meteorite ALH84001 could have formed by the thermal decomposition of the impure carbonate matrix in which they are embedded; second, the chemical purity of magnetite has been previously used to identify biogenic magnetite; and, third, previous studies of thermal decomposition of impure (Mg,Ca,Mn)-siderites, which have been investigated under a wide variety of conditions by numerous researchers, invariably yields a mixed metal oxide phase as the product and not chemically pure magnetite. The explanation for this observation is that these siderites all possess the same crystallographic structure (Calcite; R3c) so solid solutions between these carbonates are readily formed and can be viewed on an atomic scale as two chemically different but structurally similar lattices.

McKay, D.S.↗
NASA NTRS2010

Cryogenic Carbonate Formation on Mars: Clues from Stable Isotope Variations Seen in Experimental Studies

Discoveries of large deposits of sedimentary materials on the planet Mars by landers and orbiters have confirmed the widely held hypothesis that water has played a crucial role in the development of the martian surface. Recent studies have indicated that both water ice and liquid water may have been present and in the case of water ice perhaps is still present on or near the surface of Mars. However, there remains much controversy about the prevailing atmospheric conditions and climate of Mars during its history and whether liquid water existed on the martian surface simply during discrete geological events or whether this water was present over relatively much longer geologic time periods. The recent identification of Ca-rich carbonate by the Phoenix lander as well as its measurement of the isotopic composition of atmospheric CO2 has shown the importance of understanding the carbonates on Mars as an important sink of atmospheric carbon. This work compliments that of our past experiments where we produced cryogenic calcite in open containers, as analogs for terrestrial aufeis formation, and as a means for evaluating the fractionation of C-13 in CO2 during bicarbonate freezing [13]. Unlike our previous experiments in which carbonates were grown in ambient laboratory condition in open containers (atmospheric pressure and composition), this work attempts to quantify the amount of delta C-13 enrichment possible in both fluids and secondary carbonates formed from freezing of bicarbonate fluids under martian-like atmospheric conditions. Morphologic textures of produced carbonates in these experiments are also examined under SEM in order to identify the effect that the cryogenic freezing process has on the mineral's mineralogy. Understanding the role of kinetic isotope fractionation during formation of carbonates under martian-like conditions will aid in our ability to quantify the isotopic composition of the carbonate sink furthering our ability to model the climate history of Mars.

Socki, Richard A.↗
NASA NTRS2010

Mud Volcanoes - Analogs to Martian Cones and Domes (by the Thousands!)

Mud volcanoes are mounds formed by low temperature slurries of gas, liquid, sediments and rock that erupt to the surface from depths of meters to kilometers. They are common on Earth, with estimates of thousands onshore and tens of thousands offshore. Mud volcanoes occur in basins with rapidly-deposited accumulations of fine-grained sediments. Such settings are ideal for concentration and preservation of organic materials, and mud volcanoes typically occur in sedimentary basins that are rich in organic biosignatures. Domes and cones, cited as possible mud volcanoes by previous authors, are common on the northern plains of Mars. Our analysis of selected regions in southern Acidalia Planitia has revealed over 18,000 such features, and we estimate that more than 40,000 occur across the area. These domes and cones strongly resemble terrestrial mud volcanoes in size, shape, morphology, associated flow structures and geologic setting. Geologic and mineralogic arguments rule out alternative formation mechanisms involving lava, ice and impacts. We are studying terrestrial mud volcanoes from onshore and submarine locations. The largest concentration of onshore features is in Azerbaijan, near the western edge of the Caspian Sea. These features are typically hundreds of meters to several kilometers in diameter, and tens to hundreds of meters in height. Satellite images show spatial densities of 20 to 40 eruptive centers per 1000 square km. Many of the features remain active, and fresh mud flows as long as several kilometers are common. A large field of submarine mud volcanoes is located in the Gulf of Cadiz, off the Atlantic coasts of Morocco and Spain. High-resolution sonar bathymetry reveals numerous km-scale mud volcanoes, hundreds of meters in height. Seismic profiles demonstrate that the mud erupts from depths of several hundred meters. These submarine mud volcanoes are the closest morphologic analogs yet found to the features in Acidalia Planitia. We are also conducting laboratory analyses of surface samples collected from mud volcanoes in Azerbaijan, Taiwan and Japan. X-ray diffraction, visible / near infrared reflectance spectroscopy and Raman spectroscopy show that the samples are dominated by mixed-layer smectite clays, along with quartz, calcite and pyrite. Thin section analysis by optical and scanning electron microscopy confirms the mineral identifications. These samples also contain chemical and morphological biosignatures, including common microfossils, with evidence of partial replacement by pyrite. The bulk samples contain approximately 1 wt% total organic carbon and 0.4 mg / gm volatile hydrocarbons. The thousands of features in Acidalia Planitia cited as analogous to terrestrial mud volcanoes clearly represent an important element in the sedimentary record of Mars. Their location, in the distal depocenter for massive Hesperian-age floods, suggests that they contain fine-grained sediments from a large catchment area in the martian highlands. We have proposed these features as a new class of exploration target that can provide access to minimally-altered material from significant depth. By analogy to terrestrial mud volcanoes, these features may also be excellent sites for the sampling martian organics and subsurface microbial life, if such exist or ever existed.

Allen, Carlton C.↗
NASA NTRS2011

Cryogenic Origin for Mars Analog Carbonates in the Bockfjord Volcanic Complex Svalbard (Norway)

The Sverrefjell and Sigurdfjell eruptive centers in the Bockfjord Volcanic Complex (BVC) on Svalbard (Norway) formed by subglacial eruptions ca. 1 Ma ago. These eruptive centers carry ubiquitous magnesian carbonate deposits including dolomitemagnesite globules similar to those in the Martian meteorite ALH84001. Carbonates in mantle xenoliths are dominated by ALH84001 type carbonate globules that formed during quenching of CO2-rich mantle fluids. Lava hosted carbonates include ALH84001 type carbonate globules occurring throughout lava vesicles and microfractures and massive carbonate deposits associated with vertical volcanic vents. Massive carbonates include < or equal 5 cm thick magnesite deposits protruding downwards into clear blue ice within volcanic vents and carbonate cemented lava breccias associated with volcanic vents. Carbonate cements comprise layered deposits of calcite, dolomite, huntite, magnesite and aragonite associated with ALH84001 type carbonate globules lining lava vesicles. Combined Mossbauer, XRD and VNIR data show that breccia carbonate cements at Sverrefjell are analog to Comanche carbonates at Gusev crater.

Amundsen, H. E. F.↗
NASA NTRS2012

Thermal and Evolved Gas Analysis of "Nanophase" Carbonates: Implications for Thermal and Evolved Gas Analysis on Mars Missions

Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

Lauer, Howard V., Jr.↗
NASA NTRS2012

In Situ Chemical Characterization of Mineral Phases in Lunar Granulite Meteorite Northwest Africa 5744

Northwest Africa (NWA) 5744 meteorite is a granulitic and troctolitic lunar breccia which may represent nearly pristine lunar crust (Fig. 1). NWA 5744 is unusually magnesian compared to other lunar breccias, with bulk [Mg/(Mg+Fe)] ~ 0.79 [1, 2]. Inspection shows impactor content is likely to be very minor, with low Ni content and a lack of metal grains. Some terrestrial contamination is present, evidenced by calcite within cracks. NWA 5744 has notably low concentrations of incompatible trace elements (ITEs) [2]. The goal of this study is to attempt to classify this lunar granulite through analyses of in situ phases.

Kent, J. J.↗
NASA NTRS2011

Characterizing Volcanic Eruptions on Venus: Some Realistic (?) Scenarios

When Pioneer Venus arrived at Venus in 1978, it detected anomalously high concentrations of SO2 at the top of the troposphere, which subsequently declined over the next five years. This decline in SO2 was linked to some sort of dynamic process, possibly a volcanic eruption. Observations of SO2 variability have persisted since Pioneer Venus. More recently, scientists from the Venus Express mission announced that the SPICAV (Spectroscopy for Investigation of Characteristics of the Atmosphere of Venus) instrument had measured varying amounts of SO2 in the upper atmosphere; VIRTIS (Visible and Infrared Thermal Imaging Spectrometer) measured no similar variations in the lower atmosphere (ESA, 4 April, 2008). In addition, Fegley and Prinn stated that venusian volcanoes must replenish SO2 to the atmosphere, or it would react with calcite and disappear within 1.9 my. Fegley and Tremain suggested an eruption rate on the order of approx 1 cubic km/year to maintain atmospheric SO2; Bullock and Grinspoon posit that volcanism must have occurred within the last 20-50 my to maintain the sulfuric acid/water clouds on Venus. The abundance of volcanic deposits on Venus and the likely thermal history of the planet suggest that it is still geologically active, although at rates lower than Earth. Current estimates of resurfacing rates range from approx 0.01 cubic km/yr to approx 2 cubic km/yr. Demonstrating definitively that Venus is still volcanically active, and at what rate, would help to constrain models of evolution of the surface and interior, and help to focus future exploration of Venus.

Stofan, E. R.↗
NASA NTRS2012

Calibration and Sequence Development Status for the Sample Analysis at Mars Investigation on the Mars Science Laboratory

The measurement goals of the Sample Analysis at Mars (SAM) instrument suite on the "Curiosity" Rover of the Mars Science Laboratory (MSL) include chemical and isotopic analysis of organic and inorganic volatiles for both atmospheric and solid samples [1,2]. SAM directly supports the ambitious goals of the MSL mission to provide a quantitative assessment of habitability and preservation in Gale crater by means of a range of chemical and geological measurements [3]. The SAM FM combined calibration and environmental testing took place primarily in 2010 with a limited set of tests implemented after integration into the rover in January 2011. The scope of SAM FM testing was limited both to preserve SAM consumables such as life time of its electromechanical elements and to minimize the level of terrestrial contamination in the SAM instrument. A more comprehensive calibration of a SAM-like suite of instruments will be implemented in 2012 with calibration runs planned for the SAM testbed. The SAM Testbed is nearly identical to the SAM FM and operates in a ambient pressure chamber. The SAM Instrument Suite: SAM's instruments are a Quadrupole Mass Spectrometer (QMS), a 6-column Gas Chromatograph (GC), and a 2-channel Tunable Laser Spectrometer (TLS). Gas Chromatography Mass Spectrometry is designed for identification of even trace organic compounds. The TLS [5] secures the C, H, and O isotopic composition in carbon dioxide, water, and methane. Sieved materials are delivered from the MSL sample acquisition and processing system to one of68 cups of the Sample Manipulation System (SMS). 59 of these cups are fabricated from inert quartz. After sample delivery, a cup is inserted into one of 2 ovens for evolved gas analysis (EGA ambient to >9500C) by the QMS and TLS. A portion of the gas released can be trapped and subsequently analyzed by GCMS. Nine sealed cups contain liquid solvents and chemical derivatization or thermochemolysis agents to extract and transform polar molecules such as amino acids, nucleobases, and carboxylic acids into compounds that are sufficiently volatile to transmit through the GC columns. The remaining 6 cups contain calibrants. SAM FM Calibration Overview: The SAM FM calibration in the Mars chamber employed a variety of pure gases, gas mixtures, and solid materials. Isotope calibration runs for the TLS utilized 13C enriched C02 standards and 0 enriched CH4. A variety of fluorocarbon compounds that spanned the entire mass range of the QMS as well as C3-C6 hydrocarbons were utilized for calibration of the GCMS. Solid samples consisting of a mixture of calcite, melanterite, and inert silica glass either doped or not with fluorocarbons were introduced into the SAM FM cups through the SAM inlet funnel/tube system.

Mahaffy, Paul R.↗
NASA NTRS2012

Investigations Using Laboratory Testbeds to Interpret Flight Instrument Datasets from Mars Robotic Missions

The Astromaterials Research and Exploration Science Directorate at the NASA Johnson Space Center (JSC) has laboratory instrumentation that mimic the capabilities of corresponding flight instruments to enable interpretation of datasets returned from Mars robotic missions. The lab instruments have been and continue to be applied to datasets for the Moessbauer Spectrometer (MB) on the Mars Exploration Rovers (MER), the Thermal & Evolved Gas Analyzer (TEGA) on the Mars Phoenix Scout, the CRISM instrument on the Mars Reconnaissance Orbiter Missions and will be applied to datasets for the Sample Analysis at Mars (SAM), Chemistry and Mineralogy (CheMin) and Chemistry & Camera (ChemCam) instruments onboard the Mars Science Laboratory (MSL). The laboratory instruments can analyze analog samples at costs that are substantially lower than engineering models of flight instruments, but their success to enable interpretation of flight data depends on how closely their capabilities mimic those of the flight instrument. The JSC lab MB instruments are equivalent to the MER instruments except without flight qualified components and no reference channel Co-57 source. Data from analog samples were critical for identification of Mg-Fe carbonate at Gusev crater. Fiber-optic VNIR spectrometers are used to obtain CRISM-like spectral data over the range 350-2500 nm, and data for Fephyllosilicates show irreversible behavior in the electronic transition region upon dessication. The MB and VNIR instruments can be operated within chambers where, for example, the absolute H2O concentration can be measured and controlled. Phoenix's TEGA consisted of a calorimeter coupled to a mass spectrometer (MS). The JSC laboratory testbed instrument consisted of a differential scanning calorimeter (DSC) coupled to a MS configured to operate under total pressure (12 mbar), heating rate (20 C/min), and purge gas composition (N2) analogous to the flight TEGA. TEGA detected CO2 release at both low (400-680 C) and high (725-820 C) temperature and an endothermic reaction in concert with the high temperature release. The high-temperature thermal decomposition is consistent with calcite, dolomite, or ankerite, (3-6 wt.%) or any combination of these phase based upon laboratory testbed experiments. Recent laboratory experiments suggest that the low temperature CO2 release was caused by a reaction between calcium carbonate and hydrated magnesium perchlorate; although, CO2 release by the oxidation of organic materials and Fe-/Mg-rich carbonates cannot be ruled out. MSL landed in Gale crater on August 5, 2012. Although numerous analog samples have been analyzed on the JSC laboratory testbeds, no SAM, CheMin, or ChemCam analyses have been acquired by MSL to date. The JSC SAM laboratory testbed consists of a thermal analyzer coupled with a MS configured to operate under total pressure (30 mbar), heating rate (35 C/min), and purge gas composition (He) analogous to the flight SAM. The CheMin and ChemCam laboratory testbeds were developed and built by inXitu, Inc. and Los Alamos National Laboratory, respectively, to acquire datasets relevant to the MSL CheMin and ChemCam flight instruments.

Ming, D. W.↗
NASA NTRS2013

Assessing Habitability: Lessons from the Phoenix Mission

The Phoenix mission's key objective was to search for a habitable zone. The Phoenix lander carried a robotic arm with digging scoop to collect soil and icy material for analysis with an instrument payload that included volatile mineral and organic analysis(3) and soil ionic chemistry analysis (4). Results from Phoenix along with theoretical modeling and other previous mission results were used to evaluate the habitability of the landing site by considering four factors that characterize the environments ability to support life as we know it: the presence of liquid water, the presence of an energy source to support metabolism, the presence of nutrients containing the fundamental building blocks of life, and the absence of environmental conditions that are toxic to or preclude life. Phoenix observational evidence for the presence of liquid water (past or present) includes clean segregated ice, chemical etching of soil grains, calcite minerals in the soil and variable concentrations of soluble salts5. The maximum surface temperature measured was 260K so unfrozen water can form only in adsorbed films or saline brines but warmer climates occur cyclically on geologically short time scales due to variations in orbital parameters. During high obliquity periods, temperatures allowing metabolism extend nearly a meter into the subsurface. Phoenix discovered ~1%w/w perchlorate salt in the soil, a chemical energy source utilized by a wide range of microbes. Nutrient sources including C, H, N, O, P and S compounds are supplied by known atmospheric sources or global dust. Environmental conditions are within growth tolerance for terrestrial microbes. Summer daytime temperatures are sufficient for metabolic activity, the pH is 7.8 and is well buffered and the projected water activity of a wet soil will allow growth. In summary, martian permafrost in the north polar region is a viable location for modern life. Stoker et al. presented a formalism for comparing the habitability of various regions visited to date on Mars that involved computing a habitability probability, defined as the product of probabilities for the presence of liquid water (P(sub lw)), energy (P(sub e)), nutrients (P(sub ch)), and a benign environment (P(sub b)). Using this formalism, they argued that the Phoenix site was the most habitable of any site visited to date by landed missions and warranted a follow up mission to search for modern evidence of life. This paper will review that conclusion in view of more recent information from the Mars Exploration Rovers and Mars Science Lander missions.

Stoker, Carol R.↗
NASA NTRS2012

Linking the 8.2 ka Event and its Freshwater Forcing in the Labrador Sea

The 8.2 ka event was the last deglacial abrupt climate event. A reduction in the Atlantic meridional overturning circulation (AMOC) attributed to the drainage of glacial Lake Agassiz may have caused the event, but the freshwater signature of Lake Agassiz discharge has yet to be identified in (delta)18O of foraminiferal calcite records from the Labrador Sea, calling into question the connection between freshwater discharge to the North Atlantic and AMOC strength. Using Mg/Ca-paleothermometry, we demonstrate that approx. 3 C of near-surface ocean cooling masked an 1.0 % decrease in western Labrador Sea (delta)18O of seawater concurrent with Lake Agassiz drainage. Comparison with North Atlantic (delta)18O of seawater records shows that the freshwater discharge was transported to regions of deep-water formation where it could perturb AMOC and force the 8.2 ka event.

Hoffman, Jeremy S.↗
NASA NTRS2013

Mid-infrared Study of Stones from the Sutters Mill Meteorite

The Sutter's Mill meteorite fell in northern California on April 22, 2012, and numerous pieces have been recovered and studied with several analytical techniques [1]. We present a Fourier-transform infrared (FTIR) spectroscopy analysis of fragments from several stones of the meteorite. Methods and analysis: Infrared spectra of samples SM2 and SM12 were recorded with a Nicolet iN10 MX FTIR microscope in the mid-IR range (4000-650/cm; spectral resolution 4/cm), while samples SM20 and SM30 were analyzed with a synchrotron-based Nicolet Continuum IR microscope in the same range. Samples were deposited on a clean glass slide, crushed with either a stainless steel roller tool or between 2 slides, and placed directly on the focal plane of the microscopes. Results: IR spectra of non-fusion crust samples show several absorption features associated with minerals such as olivines, phyllosilicates, carbonates (calcite and dolomite), and pyroxenes, as well as organics [2]. The carbonates display a main, broad band centered at 1433/cm, with additional bands at 2515/cm, 1797/cm, 882/cm, and 715/cm. Features associated with phyllosilicates include a symmetric Si-O stretching mode band centered at 1011/cm and several O-H stretching mode bands―a broad band centered at 3415/cm that is probably due to adsorbed H2O, and occasionally a much weaker, narrower feature centered near 3680/cm due to structural O-H. Features observed in the 2985-2855/cm range suggest the presence of aliphatic -CH3 and -CH2- groups. However, some of these bands show unusual relative intensities, mainly because of carbonate overtone bands that fall in the same spectral range, which can make the identification of C-H stretching bands problematic. The positions and relative strengths of the aliphatic -CH2- and -CH3 features, where they can be distinguished from overlapping carbonate bands, are consistent with those in interplanetary dust particles (IDPs) and Murchison. Finally, the absence of a strong C=O absorption feature near 1700/cm distinguishes the organics in the Sutter's Mill meteorite from that in most IDPs and in Murchison, but is consistent with the organic matter in Tagish Lake.

mid-infrared study↗
NASA NTRS2013

Carbonate Mineral Formation on Mars: Clues from Stable Isotope Variation Seen in Cryogenic Laboratory Studies of Carbonate Salts

The geologic history of water on the planet Mars is intimately connected to the formation of carbonate minerals through atmospheric CO2 and its control of the climate history of Mars. Carbonate mineral formation under modern martian atmospheric conditions could be a critical factor in controlling the martian climate in a means similar to the rock weathering cycle on Earth. The combination of evidence for liquid water on the martian surface and cold surface conditions suggest fluid freezing could be very common on the surface of Mars. Cryogenic calcite forms readily when a rise in pH occurs as a result of carbon dioxide degassing quickly from freezing Ca-bicarbonate-rich water solutions. This is a process that has been observed in some terrestrial settings such as arctic permafrost cave deposits, lakebeds of the Dry Valleys of Antarctica, and in aufeis (river icings) from rivers of N.E. Alaska. We report here the results of a series of laboratory experiments that were conducted to simulate potential cryogenic carbonate formation on the planet Mars. These results indicate that carbonates grown under martian conditions (controlled atmospheric pressure and temperature) show enrichments from starting bicarbonate fluids in both carbon and oxygen isotopes beyond equilibrium values with average delta13C(DIC-CARB) values of ~20.5%0 which exceed the expected equilibrium fractionation factor of [10(sup 3) ln alpha = ~13%0] at 0 degC. Oxygen isotopes showed a smaller enrichment with delta18O(H2O-CARB) values of ~35.5%0, slightly exceeding the equilibrium fractionation factor of [10(sup 3) ln alpha = ~34%0 ] at 0degC. Large kinetic carbon isotope effects during carbonate precipitation could substantially affect the carbon isotope evolution of CO2 on Mars allowing for more efficient removal of 13C from the Noachian atmosphere enriched by atmospheric loss. This mechanism would be consistent with the observations of large carbon isotope variations in martian materials despite the relative paucity of carbonate minerals in the martian crust.

Socki, Richard↗
NASA NTRS2013

Mid-Infrared Study of Samples from Multiple Stones from the Sutters Mill Meteorite

The Sutter's Mill meteorite fell in N. California on April 22, 2012 and numerous pieces have been recovered and studied. We present Fourier transform infrared (FTIR) spectra of fragments from several stones of the meteorite. Methods and analysis: Infrared spectra of the samples were recorded with a Nicolet iN10 MX FTIR microscope in the mid-IR range (4000-675/cm; spectral resolution 4/cm). All samples were deposited on a clean glass slide, crushed with a stainless steel roller tool, and placed directly on the focal plane of the microscope. IR spectra were collected by averaging 128 scans. Results: Preliminary IR spectra of the non-fusion crust samples show mineral compositions that are dominated by phyllosilicates, carbonates, or mixtures of both [2]. The carbonates display a dominant, broad band centered at 1433/cm, with additional bands at 2515/cm, 1797/cm, 882/cm, and 715/cm). Features associated with phyllosilicates include a symmetric Si-O stretching mode band centered at 1011/cm and several O-H stretching mode bands. The O-H shows up in two forms (1) a broadband centered at 3415/cm that is probably largely due to adsorbed H2O and (2) a much weaker, narrower feature centered near 3680/cm due to structural -OH. Features observed in the 2985-2855/cm range suggest the presence of aliphatic -CH3 and -CH2- groups. The relative intensities of the bands in this range are somewhat unusual. Typically, the asymmetric aliphatic CH stretching bands are stronger than the symmetric stretching bands, but in this case the reverse is true. This unusual pattern is well matched by the aliphatic features seen in the spectrum of a terrestrial calcite (CaCO3) standard. This observation, and the fact that the strength of the carbonate and aliphatic bands seem to correlate, suggest the organics are associated with the carbonates. Conclusions: IR spectra of samples from the Sutter's Mill meteorite show absorption features associated with carbonates, phyllosilicates, and organics. Both the unusual band profile of the aliphatic C-H stretching mode bands and their correlation with the strength of the carbonate bands suggests the organics and the carbonates are associated in some manner.

Sutter's mill↗