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At least 667 records · Page 37

Major Volatiles from MSL SAM Evolved Gas Analyses: Yellowknife Bay Through Lower Mount Sharp

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of <150 μm fines from five sites at Gale Crater. Three were in Yellowknife Bay: the Rocknest aeolian bedform ("RN") and drilled Sheepbed mudstone from sites John Klein ("JK") and Cumberland ("CB"). One was drilled from the Windjana ("WJ") site on a sandstone of the Kimberly formation investigated on route to Mount Sharp. Another was drilled from the Confidence Hills ("CH") site on a sandstone of the Murray Formation at the base of Mt. Sharp (Pahrump Hills). Outcrops are sedimentary rocks that are largely of fluvial or lacustrine origin, with minor aeolian deposits.. SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments. The identity and evolution temperature (T) of evolved gases can support CheMin mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with XRD (e.g., X-ray amorphous phases). They can also give constraints on sample organic chemistry. Here, we discuss trends in major evolved volatiles from SAM EGA analyses to date.

McAdam, A. C.↗

Methane as a Diagnostic Tracer of Changes in the Brewer-Dobson Circulation of the Stratosphere

This study makes use of time series of methane (CH4/ data from the Halogen Occultation Experiment (HALOE) to detect whether there were any statistically significant changes of the Brewer-Dobson circulation (BDC) within the stratosphere during 1992-2005. The HALOE CH4 profiles are in terms of mixing ratio versus pressure altitude and are binned into latitude zones within the Southern Hemisphere and the Northern Hemisphere. Their separate time series are then analyzed using multiple linear regression (MLR) techniques. The CH4 trend terms for the Northern Hemisphere are significant and positive at 10 N from 50 to 7 hPa and larger than the tropospheric CH4 trends of about 3%decade(exp -1) from 20 to 7 hPa. At 60 N the trends are clearly negative from 20 to 7 hPa. Their combined trends indicate an acceleration of the BDC in the middle stratosphere of the Northern Hemisphere during those years, most likely due to changes from the effects of wave activity. No similar significant BDC acceleration is found for the Southern Hemisphere. Trends from HALOE H2O are analyzed for consistency. Their mutual trends with CH4 are anti-correlated qualitatively in the middle and upper stratosphere, where CH4 is chemically oxidized to H2O. Conversely, their mutual trends in the lower stratosphere are dominated by their trends upon entry to the tropical stratosphere. Time series residuals for CH4 in the lower mesosphere also exhibit structures that are anti-correlated in some instances with those of the tracer-like species HCl. Their occasional aperiodic structures indicate the effects of transport following episodic, wintertime wave activity. It is concluded that observed multi-year, zonally averaged distributions of CH4 can be used to diagnose major instances of wave-induced transport in the middle atmosphere and to detect changes in the stratospheric BDC.

Remsberg, E. E.↗

Nutrient Recovery of Plant Leachates Under Thermal, Biological, and Photocatalytic Pretreatments

Nutrient recovery has always been a problem for long distance and long-term space missions. To allow humans to man these missions, a steady source of oxygen, water, and food are necessary for survival beyond Earth's atmosphere. Plants are currently an area of interest since they are capable of providing all three resources for life sustainability. We are currently interested in nutrient recovery for future plant growth and simple aqueous leachate extractions can recover some of the nutrients. However, leaching plants also removes water-soluble organic plant wastes, which inhibits plant growth if not separated properly. To combat the issues with waste and maximize nutrient recovery, we are attempting to pre-treat the plant matter using biological, thermal, and photocatalytic methods before subjecting the solution with variable-strength acid digestion. For the biological method, the inoculums: mixed heterotrophic/nitrifying bioreactor effluent and Trichoderma vessei are used in an attempt to liberate more nutrients from the plant matter. For the thermal method, plants are subjected to varying temperatures at different retention times to determine nutrient recovery. Lastly, the photocatalytic method utilizes TiO (sub 2)'s oxidizing abilities under specific pHs and retention times to reduce organic wastes and improve nutrient gains. A final acid digestion serves to liberate nutrients even further in order to maximize recovery. So far, we have tested ideal acid digestion variables for practicality and performance in our experiments. We found that a low retention time of 10 minutes and a high acid concentration of 0.1 and 1 mole HCl were the most effective at nutrient recovery. For space travel purposes, 0.1 mole currently looks like a viable acid digestion to use since it is relatively effective and sustainable from a mass and energy balance if acid recovery can be performed on waste brines. Biological pretreatments do not look to be too effective and the thermal and photocatalytic methods may be preferred since they show a potential to recover more than 70 percent of the nutrients.

Photocatalytic↗

NASA's Corrosion Technology Laboratory at the Kennedy Space Center: Anticipating, Managing, and Preventing Corrosion

The marine environment at NASAs Kennedy Space Center (KSC) has been documented by ASM International (formerly American Society for Metals) as the most corrosive in North America. With the introduction of the Space Shuttle in 1981, the already highly corrosive conditions at the launch pads were rendered even more severe by the highly corrosive hydrochloric acid (HCl) generated by the solid rocket boosters (SRBs). Numerous failures at the launch pads are caused by corrosion. The structural integrity of ground infrastructure and flight hardware is critical to the success, safety, cost, and sustainability of space missions. NASA has over fifty years of experience dealing with unexpected failures caused by corrosion and has developed expertise in corrosion control in the launch and other environments. The Corrosion Technology Laboratory at KSC evolved, from what started as an atmospheric exposure test site near NASAs launch pads, into a capability that provides technical innovations and engineering services in all areas of corrosion for NASA, external partners, and customers.This paper provides a chronological overview of NASAs role in anticipating, managing, and preventing corrosion in highly corrosive environments. One important challenge in managing and preventing corrosion involves the detrimental impact on humans and the environment of what have been very effective corrosion control strategies. This challenge has motivated the development of new corrosion control technologies that are more effective and environmentally friendly. Strategies for improved corrosion protection and durability can have a huge impact on the economic sustainability of human spaceflight operations.

Corrosion Control↗

The Origin of Amino Acids in Lunar Regolith Samples

We analyzed the amino acid content of seven lunar regolith samples returned by the Apollo 16 and Apollo 17 missions and stored under NASA curation since collection using ultrahigh-performance liquid chromatography with fluorescence detection and time-of-flight mass spectrometry. Consistent with results from initial analyses shortly after collection in the 1970s, we observed amino acids at low concentrations in all of the curated samples, ranging from 0.2 parts-per-billion (ppb) to 42.7 ppb in hot-water extracts and 14.5 ppb to 651.1 ppb in 6M HCl acid-vapor-hydrolyzed, hot-water extracts. Amino acids identified in the Apollo soil extracts include glycine, D- and L-alanine, D- and L-aspartic acid, D- and L-glutamic acid, D- and L-serine, L-threonine, and L-valine, all of which had previously been detected in lunar samples, as well as several compounds not previously identified in lunar regoliths: -aminoisobutyric acid (AIB), D-and L-amino-n-butyric acid (-ABA), DL-amino-n-butyric acid, -amino-n-butyric acid, -alanine, and -amino-n-caproic acid. We observed an excess of the L enantiomer in most of the detected proteinogenic amino acids, but racemic alanine and racemic -ABA were present in some samples.

lunar regolith↗

Volcanic Eruptions and Climate

Volcanic eruptions represent some of the most climatically important and societally disruptive short-term events in human history. Large eruptions inject ash, dust, sulfurous gases (e.g. SO2, H2S), halogens (e.g. Hcl and Hbr), and water vapor into the Earth's atmosphere. Sulfurous emissions principally interact with the climate by converting into sulfate aerosols that reduce incoming solar radiation, warming the stratosphere and altering ozone creation, reducing global mean surface temperature, and suppressing the hydrological cycle. In this issue, we focus on the history, processes, and consequences of these large eruptions that inject enough material into the stratosphere to significantly affect the climate system. In terms of the changes wrought on the energy balance of the Earth System, these transient events can temporarily have a radiative forcing magnitude larger than the range of solar, greenhouse gas, and land use variability over the last millennium. In simulations as well as modern and paleoclimate observations, volcanic eruptions cause large inter-annual to decadal-scale changes in climate. Active debates persist concerning their role in longer-term (multi-decadal to centennial) modification of the Earth System, however.

Volcanoes↗

Effect of the Presence of Chlorates and Perchlorates on the Pyrolysis of Organic Compounds: Implications for Measurements Done with the SAM Experiment Onboard the Curiosity Rover

The Mars Science Laboratory (MSL) Curiosity Rover carries a suite of instruments, one of which is the Sample Analysis at Mars (SAM) experiment. SAM is devoted to the in situ molecular analysis of gases evolving from solid samples collected by Curiosity on Mars surface/sub-surface. Among its three analytical devices, SAM has a gaschromatograph coupled to a quadrupole mass spectrometer (GC-QMS). The GC-QMS is devoted to the separation and identification of organic and inorganic material. Before proceeding to the GC-QMS analysis, the solid sample collected by Curiosity is subjected to a thermal treatment thanks to the pyrolysis oven to release the volatiles into the gas processing system. Depending on the sample, a derivatization method by wet chemistry: MTBSTFA of TMAH can also be applied to analyze the most refractory compounds. The GC is able to separate the organic molecules which are then detected and identified by the QMS (Figure 1). For the second time after the Viking landers in 1976, SAM detected chlorinated organic compounds with the pyrolysis GC-QMS experiment. The detection of perchlorates salts (ClO4-) in soil at the Phoenix Landing site suggests that the chlorohydrocarbons detected could come from the reaction of organics with oxychlorines. Indeed, laboratory pyrolysis experiments have demonstrated that oxychlorines decomposed into molecular oxygen and volatile chlorine (HCl and/or Cl2) when heated which then react with the organic matter in the solid samples by oxidation and/or chlorination processes.

Millan, M.↗

Hydrogen Embrittlement

Hydrogen embrittlement (HE) is a process resulting in a decrease in the fracture toughness or ductility of a metal due to the presence of atomic hydrogen. In addition to pure hydrogen gas as a direct source for the absorption of atomic hydrogen, the damaging effect can manifest itself from other hydrogen-containing gas species such as hydrogen sulfide (H2S), hydrogen chloride (HCl), and hydrogen bromide (HBr) environments. It has been known that H2S environment may result in a much more severe condition of embrittlement than pure hydrogen gas (H2) for certain types of alloys at similar conditions of stress and gas pressure. The reduction of fracture loads can occur at levels well below the yield strength of the material. Hydrogen embrittlement is usually manifest in terms of singular sharp cracks, in contrast to the extensive branching observed for stress corrosion cracking. The initial crack openings and the local deformation associated with crack propagation may be so small that they are difficult to detect except in special nondestructive examinations. Cracks due to HE can grow rapidly with little macroscopic evidence of mechanical deformation in materials that are normally quite ductile. This Technical Memorandum presents a comprehensive review of experimental data for the effects of gaseous Hydrogen Environment Embrittlement (HEE) for several types of metallic materials. Common material screening methods are used to rate the hydrogen degradation of mechanical properties that occur while the material is under an applied stress and exposed to gaseous hydrogen as compared to air or helium, under slow strain rates (SSR) testing. Due to the simplicity and accelerated nature of these tests, the results expressed in terms of HEE index are not intended to necessarily represent true hydrogen service environment for long-term exposure, but rather to provide a practical approach for material screening, which is a useful concept to qualitatively evaluate the severity of hydrogen embrittlement. The effects of hydrogen gas on mechanical properties such as tensile strength, ductility, fracture, low and high cycle fatigue, crack growth rate, and creep rupture are analyzed with respect to the general trends established from the HEE index values. It is observed that the severity of HE effects is also influenced by environmental factors such as pressure, temperature, and hydrogen gas purity. The severity of HE effects is also influenced by material factors such as surface finish, heat treatment, and product forms, compositions, grain direction, and crystal orientations.

Jonathan A. Lee↗

A Modular Atmospheric Propagation Program (MAPP)

A computer model of the atmosphere has been developed that will solve a wide variety of lidar and atmospheric propagation problems. The lidar system calculations involve the prediction of path loss and lidar signal return for a variety of atmospheric conditions and lidar system configurations. The program contains a very large data base of absorption and attenuation coefficients for all of the naturally occurring gases and several gaseous pollutants such as S02, N02, NO, N20, 03, HCL, etc. The spectral range of this data base extends from the ultra-violet (1200 angstroms) through the infra-red. Several aerosol models are included in the program to account for the effects of this important scattering mechanism.

Wright, M. L.↗

Oxychlorine Detections on Mars: Implications for Cl Cycling

The Sample Analysis at Mars (SAM) instrument has detected evolved O2 and HCl indicating the presence of perchlorate and/or chlorate (oxychlorine) in all 11 sediments analyzed to date. The hyperarid martian climate is believed to have allowed accumulation of oxychlorine and assumed chloride contents similar to those in hyperarid terrestrial settings. The linear correlation of oxychlorine and chloride of Gale Crater sediments is low (r (sup 2) equals 0.64). Correlations present in hyperarid Antarctica and the Atacama Desert are attributed to unaltered atmospheric source coupled with minimal redox cycling by biological activity. Terrestrial semi-arid to arid settings have low correlations similar to Gale Crater and are attributed to additional inputs of Cl minus from sea salt, dust, and/or proximal playa settings, and possible reduction of oxychlorine phases during wetter periods. While microbiological processes could contribute to low oxychlorine/chloride correlations on Mars, several abiotic mechanisms are more likely, such as changing oxychlorine production rates with time and/or post-depositional geochemical redox processes that altered the Gale Crater oxychlorine and chloride contents.

Sutter, B.↗

Five-Channel Infrared Laser Absorption Spectrometer for Combustion Product Monitoring Aboard Manned Spacecraft

Continuous combustion product monitoring aboard manned spacecraft can prevent chronic exposure to hazardous compounds and also provides early detection of combustion events. As future missions extend beyond low-Earth orbit, analysis of returned environmental samples becomes impractical and safety monitoring should be performed in situ. Here, we describe initial designs of a five-channel tunable laser absorption spectrometer to continuously monitor combustion products with the goal of minimal maintenance and calibration over long-duration missions. The instrument incorporates dedicated laser channels to simultaneously target strong mid-infrared absorption lines of CO, HCl, HCN, HF, and CO2. The availability of low-power-consumption semiconductor lasers operating in the 2 to 5 micron wavelength range affords the flexibility to select absorption lines for each gas with maximum interaction strength and minimal interference from other gases, which enables the design of a compact and mechanically robust spectrometer with low-level sensitivity. In this paper, we focus primarily on absorption line selection based on the availability of low-power single-mode semiconductor laser sources designed specifically for the target wavelength range.

Briggs, Ryan M.↗

Sulfur-Bearing Phases Detected by Evolved Gas Analysis of the Rocknest Aeolian Deposit, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument suite detected SO2, H2S, OCS, and CS2 from approx.450 to 800 C during evolved gas analysis (EGA) of materials from the Rocknest aeolian deposit in Gale Crater, Mars. This was the first detection of evolved sulfur species from a Martian surface sample during in situ EGA. SO2(approx. 3-22 micro-mol) is consistent with the thermal decomposition of Fe sulfates or Ca sulfites, or evolution/desorption from sulfur-bearing amorphous phases. Reactions between reduced sulfur phases such as sulfides and evolved O2 or H2O in the SAM oven are another candidate SO2 source. H2S (approx.41-109 nmol) is consistent with interactions of H2O, H2 and/or HCl with reduced sulfur phases and/or SO2 in the SAM oven. OCS (approx.1-5 nmol) and CS2(approx.0.2-1 nmol) are likely derived from reactions between carbon-bearing compounds and reduced sulfur. Sulfates and sulfites indicate some aqueous interactions, although not necessarily at the Rocknest site; Fe sulfates imply interaction with acid solutions whereas Ca sulfites can form from acidic to near-neutral solutions. Sulfides in the Rocknest materials suggest input from materials originally deposited in a reducing environment or from detrital sulfides from an igneous source. The presence of sulfides also suggests that the materials have not been extensively altered by oxidative aqueous weathering. The possibility of both reduced and oxidized sulfur compounds in the deposit indicates a nonequilibrium assemblage. Understanding the sulfur mineralogy in Rocknest materials, which exhibit chemical similarities to basaltic fines analyzed elsewhere on Mars, can provide insight in to the origin and alteration history of Martian surface materials.

evolved gas analysis↗

Evolved Gas Analyses of the Murray Formation in Gale Crater, Mars: Results of the Curiosity Rover's Sample Analysis at Mars (SAM) Instrument

The Sample Analysis at Mars (SAM) instrument aboard the Mars Science Laboratory rover has analyzed 13 samples from Gale Crater. All SAM-evolved gas analyses have yielded a multitude of volatiles (e.g., H2O, SO2, H2S, CO2, CO, NO, O2, HCl) [1- 6]. The objectives of this work are to 1) Characterize recent evolved SO2, CO2, O2, and NO gas traces of the Murray formation mudstone, 2) Constrain sediment mineralogy/composition based on SAM evolved gas analysis (SAM-EGA), and 3) Discuss the implications of these results relative to understanding the geological history of Gale Crater.

Sutter, B.↗

Combustion Products Monitor: Trade Study Testing

Current combustion products monitoring on the International Space Station (ISS) uses a handheld device (Compound Specific Analyzer-Combustion Products, CSA-CP) containing electrochemical sensors used to measure the concentration of carbon monoxide (CO), hydrogen chloride (HCl), hydrogen cyanide (HCN), and oxygen (O2). The CO sensor in this device accounts for a well-known cross-sensitivity with hydrogen (H2), which is important, as ISS air can contain up to 100 ppm H2. Unfortunately, this current device is being discontinued, and due to space constraints, the new model cannot accommodate the size of the current CO sensor. Therefore, a trade study was conducted in order to determine which CO sensors on the market were available with compensation for H2, and which instruments used these sensors, while also measuring HCN, O2, and carbon dioxide (CO2). The addition of CO2 to the device is helpful, as current monitoring of this gas requires a second hand-held monitor. By providing a device that will monitor both combustion products and CO2, volume and up-mass can be reduced as these monitors are delivered to ISS.

Wallace, William T.↗

Influence of Oxychlorine Phases During the Pyrolysis of Organic Molecules: Implications for the Quest of Organics on Mars with the SAM Experiment Onboard the Curiosity Rover

One among the main objectives of the Sample Analysis at Mars (SAM) experiment is the in situ molecular analysis of gases evolving from solid samples heated up to approximately 850 degrees Centigrade, and collected by Curiosity on Mars surface/sub-surface in Gale crater. With this aim, SAM uses a gas-chromatograph coupled to a quadrupole mass spectrometer (GC-QMS) devoted to separate, detect and identify both volatile inorganic and organic compounds. SAM detected chlorinated organic molecules produced in evolved gas analysis (EGA) experiments. Several of these were also detected by the Viking experiments in 1976. SAM also detected oxychlorine compounds that were present at the Phoenix landing site. The oxychlorines may be prevelant over much of the martian surface. The C1 to C3 aliphatic chlorohydrocarbons (chloromethane and di- and trichloromethane) detected by SAM were attributed to reaction products occurring between the oxychlorines phases and the organic compounds coming from SAM instrument background. But SAM also showed the presence of a large excess of chlorobenzene and C2 to C4 dichloroalkanes among the volatile species released by the Cumberland sample of the Sheepbed mudstone. For the first time in the history of the Mars exploration, this proved the presence of Mars indigenous organic material at the Mars' surface. However, the identification of the precursor organic compounds of these chlorohydrocarbons is difficult due to the complexity of the reactions occurring during the sample pyrolysis. Laboratory pyrolysis experiments have demonstrated that oxychlorines phases such as perchlorates and chlorates, decomposed into dioxygen and volatile chlorine bearing molecules (HCl and/or Cl2) during the pyrolysis. These chemical species can then react with the organic molecules present in the martian solid samples through oxidation, chlorination and oxychlorination processes.

Millan, M.↗

Constraints on the Mineralogy of Gale Crater Mudstones from MSL SAM Evolved Water

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analysed more than 150 micron fines from 14 sites at Gale Crater. Here we focus on the mudstone samples. Two were drilled from sites John Klein (JK) and Cumberland (CB) in the Sheepbed mudstone. Six were drilled from Murray Formation mudstone: Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP), Buckskin (BK), Oudam (OU), Marimba (MB). SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases, including organic fragments. The identity and evolution temperature of evolved gases can support CheMin mineral detection and place constraints on trace volatile-bearing phases or phases difficult to characterize with X-ray diffraction (e.g., amorphous phases). Here we will focus on SAM H2O data and comparisons to SAM-like analyses of key reference materials.

McAdam, A. C.↗

20 Years of ClO Measurements in the Antarctic Lower Stratosphere

We present 20 years (1996-2015) of austral springtime measurements of chlorine monoxide (ClO) over Antarctica from the Chlorine Oxide Experiment (ChlOEl) ground-based millimeter wave spectrometer at Scott Base, Antarctica, as well 12 years (2004-2015) of ClO measurements from the Aura Microwave Limb Sounder (MLS). From August onwards we observe a strong increase in lower stratospheric ClO, with a peak column amount usually occurring in early September. From mid-September onwards we observe a strong decrease in ClO. In order to study interannual differences, we focus on a 3-week period from 28 August to 17 September for each year and compare the average column ClO anomalies. These column ClO anomalies are shown to be highly correlated with the average ozone mass deficit for September and October of each year. We also show that anomalies in column ClO are strongly anti-correlated with 30 hPa temperature anomalies, both on a daily and an interannual timescale. Making use of this anti-correlation we calculate the linear dependence of the interannual variations in column C1O on interannual variations in temperature. By making use of this relationship, we can better estimate the underlying trend in the total chlorine (Cl(sub y) = HCl + ClONO2 + HOCl + 2 x Cl2 + 2 x Cl2+ ClO + Cl). The resultant trends in Cl(sub y), which determine the long-term trend in ClO, are estimated to be -0.5 +/-0.2, -1.40.9, and -0.60.4% per year, for zonal MLS, Scott Base MLS (both 2004-2015), and ChlOE (1996-2015) respectively. These trends are within 1sigma of trends in stratospheric Cl(sub y) previously found at other latitudes. The decrease in ClO is consistent with the trend expected from regulations enacted under the Montreal Protocol.

temperature anomalies↗

Boron Nitride Nanoribbons from Exfoliation of Boron Nitride Nanotubes

Two types of boron nitride nanotubes (BNNTs) were exfoliated into boron nitride nanoribbons (BNNR), which were identified using transmission electron microscopy: (1) commercial BNNTs with thin tube walls and small diameters. Tube unzipping was indicated by a large decrease of the sample's surface area and volume for pores less than 2 nm in diameter. (2) BNNTs with large diameters and thick walls synthesized at NASA Glenn Research Center. Here, tube unraveling was indicated by a large increase in external surface area and pore volume. For both, the exfoliation process was similar to the previous reported method to exfoliate commercial hexagonal boron nitride (hBN): Mixtures of BNNT, FeCl3, and NaF (or KF) were sequentially treated in 250 to 350 C nitrogen for intercalation, 500 to 750 C air for exfoliation, and finally HCl for purification. Property changes of the nanosized boron nitride throughout this process were also similar to the previously observed changes of commercial hBN during the exfoliation process: Both crystal structure (x-ray diffraction data) and chemical properties (Fourier-transform infrared spectroscopy data) of the original reactant changed after intercalation and exfoliation, but most (not all) of these changes revert back to those of the reactant once the final, purified products are obtained.

boron nitride nanotube↗