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NASA NTRS2011

Rapid Transpacific Transport in Autumn Observed by the A-Train Satellites

Transpacific transport of dust and pollutants is well documented for spring, but less so for other seasons. Here we investigate rapid transpacific transport in autumn utilizing the A-train satellites. In three episodes studied as examples, SO2 plumes over East Asia were detected by the Ozone Monitoring Instrument aboard the Aura satellite, and found to reach North America in 5-6 days. They were likely derived from anthropogenic sources, given that identical transport patterns of CO, a tracer for incomplete combustion, were simultaneously observed by the Aqua satellite. Trajectory analysis and meteorological data were employed to explore the meteorological circumstances surrounding these events: like many of their counterparts in spring, all three plumes were lifted to the free troposphere in warm conveyor belt associated with mid-latitude wave cyclones, and their migration to downwind region was regulated by the meteorology over the East Pacific. These cases provide further evidence that a fraction of S02 could escape wet scavenging, and be transported at much greater efficiency than NOx (NO + N02). An analysis of the S02 and CO data from September to November during 2005-2008 found 16 S02 long-range transport episodes, out of 62 Asian outflow events. While the counts are sensitive to the choice of criteria, they suggest that the long-range transport of Asian sulfur species occurs quite frequently, and could exert strong impacts on large downstream areas. This study also highlights the importance of transpacific transport in autumn, which has thus far been rarely studied and deserves more attention from the community.

Li. Can↗
NASA NTRS2009

Evolved Gas Measurements Planned for the Lower Layers of the Gale Crater Mound with the Sample Analysis at Mars Instrument Suite

The lower mound strata of Gale Crater provide a diverse set of chemical environments for exploration by the varied tools of the Curiosity Rover of the Mars Science Laboratory (MSL) Mission. Orbital imaging and spectroscopy clearly reveal distinct layers of hydrated minerals, sulfates, and clays with abundant evidence of a variety of fluvial processes. The three instruments of the MSL Sample Analysis at aMars (SAM) investigation, the Quadrupole Mass Spectrometer (QMS), the Tunable Laser Spectrometer (TLS), and the Gas Chromatograph (GC) are designed to analyze either atmospheric gases or volatiles thermally evolved or chemically extracted from powdered rock or soil. The presence or absence of organic compounds in these layers is of great interest since such an in situ search for this type of record has not been successfully implemented since the mid-60s Viking GCMS experiments. However, regardless of the outcome of the analysis for organics, the abundance and isotopic composition of thermally evolved inorganic compounds should also provide a rich data set to complement the mineralogical and elemental information provided by other MSL instruments. In addition, these evolved gas analysis (EGA) experiments will help test sedimentary models proposed by Malin and Edgett (2000) and then further developed by Milliken et al (2010) for Gale Crater. In the SAM EGA experiments the evolution temperatures of H2O, CO2, SO2, O2, or other simple compounds as the samples are heated in a helium stream to 1000 C provides information on mineral types and their associations. The isotopic composition of O, H, C, and S can be precisely determined in several evolved compounds and compared with the present day atmosphere. Such SAM results might be able to test mineralogical evidence of changing sedimentary and alteration processes over an extended period of time. For example, Bibring et al (2006) have suggested such a major shift from early nonacidic to later acidic alteration. We will illustrate through a variety of evolved gas experiments implemented under SAM-like gas flow and temperature ramp conditions on terrestrial analog minerals on high fidelity Sam breadboards the type of chemical information we expect SAM to provide.

Mahaffy, Paul↗
NASA NTRS2012

Miniaturized Hollow-Waveguide Gas Correlation Radiometer (GCR) for Trace Gas Detection in the Martian Atmosphere

Gas correlation radiometry (GCR) has been shown to be a sensitive and versatile method for detecting trace gases in Earth's atmosphere. Here, we present a miniaturized and simplified version of this instrument capable of mapping multiple trace gases and identifying active regions on the Mars surface. Reduction of the size and mass of the GCR instrument has been achieved by implementing a lightweight, 1 mm inner diameter hollow-core optical fiber (hollow waveguide) for the gas correlation cell. Based on a comparison with an Earth orbiting CO2 gas correlation instrument, replacement of the 10 meter mUltipass cell with hollow waveguide of equivalent pathlength reduces the cell mass from approx 150 kg to approx 0.5 kg, and reduces the volume from 1.9 m x 1.3 m x 0.86 m to a small bundle of fiber coils approximately I meter in diameter by 0.05 m in height (mass and volume reductions of >99%). This modular instrument technique can be expanded to include measurements of additional species of interest including nitrous oxide (N2O), hydrogen sulfide (H2S), methanol (CH3OH), and sulfur dioxide (SO2), as well as carbon dioxide (CO2) for a simultaneous measure of mass balance.

Wilson, Emily L.↗
NASA NTRS2012

Miniaturized Gas Correlation Radiometer for the Detection of Trace Gases in the Martian Atmosphere

We present a miniaturized and simplified version of a gas correlation radiometer (GCR) capable of simultaneously mapping multiple trace gases and identifying active regions on the Mars surface. Gas correlation radiometry (GCR) has been shown to be a sensitive and versatile method for detecting trace gases in Earth's atmosphere. Reduction of the size and mass of the GCR was achieved by implementing compact, light-weight 1 mm inner diameter hollow-core optical fibers (hollow waveguides) as the gas correlation cells. In a comparison with an Earth orbiting CO2 GCR instrument, exchanging the 10 m multipass cells with hollow waveguide gas correlation cells of equivalent path length reduces the mass from approximately 150 kg to approximately 0.5 kg, and reduces the volume from 1.9 m x 1.3 m x 0.86 m to a small bundle of fiber coils approximately 1 meter in diameter by 0.05 m in height (mass and volume reductions of greater than 99%). A unique feature of this instrument is its stackable module design, with a single module for each trace gas. Each of the modules is self-contained, and fundamentally identical; differing by the bandpass filter wavelength range and gas mixtures inside the hollow-waveguide absorption cells. The current configuration contains four stacked modules for simultaneous measurements of methane (CH4), formaldehyde (H2CO), water vapor (H2O), and deuterated water vapor (HDO) but could easily be expanded to include measurements of additional species of interest including nitrous oxide (N2O), hydrogen sulfide (H2S), methanol (CH3OH), and sulfur dioxide (SO2), as well as carbon dioxide (CO2) for a simultaneous measure of mass balance. Preliminary results indicate that a 1 ppb detection limit is possible for both formaldehyde and methane with one second of averaging. Using non-optimized components, we have demonstrated an instrument sensitivity equivalent to approximately 30 ppb for formaldehyde, and approximately 500 ppb for methane. We expect custom bandpass filters and 6 m long waveguides to significantly improve these promising results. Ongoing testing is being conducted on water vapor and deuterated water vapor.

Melroy, Hilary R.↗
NASA NTRS2011

Determining the Local Abundance of Martian Methane and its 13-C/l2-C and D/H Isotopic Ratios for Comparison with Related Gas and Soil Analysis on the 2011 Mars Science Laboratory (MSL) Mission

Understanding the origin of Martian methane will require numerous complementary measurements from both in situ and remote sensing investigations and laboratory work to correlate planetary surface geophysics with atmospheric dynamics and chemistry. Three instruments (Quadrupole Mass Spectrometer (QMS), Gas Chromatograph (GC) and Tunable Laser Spectrometer (TLS)) with sophisticated sample handling and processing capability make up the Sample Analysis at Mars (SAM) analytical chemistry suite on NASA s 2011 Mars Science Laboratory (MSL) Mission. Leveraging off the SAM sample and gas processing capability that includes methane enrichment, TLS has unprecedented sensitivity for measuring absolute methane (parts-per-trillion), water, and carbon dioxide abundances in both the Martian atmosphere and evolved from heated soil samples. In concert with a wide variety of associated trace gases (e.g. SO2, H2S, NH3, higher hydrocarbons, organics, etc.) and other isotope ratios measured by SAM, TLS will focus on determining the absolute abundances of methane, water and carbon dioxide, and their isotope ratios: 13C/12C and D/H in methane; 13C/12C and 18O/17O/16O in carbon dioxide; and 18O/17O/16O and D/H in water. Measurements near the MSL landing site will be correlated with satellite (Mars Express, Mars 2016) and ground-based observations.

Webster, Christopher R.↗
NASA NTRS2012

Global and Regional Seasonal Variability of Mid-Tropospheric CO2 as Measured by the Atmospheric Infrared Sounder (AIRS)

The Atmospheric Infrared Sounder (AIRS) is a hyperspectral infrared instrument on the Earth Observing System (EOS) Aqua Spacecraft, launched on May 4, 2002 into a near polar sun-synchronous orbit. AIRS has 2378 infrared channels ranging from 3.7 ?m to 15.4 ?m and a 13.5 km footprint at nadir. AIRS, in conjunction with the Advanced Microwave Sounding Unit (AMSU), produces temperature profiles with 1K/km accuracy on a global scale, as well as water vapor profiles and trace gas amounts for CO2, CO, SO2, O3 and CH4. AIRS CO2 climatologies have been shown to be useful for identifying anomalies associated with geophysical events such as El Nino-Southern Oscillation or Madden-Julian oscillation. In this study, monthly representations of mid-tropospheric CO2 are constructed from 10 years of AIRS Version 5 monthly Level 3 data. We compare the AIRS mid-tropospheric CO2 representations to ground-based measurements from the Scripps and National Oceanic and Atmospheric Administration Climate Modeling and Diagnostics Laboratory (NOAA CMDL) ground networks to better understand the phase lag of the CO2 seasonal cycle between the surface and middle troposphere. Results show only a small phase lag in the tropics that grows to approximately two months in the northern latitudes.

satellite↗
NASA NTRS2013

Carbon and Sulfur Isotopic Composition of Rocknest Soil as Determined with the Sample Analysis at Mars(SAM) Quadrupole Mass Spectrometer

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity rover got its first taste of solid Mars in the form of loose, unconsolidated materials (soil) acquired from an aeolian bedform designated Rocknest. Evolved gas analysis (EGA) revealed the presence of H2O as well as O-, C- and S-bearing phases in these samples. CheMin did not detect crystalline phases containing these gaseous species but did detect the presence of X-ray amorphous materials. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can provide clues to the nature and/or mineralogy of volatile-bearing phases through examination of temperatures at which gases are evolved from solid samples. In addition, the isotopic composition of these gases, particularly when multiple sources contribute to a given EGA curve, may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from Rocknest soil samples as measured with SAM's quadrupole mass spectrometer (QMS).

Franz, H. B.↗
NASA NTRS2013

Data from the Mars Science Laboratory CheMin XRD/XRF Instrument

The CheMin instrument on the Mars Science Laboratory (MSL) rover Curiosity uses a Co tube source and a CCD detector to acquire mineralogy from diffracted primary X-rays and chemical information from fluoresced X-rays. CheMin has been operating at the MSL Gale Crater field site since August 5, 2012 and has provided the first X-ray diffraction (XRD) analyses in situ on a body beyond Earth. Data from the first sample collected, the Rocknest eolian soil, identify a basaltic mineral suite, predominantly plagioclase (approx.An50), forsteritic olivine (approx.Fo58), augite and pigeonite, consistent with expectation that detrital grains on Mars would reflect widespread basaltic sources. Minor phases (each <2 wt% of the crystalline component) include sanidine, magnetite, quartz, anhydrite, hematite and ilmenite. Significantly, about a third of the sample is amorphous or poorly ordered in XRD. This amorphous component is attested to by a broad rise in background centered at approx.27deg 2(theta) (Co K(alpha)) and may include volcanic glass, impact glass, and poorly crystalline phases including iron oxyhydroxides; a rise at lower 2(theta) may indicate allophane or hisingerite. Constraints from phase chemistry of the crystalline components, compared with a Rocknest bulk composition from the APXS instrument on Curiosity, indicate that in sum the amorphous or poorly crystalline components are relatively Si, Al, Mg-poor and enriched in Ti, Cr, Fe, K, P, S, and Cl. All of the identified crystalline phases are volatile-free; H2O, SO2 and CO2 volatile releases from a split of this sample analyzed by the SAM instrument on Curiosity are associated with the amorphous or poorly ordered materials. The Rocknest eolian soil may be a mixture of local detritus, mostly crystalline, with a regional or global set of dominantly amorphous or poorly ordered components. The Rocknest sample was targeted by MSL for "first time analysis" to demonstrate that a loose deposit could be scooped, sieved to <150 microns, and delivered to instruments in the body of the rover. A drilled sample of sediment in outcrop is anticipated. At the time of writing this abstract, promising outcrops are in range and this talk will provide an update on data collected with the CheMin instrument.

Vaniman, David↗
NASA NTRS2013

Characterizing the Phyllosilicates and Amorphous Phases Found by MSL Using Laboratory XRD and EGA Measurements of Natural and Synthetic Materials

The Curiosity Rover landed on the Peace Vallis alluvial fan in Gale crater on August 5, 2012. A primary mission science objective is to search for past habitable environments, and, in particular, to assess the role of past water. Identifying the minerals and mineraloids that result from aqueous alteration at Gale crater is essential for understanding past aqueous processes at the MSL landing site and hence for interpreting the site's potential habitability. X-ray diffraction (XRD) data from the CheMin instrument and evolved gas analyses (EGA) from the SAM instrument have helped the MSL science team identify phases that resulted from aqueous processes: phyllosilicates and amorphous phases were measure in two drill samples (John Klein and Cumberland) obtained from the Sheepbed Member, Yellowknife Bay Fm., which is believed to represent a fluvial-lacustrine environment. A third set of analyses was obtained from scoop samples from the Rocknest sand shadow. Chemical data from the APXS instrument have helped constrain the chemical compositions of these secondary phases and suggest that the phyllosilicate component is Mg-enriched and the amorphous component is Fe-enriched, relatively Si-poor, and S- and H-bearing. To refine the phyllosilicate and amorphous components in the samples measured by MSL, we measured XRD and EGA data for a variety of relevant natural terrestrial phyllosilicates and synthetic mineraloids in laboratory testbeds of the CheMin and SAM instruments. Specifically, Mg-saturated smectites and vermiculites were measured with XRD at low relative humidity to understand the behavior of the 001 reflections under Mars-like conditions. Our laboratory XRD measurements suggest that interlayer cation composition affects the hydration state of swelling clays at low RH and, thus, the 001 peak positions. XRD patterns of synthetic amorphous materials, including allophane, ferrihydrite, and hisingerite were used in full-pattern fitting (FULLPAT) models to help determine the types and abundances of amorphous phases in the martian rocks and sand shadow. These models suggest that the rocks and sand shadow are composed of approx 30% amorphous phases. Sulfate-adsorbed allophane and ferrihydrite were measured by EGA to further understand the speciation of the sulfur present in the amorphous component. These data indicate that sulfate adsorbed onto the surfaces of amorphous phases could explain a portion of the SO2 evolution in the Rocknest SAM data. The additional constraints placed on the mineralogy and chemistry of the aqueous alteration phases through our laboratory measurements can help us better understand the nature of the fluids that affected the different samples and devise a history of aqueous alteration for the Sheepbed Member of the Yellowknife Bay Fm. at Gale crater.

Rampe, Elizabeth B.↗
NASA NTRS2014

Evaluating the Adsorptive Capabilites of Chemsorb 1000 and Chemsorb 1425

The removal of trace contaminants from spacecraft cabin air is necessary for crew health and comfort during long duration space exploration missions. The air revitalization technologies used in these future exploration missions will evolve from current ISS ISS State-of-Art (SOA) and is being designed and tested by the Advanced Exploration Systems (AES) Program's Atmosphere Resource Recovery and Environmental Monitoring (ARREM) project. The ARREM project is working to mature optimum atmosphere revitalization and environmental monitoring system architectures to enable exploration beyond Lower Earth Orbit (LEO). The Air Revitalization Lab at KSC is one of six NASA field centers participating in the ARREM that specializes in adsorbent and catalyst characterization with simulated spacecraft gas streams using combinations of pressure, O2 partial pressure, CO2 partial pressure, and humidity that are representative of a range of anticipated cabin atmospheric conditions and loads. On board ISS, the Trace Contaminant Control Subassembly (TCCS) provides active control of trace contaminants from the cabin atmosphere utilizing physical adsorption, thermal catalytic oxidation, and chemical adsorption processes. High molecular weight contaminants and ammonia (NH3) are removed a granular activated carbon treated with approx. 10% by weight phosphoric acid (H3PO4) (B-S Type 3032 4×6 mesh), which is expendable and is periodically refurbished. The Type 3032 granular activated carbon bed is no longer commercially available and therefore it is important to characterize the efficiency and capacity of commercially available NH3 sorbents. This paper describes the characterization of two Molecular Products LTD activated carbons: Chemsorb 1000 and Chemsorb 1425. Untreated activated carbons (e.g. Chemsorb 1000) remove contaminants by physisorption, which concentrates the contaminant within the pores of the carbon while letting air to pass through the sorbent4. Low molecular weight or polar gases (e.g. HCl, SO2, formaldehyde, and NH3) are not removed by physisorption and typically require chemisorption for removal. Treated activated carbons (e.g. Chemsorb 1425) are impregnated with a a chemical agent (e.g. phosphoric acid) that reacts with those gases, converting them to solids or salts within the carbon and removes them from the air stream. This process occurs via neutralization or catalysis reactions and adsorption capacity is exhaustedwhen the available impregnated chemicals are consumed. Moisture affects removal performance since adsorption sites within the pores are filled with water. The performance of impregnated carbons may be enhanced by moisture content because the mechanisms of contaminant removal are chemical reactions that occur in reagents contained within the pores. The adsorptive capacity data (mol/kg) of Chemsorb 1000 and 1425 for gas mixtures (ethanol, acetone, toluene, acetaldehyde, dichloromethane, and xylene) was measured with 40% relative humidity at 23 deg C air temperature. The adsorptive capacity data (mol/kg) of Chemsorb 1425 was measured using NH3 gas streams.

adsorptive capacities↗
NASA NTRS2013

A Multimodel Assessment of the Influence of Regional Anthropogenic Emission Reductions on Aerosol Direct Radiative Forcing and the Role of Intercontinental Transport

In this study, we assess changes of aerosol optical depth (AOD) and direct radiative forcing (DRF) in response to the reduction of anthropogenic emissions in four major pollution regions in the Northern Hemisphere by using results from nine global models in the framework of the Hemispheric Transport of Air Pollution (HTAP). DRF at top of atmosphere (TOA) and surface is estimated based on AOD results from the HTAP models and AOD-normalized DRF (NDRF) from a chemical transport model. The multimodel results show that, on average, a 20% reduction of anthropogenic emissions in North America, Europe, East Asia, and South Asia lowers the global mean AOD (all-sky TOA DRF) by 9.2% (9.0%), 3.5% (3.0%), and 9.4% (10.0%) for sulfate, particulate organic matter (POM), and black carbon (BC), respectively. Global annual average TOA all-sky forcing efficiency relative to particle or gaseous precursor emissions from the four regions (expressed as multimodel mean +/- one standard deviation) is -3.5 +/-0.8, -4.0 +/- 1.7, and 29.5+/-18.1mW / sq m per Tg for sulfate (relative to SO2), POM, and BC, respectively. The impacts of the regional emission reductions on AOD and DRF extend well beyond the source regions because of intercontinental transport (ICT). On an annual basis, ICT accounts for 11 +/- 5% to 31 +/- 9% of AOD and DRF in a receptor region at continental or subcontinental scale, with domestic emissions accounting for the remainder, depending on regions and species. For sulfate AOD, the largest ICT contribution of 31 +/- 9% occurs in South Asia, which is dominated by the emissions from Europe. For BC AOD, the largest ICT contribution of 28 +/- 18% occurs in North America, which is dominated by the emissions from East Asia. The large spreads among models highlight the need to improve aerosol processes in models, and evaluate and constrain models with observations.

Europe↗
NASA NTRS2013

Stratospheric Ozone Response in Experiments G3 and G4 of the Geoengineering Model Intercomparison Project (GeoMIP)

Geoengineering with stratospheric sulfate aerosols has been proposed as a means of temporarily cooling the planet, alleviating some of the side effects of anthropogenic CO2 emissions. However, one of the known side effects of stratospheric injections of sulfate aerosols is a decrease in stratospheric ozone. Here we show results from two general circulation models and two coupled chemistry climate models that have simulated stratospheric sulfate aerosol geoengineering as part of the Geoengineering Model Intercomparison Project (GeoMIP). Changes in photolysis rates and upwelling of ozone-poor air in the tropics reduce stratospheric ozone, suppression of the NOx cycle increases stratospheric ozone, and an increase in available surfaces for heterogeneous chemistry modulates reductions in ozone. On average, the models show a factor 20-40 increase of the sulfate aerosol surface area density (SAD) at 50 hPa in the tropics with respect to unperturbed background conditions and a factor 3-10 increase at mid-high latitudes. The net effect for a tropical injection rate of 5 Tg SO2 per year is a decrease in globally averaged ozone by 1.1-2.1 DU in the years 2040-2050 for three models which include heterogeneous chemistry on the sulfate aerosol surfaces. GISS-E2-R, a fully coupled general circulation model, performed simulations with no heterogeneous chemistry and a smaller aerosol size; it showed a decrease in ozone by 9.7 DU. After the year 2050, suppression of the NOx cycle becomes more important than destruction of ozone by ClOx, causing an increase in total stratospheric ozone. Contribution of ozone changes in this experiment to radiative forcing is 0.23 W m-2 in GISS-E2-R and less than 0.1 W m-2 in the other three models. Polar ozone depletion, due to enhanced formation of both sulfate aerosol SAD and polar stratospheric clouds, results in an average 5 percent increase in calculated surface UV-B.

aerosol↗
NASA NTRS2014

Carbon and Sulfur Isotopic Composition of Yellowknife Bay Sediments: Measurements by the Sample Analysis at Mars (SAM) Quadrupole Mass Spectrometer

Since landing at Gale Crater in Au-gust 2012, the Sample Analysis at Mars (SAM) instru-ment suite on the Mars Science Laboratory (MSL) “Curiosity” rover has analyzed solid samples from the martian regolith in three locations, beginning with a scoop of aeolian deposits from the Rocknest (RN) sand shadow. Curiosity subsequently traveled to Yellowknife Bay, where SAM analyzed samples from two separate holes drilled into the Sheepbed Mudstone, designated John Klein (JK) and Cumberland (CB). Evolved gas analysis (EGA) of all samples revealed the presence of H2O as well as O-, C- and S-bearing phas-es, in most cases at abundances below the detection limit of the CheMin instrument. In the absence of definitive mineralogical identification by CheMin, SAM EGA data can help provide clues to the mineralogy of volatile-bearing phases through examination of tem-peratures at which gases are evolved from solid sam-ples. In addition, the isotopic composition of these gas-es may be used to identify possible formation scenarios and relationships between phases. Here we report C and S isotope ratios for CO2 and SO2 evolved from the JK and CB mudstone samples as measured with SAM’s quadrupole mass spectrometer (QMS) and draw com-parisons to RN.

Franz, H. B.↗
NASA NTRS2013

Emissions Estimation from Satellite Retrievals: a Review of Current Capability

Since the mid-1990s a new generation of Earth-observing satellites has been able to detect tropospheric air pollution at increasingly high spatial and temporal resolution. Most primary emitted species can be measured by one or more of the instruments. This review article addresses the question of how well we can relate the satellite measurements to quantification of primary emissions and what advances are needed to improve the usability of the measurements by U.S. air quality managers. Built on a comprehensive literature review and comprising input by both satellite experts and emission inventory specialists, the review identifies several targets that seem promising: large point sources of NOx and SO2, species that are difficult to measure by other means (NH3 and CH4, for example), area sources that cannot easily be quantified by traditional bottom-up methods (such as unconventional oil and gas extraction, shipping, biomass burning, and biogenic sources), and the temporal variation of emissions (seasonal, diurnal, episodic). Techniques that enhance the usefulness of current retrievals (data assimilation, oversampling, multi-species retrievals, improved vertical profiles, etc.) are discussed. Finally, we point out the value of having new geostationary satellites like GEO-CAPE and TEMPO over North America that could provide measurements at high spatial (few km) and temporal (hourly) resolution.

air quality↗
NASA NTRS2014

SAM-Like Evolved Gas Analyses of Phyllosilicate Minerals and Applications to SAM Analyses of the Sheepbed Mudstone, Gale Crater, Mars

While in Yellowknife Bay, the Mars Science Laboratory Curiosity rover collected two drilled samples, John Klein (hereafter "JK") and Cumberland ("CB"), from the Sheepbed mudstone, as well as a scooped sample from the Rocknest aeolian bedform ("RN"). These samples were sieved by Curiosity's sample processing system and then several subsamples of these materials were delivered to the Sample Analysis at Mars (SAM) instrument suite and the CheMin X-ray diffraction/X-ray fluorescence instrument. CheMin provided the first in situ X-ray diffraction-based evidence of clay minerals on Mars, which are likely trioctahedral smectites (e.g., Fe-saponite) and comprise ~20 wt% of the mudstone samples [1]. SAM's evolved gas analysis (EGA) mass spectrometry analyses of JK and CB subsamples, as well as RN subsamples, detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases evolved during pyrolysis. The identity of evolved gases and temperature( s) of evolution can augment mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or those phases difficult to characterize with XRD (e.g., X-ray amorphous phases). Here we will focus on the SAM H2O data, in the context of CheMin analyses, and comparisons to laboratory SAM-like analyses of several phyllosilicate minerals including smectites.

McAdam, A. C.↗
NASA NTRS2014

Global and Regional Impacts of HONO on the Chemical Composition of Clouds and Aerosols

Recently, realistic simulation of nitrous acid (HONO) based on the HONO/NO(sub x) ratio of 0.02 was found to have a significant impact on the global budgets of HO(sub x) (OH + HO2) and gas phase oxidation products in polluted regions, especially in winter when other photolytic sources are of minor importance. It has been reported that chemistry-transport models underestimate sulphate concentrations, mostly during winter. Here we show that simulating realistic HONO levels can significantly enhance aerosol sulphate (S(VI)) due to the increased formation of H2SO4. Even though in-cloud aqueous phase oxidation of dissolved SO2 (S(IV)) is the main source of S(VI), it appears that HONO related enhancement of H2O2 does not significantly affect sulphate because of the predominantly S(IV) limited conditions, except over eastern Asia. Nitrate is also increased via enhanced gaseous HNO3 formation and N2O5 hydrolysis on aerosol particles. Ammonium nitrate is enhanced in ammonia-rich regions but not under ammonia-limited conditions. Furthermore, particle number concentrations are also higher, accompanied by the transfer from hydrophobic to hydrophilic aerosol modes. This implies a significant impact on the particle lifetime and cloud nucleating properties. The HONO induced enhancements of all species studied are relatively strong in winter though negligible in summer. Simulating realistic HONO levels is found to improve the model measurement agreement of sulphate aerosols, most apparent over the US. Our results underscore the importance of HONO for the atmospheric oxidizing capacity and corroborate the central role of cloud chemical processing in S(IV) formation.

HONO↗
NASA NTRS2015

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.↗
NASA NTRS2015

Mineralogical Indicators for Climate Change on Mars: Evidence from Landed Missions

Mineralogical and geochemical data returned by a flotilla of Mars orbiters and landers over the past 10 years has substantially enhanced our understanding on the evolution of the atmosphere and climate. Instruments onboard Mars Express and MRO discovered widespread deposits of phyllosilicates that formed during the Noachian followed by formation of sulfates into the Hesperian. The formation of extensive valley networks along with these layered deposits of phyllosilicates and sulfates during the late Noachian/ early Hesperian indicate a past martian climate that was capable of maintaining liquid water at the surface. The planet's climate changed substantially after these early 'episodes' of water and very little aqueous alteration has occurred over the past 3.5 Gyrs . A key to understanding Mars past climate is to identify, characterize, and age date secondary minerals that have formed by reaction with volatile compounds, e.g., H2O, CO2, SO2. Here, we summarize the detection of secondary minerals at the four landing sites visited over the past 10 years. We also provide potential pathways for their formation and implications for past climate change on Mars.

Ming, D. W.↗