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Detection of Organic Constituents Including Chloromethylpropene in the Analyses of the ROCKNEST Drift by Sample Analysis at Mars (SAM)

key challenge in assessing the habitability of martian environments is the detection of organic matter - a requirement of all life as we know it. The Curiosity rover, which landed on August 6, 2012 in Gale Crater of Mars, includes the Sample Analysis at Mars (SAM) instrument suite capable of in situ analysis of gaseous organic components thermally evolved from sediment samples collected, sieved, and delivered by the MSL rover. On Sol 94, SAM received its first solid sample: scooped sediment from Rocknest that was sieved to <150 m particle size. Multiple 10-40 mg portions of the scoop #5 sample were delivered to SAM for analyses. Prior to their introduction, a blank (empty cup) analysis was performed. This blank served 1) to clean the analytical instrument of SAMinternal materials that accumulated in the gas processing system since integration into the rover, and 2) to characterize the background signatures of SAM. Both the blank and the Rocknest samples showed the presence of hydrocarbon components.

Eigenbrode, J. L.↗

The Investigation of Chlorates as a Possible Source of Oxygen and Chlorine Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detect-ed O2 and HCl gas releases from the Rocknest (RN) eolian bedform and the John Klein (JK) and Cumberland (CB) drill hole materials in Gale Crater. Chlorinated hydrocarbons have also been detected by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS). These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander’s Wet Chemistry Laboratory (WCL) suggesting perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate does cause O2 release temperatures to be closer match to the SAM O2 release data but more work is required in evaluating the catalytic effects of Fe mineralogy on perchlorate decomposition. Chlorates (ClO3-) are relevant Mars materials and potential O2 and Cl sources. The objective of this work is to evaluate the thermal decomposition of select chlorate (ClO3-) salts as possible sources of the O2 and HCl releases in the Gale Crater materials.

Sutter, B.↗

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.↗

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.↗

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.↗

Initial SAM Calibration Gas Experiments on Mars: Quadrupole Mass Spectrometer Results and Implications

The Sample Analysis at Mars (SAM) instrument suite of the Mars Science Laboratory (MSL) Curiosity rover is equipped to analyze both martian atmospheric gases and volatiles released by pyrolysis of solid surface materials, with target measurements including chemical and isotopic composition (Mahaffy et al., 2012). To facilitate assessment of instrument performance and validation of results obtained on Mars, SAM houses a calibration cell containing CO2, Ar, N2, Xe, and several fluorinated hydrocarbon compounds (Franz et al., 2014; Mahaffy et al., 2012). This report describes the first two experiments utilizing this calibration cell on Mars and gives results from analysis of data acquired with the SAM Quadrupole Mass Spectrometer (QMS). These data support the accuracy of isotope ratios obtained with the QMS (Conrad et al., 2016; Mahaffy et al., 2013) and provide ground-truth for reassessment of analytical constants required for atmospheric measurements, which were reported in previous contributions (Franz et al., 2015, 2014). The most significant implication of the QMS data involves reinterpretation of pre-launch contamination previously believed to affect only CO abundance measurements (Franz et al., 2015) to affect N2 abundances, as well. The corresponding adjustment to the N2 calibration constant presented here brings the atmospheric volume mixing ratios for Ar and N2 retrieved by SAM into closer agreement with those reported by the Viking mission (Owen et al., 1977; Oyama and Berdahl, 1977).

Sample Analysis at Mars Investigation↗

POIWG 46 Space Acceleration Measurement System (SAMS) Splinter Session

This splinter session presentation will provide users with an overview of the Space Acceleration Measurement System (SAMS) capabilities and services. It will depict the current configuration of SAMS on the International Space Station (ISS) and show current and future planned allocation of SAMS resources on the ISS. This presentation has a items seeking feedback or resolution for the first wireless deployment of SAMS sensors on the space station.

Hrovat, Ken↗

A Suite of High-Resolution Atmospheric Carbon Dioxide Simulations in Support of the OCO-3 Snapshot Area Mapping (SAM) Mode Observation: PSU-WRF, CSU-OLAM and NASA GEOS

Cities and power plants are responsible more than 70% of GHG emissions. The emissions from the subnational localized sources need to be accurately quantified and properly managed in order to achieve the Paris Climate Agreement goals. The accurate estimation of these emission is also crucial for assessing the capacity of natural sinks to uptake the carbon released into the atmosphere that ultimately defines our emission allowance for the 1.5 or 2.0 degree temperature goals. New data collected by the Orbiting Carbon Observatory 3 (OCO-3) Snapshot Area Mapping (SAM) observations should provide a tremendous new opportunity for us to study CO2 emissions from targeted large localized sources, such as cities, power plants and beyond. Since 2018 (prior to the OCO-3 launch), we have studied the observational strategies for the SAM mode observation in order to collect the useful data for estimating CO2 emissions from target sources. To maximize the benefit of the SAM mode observation data for quantifying CO2 emission, it is important to define how to observe the localized sources depending on the local environmental and emission specificities. We employ a suite of state-of-the-art CO2 modeling systems, such as PSU's WRF-CO2, CSU's OLAM and NASA's GEOS models. All of these CO2 modeling systems are prescribedwith the high-resolution fuel CO2 emission estimates from the ODIAC data product to achieve realistic urban CO2 variations. We focus on cities with established ground-based observation networks, such as Los Angeles, Indianapolis, and Paris. We have examined the urban emission signal detectability in response to the influence of local background conditions that can observed by the SAM and biospheric contributions that will be a new challenge for urban emission inverse estimation. Based on the results of our simulation experiments, we plan to propose city-specific observation strategies. Upon the availability of the OCO-3 data, we will attempt to estimate city emissions using inverse models. We also developed synthetic OCO-3 data using NASA's GEOS5 model, which should be useful to assess the utility of the OCO-3 data in combination with data collected by carbon satellites in other orbits, such as NASA's OCO-2 and Japanese GOSAT-1/2. The synthetic data also provide an opportunity to study the errors due to clouds and aerosols, which have been not fully studied in the past.

Oda, Tomohiro↗

The Influence of Mineralogy on Recovering Organic Acids from Mars Analogue Materials Using the One-Pot Derivatization Experiment on the Sample Analysis at Mars(SAM) Instrument Suite

The search for complex organic molecules on Mars, including important biomolecules such as amino acids and carboxylic acids, will require a chemical extraction and a derivatization step to transform these organic compounds into species that are sufficiently volatile to be detected by gas chromatography mass spectrometry (GCMS). We have developed a ''one-pot'' extraction and chemical derivatization protocol using N-methyl-N-(tert-butyldimethylsilyl) trifluoroacetamide (MTBSTFA) and dimethylformamide (DMF) for the Sample Analysis at Mars (SAM) experiment instrument suite on NASA's the Mars Science Laboratory (MSL) mission. The temperature and duration of the derivatization reaction, pre-concentration of chemical derivatives, and gas chromatographic separation parameters have been optimized under SAM instrument design constraints. MTBSTFA/DMF extraction and derivatization at 300 1C for several minutes of a variety of terrestrial Mars analog materials facilitated the detection of amino acids and carboxylic acids in a surface soil sample collected from the Atacama Desert and a carbonate-rich stromatolite sample from Svalbard. However, the rapid reaction of MTBSTFA with water in several analog materials that contained high abundances of hydrated minerals, and the possible deactivation of derivatized compounds by iron oxides, as detected by XRD/XRF using the CheMin field unit Terra, proved to be highly problematic for the direct extraction of organics using MTBSTFA. The combination of pyrolysis and two different wet-chemical derivatization methods employed by SAM should enable a wide range of organic compounds to be detected by GCMS if present on Mars.

MSL↗

Detection of Organics at Mars: How Wet Chemistry Onboard SAM Helps

For the first time in the history of space exploration, a mission of interest to astrobiology could be able to analyze refractory organic compounds in the soil of Mars. Wet chemistry experiment allow organic components to be altered in such a way that improves there detection either by releasing the compounds from sample matricies or by changing the chemical structure to be amenable to analytical conditions. The latter is particular important when polar compounds are present. Sample Analysis at Mars (SAM), on the Curiosity rover of the Mars Science Laboratory mission, has onboard two wet chemistry experiments: derivatization and thermochemolysis. Here we report on the nature of the MTBSTFA derivatization experiment on SAM, the detection of MTBSTFA in initial SAM results, and the implications of this detection.

astrobiology↗

SAM 2 Measurements of the Polar Stratospheric Aerosol, volume 2. April 1979 to October 1979

The Stratospheric Aerosol Measurement (SAM) II sensor is abroad the Earth orbiting Nimbus 7 spacecraft proving extinction measurements of the Antarctic and Arctic stratospheric aerosol with a vertical resolution of 1 km. Representative examples and weekly averages of aerosol data and corresponding temperature profiles for the time and place of each SAM II measurement (April 29, 1979, to October 27, 1979) is presented. Contours of aerosol extinction as a function of altitude and longitude or time were plotted and weekly aerosol optical depths were calculated. Seasonal variations and variations in space (altitude and longitude) for both polar regions are easily seen. Typical values of aerosol extinction at the SAM II wavelength of 1.0 micron for the time priod were 1 to 3 x 10 to the -4th power km -1 in the main stratospheric aerosol layer. Optical depths for the stratosphere were about 0.002. Polar stratospheric clouds at altitudes between the tropopause and 20 km were observed during the Antarctic winter at various times and locations. A ready-to-use format containing a representative sample of the second 6 months of data to be used in atmospheric and climatic studies is presented.

Mccormick, M. P.↗

SAM 2 measurements of the polar stratospheric aerosol. Volume 3: October 1979 to April 1980

The Stratospheric Aerosol Measurement (SAM) II sensor is aboard the Earth-orbiting Nimbus 7 spacecraft providing extinction measurements of the Antarctic and Arctic stratospheric aerosol with a vertical resolution of 1 km. Representative examples and weekly averages of aerosol data and corresponding temperature profiles for the time and place of each SAM II measurement (Oct. 1979 through Apr. 1980) are presented. Contours of aerosol extinction as a function of altitude and longitude or time are plotted and weekly aerosol optical depths are calculated. Seasonal variations and variations in space (altitude and longitude) for both polar regions are easily seen. Typical values of aerosol extinction at the SAM II wavelength of 1.0 microns for this time period are 2 to 4 times .0001/km in the main stratospheric aerosol layer. Optical depths for the stratosphere are about 0.002 to 0.003, up slightly over normal background levels (due to the eruption of Sierra Negra, Nov. 1979). Polar stratospheric clouds at altitudes of about 22 km were observed during the Arctic winter. A ready-to-use format containing a representative sample of the third 6 months of data to be used in atmospheric and climatic studies is presented.

Mccormick, M. P.↗

A comparative study of aerosol extinction measurements made by the SAM II and SAGE satellite experiments

SAM II and SAGE are two satellite experiments designed to measure stratospheric aerosol extinction using the technique of solar occultation or limb extinction. Although each sensor is mounted aboard a different satellite, there are occasions when their measurement locations are nearly coincident, thereby providing opportunities for a measurement comparison. In this paper, the aerosol extinction profiles and daily contour plots for some of these events in 1979 are reported. The comparisons shown in this paper demonstrate that SAM II and SAGE are producing similar aerosol extinction profiles within their measurement errors and that since SAM II has been previously validated, these results show the validity of the SAGE aerosol measurements.

Yue, G. K.↗

SAM 2 and SAGE data management and processing

The data management and processing supplied by ST Systems Corporation (STX) for the Stratospheric Aerosol Measurement 2 (SAM 2) and Stratospheric Aerosol and Gas Experiment (SAGE) experiments for the years 1983 to 1986 are described. Included are discussions of data validation, documentation, and scientific analysis, as well as the archival schedule met by the operational reduction of SAM 2 and SAGE data. Work under this contract resulted in the archiving of the first seven years of SAM 2 data and all three years of SAGE data. A list of publications and presentations supported was also included.

Osborn, M. T.↗

Validation of SAM 2 and SAGE satellite

Presented are the results of a validation study of data obtained by the Stratospheric Aerosol and Gas Experiment I (SAGE I) and Stratospheric Aerosol Measurement II (SAM II) satellite experiments. The study includes the entire SAGE I data set (February 1979 - November 1981) and the first four and one-half years of SAM II data (October 1978 - February 1983). These data sets have been validated by their use in the analysis of dynamical, physical and chemical processes in the stratosphere. They have been compared with other existing data sets and the SAGE I and SAM II data sets intercompared where possible. The study has shown the data to be of great value in the study of the climatological behavior of stratospheric aerosols and ozone. Several scientific publications and user-oriented data summaries have appeared as a result of the work carried out under this contract.

Kent, G. S.↗

Comparative studies of aerosol extinction measurements made by the SAM II and SAGE II satellite experiments

Results from the Stratospheric Aerosol Measurement (SAM) II and Stratospheric Aerosol and Gas Experiment (SAGE) II are compared for measurement locations which are coincident in time and space. At 1.0 micron, the SAM II and SAGE II aerosol extinction profiles are similar within their measurement errors. In addition, sunrise and sunset aerosol extinction data at four different wavelengths are compared for occasions when the SAGE II and SAM II measurements are nearly coincident in space and about 12 hours apart.

Yue, Glenn K.↗

SAM II and lidar aerosol profile comparisons during AASE

The NASA Langley Research Center aerosol lidar system was one of several instruments that flew aboard a DC-8 during the Airborne Arctic Stratospheric Expedition. Several of the Stratospheric Aerosol Measurement II (SAM II) altitude profiles of aerosol extinction were close enough in time and space to allow for intercomparison with the lidar measurements of aerosol backscatter. Comparisons between three SAM II 1.0 micron aerosol extinction profiles and analogous profiles inferred from nearly simultaneous airborne lidar measurements are discussed. The other two comparisons show the first near-simultaneous SAM II/lidar measurements of a polar stratospheric cloud (PSC). The comparison made well within the edge of a relatively homogeneous PSC layer was also good, especially using an extinction-to-backscatter model derived from in situ PSC particle size measurements.

Osborn, M. T.↗

Denitrification of the polar winter stratosphere - Implications of SAM II cloud formation temperatures

The SAM II extinction profiles and the associated temperature profiles are used to determine the amount of denitrification of the winter polar stratospheres. Clear evidence of the denitrification process in the Antarctic data is seen. There are indications in the Arctic data that denitrification mechanisms may be at work there also. At the latitudes observed by the SAM II satellite system, denitrification begins before the formation of extensive ice clouds and may be due to sedimentation of nitric acid particles. However, the possibility of dinitrification by type II PSCs at latitudes not observed by SAM II cannot be excluded.

Hamill, Patrick↗