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Mahaffy, P. R.

Publications and source records attributed to Mahaffy, P. R..

At least 55 records · Page 3

It's a Trap! A Review of MOMA and Other Ion Traps in Space or Under Development

Since the Viking Program, quadrupole mass spectrometer (QMS) instruments have been used to explore a wide survey of planetary targets in our solar system, including (from the inner to outer reaches): Venus (Pioneer); our moon (LADEE); Mars (Viking, Phoenix, and Mars Science Laboratory); and, Saturns largest moon Titan (Cassini-Huygens). More recently, however, ion trap mass spectrometer (ITMS) instruments have found a niche as smaller, versatile alternatives to traditional quadrupole mass analyzers, capable of in situ characterization of planetary environments and the search for organic matter. For example, whereas typical QMS systems are limited to a mass range up to 500 Da and normally require multiple RF frequencies and pressures of less than 10(exp -6) mbar for optimal operation, ITMS instruments commonly reach upwards of 1000 Da or more on a single RF frequency, and function in higher pressure environments up to 10(exp -3) mbar.

ion trap↗

The Investigation of Magnesium Perchlorate/Iron Phase-mineral Mixtures 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 Cumber-land (CB) drill hole materials in Gale Crater (Fig. 1) [1,2]. Chlorinated hydrocarbons have also been detect-ed by the SAM quadrupole mass spectrometer (QMS) and gas chromatography/mass spectrometer (GCMS) [1,2,3,4]. These detections along with the detection of perchlorate (ClO4(-)) by the Mars Phoenix Lander's Wet Chemistry Laboratory (WCL) [5] suggesting perchlo-rate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of individual per-chlorates has yet to provide an unequivocal tempera-ture match to the SAM O2 and HCl release data [1,2]. Catalytic reactions of Fe phases in the Gale Crater ma-terial with perchlorates can potentially reduce the de-composition temperatures of these otherwise pure per-chlorate/chlorate phases [e.g., 6,7]. Iron mineralogy found in the Rocknest materials when mixed with Ca-perchlorate was found to cause O2 release temperatures to be closer match to the SAM O2 release data and enhance HCl gas releases. Exact matches to the SAM data has unfortnunately not been achieved with Ca-perchlorate-Fe-phase mixtures [8]. The effects of Fe-phases on magnesium perchlorate thermal decomposi-tion release of O2 and HCl have not been evaluated and may provide improved matches to the SAM O2 and HCl release data. This work will evaluate the thermal decomposition of magnesium perchlorate mixed with fayalite/magnetite phase and a Mauna Kea palagonite (HWMK 919). The objectives are to 1) summarize O2 and HCl releases from the Gale Crater materials, and 2) evaluate the O2 and HCl releases from the Mg-perchlorate + Fe phase mixtures to determine if Mg-perchlorate mixed with Fe-phases can explain the Gale Crater O2 and HCl releases.

Sutter, B.↗

Searching for Reduced Carbon on the Surface of Mars: The SAM Combustion Experiment

The search for reduced carbon has been a major focus of past and present missions to Mars. Thermal evolved gas analysis was used by the Viking and Phoenix landers and is currently in use by the Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) to characterize volatiles evolved from solid samples, including those associated with reduced organic species. SAM has the additional capability to perform a combustion experiment, in which a sample of Mars regolith is heated in the presence of oxygen and the composition of the evolved gases is measured using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS) [1]. Organics detection on the Martian surface has been complicated by oxidation and destruction during heating by soil oxidants [2], including oxychlorine compounds, and terrestrial organics in the SAM background contributed by one of the SAM wet chemistry reagents MTBSTFA (N-Methyl-N-tertbutyldimethylsilyl- trifluoroacetamide) [3,4]. Thermal Evolved Gas Analysis (TEGA) results from Phoenix show a mid temperature CO2 release between 400 C - 680 C speculated to be carbonate, CO2 adsorbed to grains, or combustion of organics by soil oxidants [5]. Low temperature CO2 evolutions (approx. 200 C - 400 C) were also present at all three sites in Gale Crater where SAM Evolved Gas Analysis (EGA) was performed, and potential sources include combustion of terrestrial organics from SAM, as well as combustion and/or decarboxylation either indigenous martian or exogenous organic carbon [4,6]. By performing an experiment to intentionally combust all reduced materials in the sample, we hope to compare the bulk abundance of CO2 and other oxidized species evolved by combustion to that evolved during an EGA experiment to estimate how much CO2 could be contributed by reduced carbon sources. In addition, C, O, and H isotopic compositions of CO2 and H2O measured by TLS can contribute information regarding the potential sources of these volatiles.

Stern, J. C.↗

Reduced and Oxidized Sulfur Compounds Detected by Evolved Gas Analyses of Materials from Yellowknife Bay, Gale Crater, Mars

Sulfate minerals have been directly detected or strongly inferred from several Mars datasets and indicate that aqueous alteration of martian surface materials has occurred. Indications of reduced sulfur phases (e.g., sulfides) from orbital and in situ investigations of martian materials have been fewer in number, but these phases are observed in martian meteorites and are likely because they are common minor phases in basaltic rocks. Here we discuss potential sources for the S-bearing compounds detected by the Mars Science Laboratory (MSL) Sample Analysis at Mars (SAM) instrument’s evolved gas analysis (EGA) experiments.

McAdam, A. C.↗

The Present Habitability Potential of Gale Crater: What We Have Learned So Far From Mars Science Laboratory

The Mars Science Laboratory mission has comprehensively interrogated the surface environment of Mars as it explores Gale Crater. Both chemical and physical attributes of the present environment have been measured over the course of the mission, enabling us to compare the present state of the martian surface with the environmental requirements of prokaryotic microbes. While this approach does not exclude the possibility of martian life that may have evolved to adapt to the present conditions, it is advantageous in that it allows us to evaluate environmental requirements of known life and also provide insight into the likelihood of forward contamination by Earth organisms with the comparison of their environmental requirements with the measured attributes of the environment at Gale Crater. We have already modeled a paleoenvironment with high habitability potential (HP) based upon chemistry, mineralogy and other geological evidence such as sedimentary structures and larger scale geomorphology [1]. In this report, we turn our attention to the present HP of the Yellowknife Bay area, including the importance of the physical environmental metrics such as atmospheric pressure, air and ground temperature, ionizing radiation, wind speed and direction, slope, etc.

Conrad, P. G.↗

Sulphur-bearing Compounds Detected by MSL SAM Evolved Gas Analysis of Materials from Yellowknife Bay, Gale Crater, Mars

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) analysed several subsamples of sample fines (<150 μm) from three sites in Yellowknife Bay, an aeolian bedform termed Rocknest (hereafter "RN") and two samples drilled from the Sheepbed mudstone at sites named John Klein ("JK") and Cumberland ("CB"). SAM's evolved gas analysis (EGA) mass spectrometry detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, OCS, CS2 and other trace gases. The identity of evolved gases and temperature (T) of evolution can support mineral detection by CheMin and place constraints on trace volatile-bearing phases present below the CheMin detection limit or difficult to characterize with XRD (e.g., X-ray amorphous phases). Here, we focus on potential constraints on phases that evolved SO2, H2S, OCS, and CS2 during thermal analysis.

McAdam, A. C.↗

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.↗

The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precision measurements of the abundance and carbon isotopic composition (delta C-13) of the evolved CO2 and hydrogen isotopic composition (delta D) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx. 550 C and above approx. 550 C.

Stern, J. C.↗

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.↗

Reconciling the Differences between the Measurements of CO2 Isotopes by the Phoenix and MSL Landers

Precise stable isotope measurements of the CO2 in the martian atmosphere have the potential to provide important constraints for our understanding of the history of volatiles, the carbon cycle, current atmospheric processes, and the degree of water/rock interaction on Mars. There have been several different measurements by landers and Earth based systems performed in recent years that have not been in agreement. In particular, measurements of the isotopic composition of martian atmospheric CO2 by the Thermal and Evolved Gas Analyzer (TEGA) instrument on the Mars Phoenix Lander and the Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) are in stark disagreement. This work attempts to use measurements of mass 45 and mass 46 of martian atmospheric CO2 by the SAM and TEGA instruments to search for agreement as a first step towards reaching a consensus measurement that might be supported by data from both instruments.

Niles, P. B.↗

Detection and Quantification of Nitrogen Compounds in the First Drilled Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL)

The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen-bearing compounds during the pyrolysis of surface materials at Yellowknife Bay in Gale Crater. Preliminary detections of nitrogen species include NO, HCN, ClCN, CH3CN, and TFMA (trifluoro-N-methyl-acetamide). Confirmation of indigenous Martian N-bearing compounds requires quantifying N contribution from the terrestrial derivatization reagents (e.g. N-methyl-N-tertbutyldimethylsilyltrifluoroacetamide, MTBSTFA and dimethylformamide, DMF) carried for SAM's wet chemistry experiment that contribute to the SAM background. Nitrogen species detected in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate, a compound that has also been identified by SAM in Mars solid samples.

Curiosity rover↗

The Combustion Experiment on the Sample Analysis at Mars (SAM) Instrument Suite on the Curiosity Rover

The combustion experiment on the Sample Analysis at Mars (SAM) suite on Curiosity will heat a sample of Mars regolith in the presence of oxygen and measure composition of the evolved gases using quadrupole mass spectrometry (QMS) and tunable laser spectrometry (TLS). QMS will enable detection of combustion products such as CO, CO2, NO, and other oxidized species, while TLS will enable precise measurements of the abundance and carbon isotopic composition (delta(sup 13)C) of the evolved CO2 and hydrogen isotopic composition (deltaD) of H2O. SAM will perform a two-step combustion to isolate combustible materials below approx.550 C and above approx.550 C. The combustion experiment on SAM, if properly designed and executed, has the potential to answer multiple questions regarding the origins of volatiles seen thus far in SAM evolved gas analysis (EGA) on Mars. Constraints imposed by SAM and MSL time and power resources, as well as SAM consumables (oxygen gas), will limit the number of SAM combustion experiments, so it is imperative to design an experiment targeting the most pressing science questions. Low temperature combustion experiments will primarily target the quantification of carbon (and nitrogen) contributed by SAM wet chemistry reagants MTBSTFA (N-Methyl-N-tert-butyldimethylsilyltrifluoroacetamide) and DMF (Dimethylformamide), which have been identified in the background of blank and sample runs and may adsorb to the sample while the cup is in the Sample Manipulation System (SMS). In addition, differences between the sample and "blank" may yield information regarding abundance and delta(sup 13)C of bulk (both organic and inorganic) martian carbon. High temperature combustion experiments primarily aim to detect refractory organic matter, if present in Cumberland fines, as well as address the question of quantification and deltaD value of water evolution associated with hydroxyl hydrogen in clay minerals.

Mars↗

Organic Molecules in the Sheepbed Mudstone, Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument on the Curiosity rover is designed to determine the inventory of organic and inorganic volatiles thermally released from solid samples using a combination of evolved gas analysis (EGA), gas chromatography mass spectrometry (GCMS), and tunable laser spectroscopy. Here we report on various chlorinated hydrocarbons (chloromethanes, chlorobenzene and dichloroalkanes) detected at elevated levels above instrument background at the Cumberland (CB) drill site, and discuss their possible sources.

Freissinet, C.↗

The Search for Ammonia in Martian Soils with Curiosity's SAM Instrument

Nitrogen is the second or third most abundant constituent of the Martian atmosphere [1,2]. It is a bioessential element, a component of all amino acids and nucleic acids that make up proteins, DNA and RNA, so assessing its availability is a key part of Curiosity's mission to characterize Martian habitability. In oxidizing desert environments it is found in nitrate salts that co-occur with perchlorates [e.g., 3], inferred to be widespread in Mars soils [4-6]. A Mars nitrogen cycle has been proposed [7], yet prior missions have not constrained the state of surface N. Here we explore Curiosity's ability to detect N compounds using data from the rover's first solid sample. Companion abstracts describe evidence for nitrates [8] and for nitriles (C(triple bond)N) [9]; we focus here on nonnitrile, reduced-N compounds as inferred from bonded N-H. The simplest such compound is ammonia (NH3), found in many carbonaceous chondrite meteorites in NH4(+) salts and organic compounds [e.g., 10].

Wray, James J.↗

Curiosity's Sample Analysis at Mars (SAM) Investigation: Overview of Results from the First 120 Sols on Mars

During the first 120 sols of Curiosity s landed mission on Mars (8/6/2012 to 12/7/2012) SAM sampled the atmosphere 9 times and an eolian bedform named Rocknest 4 times. The atmospheric experiments utilized SAM s quadrupole mass spectrometer (QMS) and tunable laser spectrometer (TLS) while the solid sample experiments also utilized the gas chromatograph (GC). Although a number of core experiments were pre-programmed and stored in EEProm, a high level SAM scripting language enabled the team to optimize experiments based on prior runs.

Mahaffy, P. R.↗

Integrated Results from Analysis of the Rocknest Aeolian Deposit by the Curiosity Rover

The Mars Science Laboratory Curiosity rover spent 45 sols (from sol 56-101) at an area called Rocknest (Fig. 1), characterizing local geology and ingesting its aeolian fines into the analytical instruments CheMin and SAM for mineralogical and chemical analysis. Many abstracts at this meeting present the contextual information and detailed data on these first solid samples analyzed in detail by Curiosity at Rocknest. Here, we present an integrated view of the results from Rocknest - the general agreement from discussions among the entire MSL Science Team.

Leshin, L. A.↗

Mars Atmospheric Escape Recorded by H, C and O Isotope Ratios in Carbon Dioxide and Water Measured by the Sam Tunable Laser Spectrometer on the Curiosity Rover

Stable isotope ratios in C, H, N, O and S are powerful indicators of a wide variety of planetary geophysical processes that can identify origin, transport, temperature history, radiation exposure, atmospheric escape, environmental habitability and biological activity [2]. For Mars, measurements to date have indicated enrichment in all the heavier isotopes consistent with atmospheric escape processes, but with uncertainty too high to tie the results with the more precise isotopic ratios achieved from SNC meteoritic analyses. We will present results to date of H, C and O isotope ratios in CO2 and H2O made to high precision (few per mil) using the Tunable Laser Spectrometer (TLS) that is part of the Sample Analysis at Mars (SAM) instrument suite on MSL s Curiosity Rover.

Webster, C. R.↗

Preliminary Interpretations of Atmospheric Stable Isotopes and Argon from Mars Science Laboratory (SAM)

Given the broad agreement between C, H, and O isotopic ratios in the modern atmosphere and the ALH 84001 meteorite, it is possible that these reservoirs were established after early atmospheric loss prior to 4 Ga. The preservation of these signals over this long period of history can be explained in several slightly different ways: 1) C, O, and H have remained static in the atmosphere and have not exchanged with the surface over the past 4 Ga; 2) C, O, and H in the atmosphere have potentially varied widely over history but have been continually buffered by larger reservoirs in the crust which have remained unchanged over the past 4 Ga. This second possibility allows for potentially large variations in atmospheric pressure to occur as CO2 is recycled back into the atmosphere from crustal reservoirs or degassed from the mantle.

Jones, J. H.↗