Engineering topics

McAdam, A. C.

Publications and source records attributed to McAdam, A. C..

At least 37 records · Page 2

NASA NTRS2016

Phosphate Stability in Diagenetic Fluids Constrains the Acidic Alteration Model for Lower Mt. Sharp Sedimentary Rocks in Gale Crater, Mars

The Mars rover Curiosity has encountered silica-enriched bedrock (as strata and as veins and associated halos of alteration) in the largely basaltic Murray Fm. of Mt. Sharp in Gale Crater. Alpha Particle X-ray Spectrometer (APXS) investigations of the Murray Fm. revealed decreasing Mg, Ca, Mn, Fe, and Al, and higher S, as silica increased (Fig. 1). A positive correlation between SiO2 and TiO2 (up to 74.4 and 1.7 wt %, respectively) suggests that these two insoluble elements were retained while acidic fluids leached more soluble elements. Other evidence also supports a silica-retaining, acidic alteration model for the Murray Fm., including low trace element abundances consistent with leaching, and the presence of opaline silica and jarosite determined by CheMin. Phosphate stability is a key component of this model because PO4 3- is typically soluble in acidic water and is likely a mobile ion in diagenetic fluids (pH less than 5). However, the Murray rocks are not leached of P; they have variable P2O5 (Fig. 1) ranging from average Mars (0.9 wt%) up to the highest values in Gale Crater (2.5 wt%). Here we evaluate APXS measurements of Murray Fm. bedrock and veins with respect to phosphate stability in acidic fluids as a test of the acidic alteration model for the Lower Mt. Sharp rocks.

Berger, J. A.↗

NASA NTRS2016

Magnesium Sulfate as a Key Mineral for the Detection of Organic Molecules on Mars Using Pyrolysis

Pyrolysis of soil or rock samples is the preferred preparation technique used on Mars to search for organic molecules up today. During pyrolysis, oxichlorines present in the soil of Mars release oxidant species that alter the organic molecules potentially contained in the samples collected by the space probes.This process can explain the difficulty experienced by in situ exploration probes to detect organic materials in Mars soil samples until recently. Within a few months, the Curiosity rover should reach and analyze for the first time soils rich in sulfates which could induce a different behavior of the organics during the pyrolysis compared with the types of soils analyzed up today. For this reason, we systematically studied the pyrolysis of organic molecules trapped in magnesium sulfate, in the presence or absence of calcium perchlorate. Our results show that organics trapped in magnesium sulfate can undergo some oxidation and sulfuration during the pyrolysis. But these sulfates are also shown to protect organics trapped inside the crystal lattice and/or present in fluid inclusions from the oxidation induced by the decomposition of calcium perchlorate and probably other oxychlorine phases currently detected on Mars. Trapped organics may also be protected from degradation processes induced by other minerals present in the sample, at least until these organics are released from the pyrolyzed sulfate mineral (700C in our experiment). Hence, we suggest magnesium sulfate as one of the minerals to target in priority for the search of organic molecules by the Curiosity and ExoMars 2018 rovers.

Francois, P.↗

NASA NTRS2015

Iron-Rich Carbonates as the Potential Source of Evolved CO2 Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater

The Sample Analysis at Mars (SAM) instrument detected at least 4 distinct CO2 release during the pyrolysis of a sample scooped from the Rocknest (RN) eolian deposit. The highest peak CO2 release temperature (478-502 C) has been attributed to either a Fe-rich carbonate or nano-phase Mg-carbonate. The objective of this experimental study was to evaluate the thermal evolved gas analysis (T/EGA) characteristics of a series of terrestrial Fe-rich carbonates under analog SAM operating conditions to compare with the RN CO2 releases. Natural Fe-rich carbonates (<53 microns) with varying Fe amounts (Fe(0.66)X(0.34)- to Fe(0.99)X(0.01)-CO3, where X refers to Mg and/or Mn) were selected for T/EGA. The carbonates were heated from 25 to 715 C (35 C/min) and evolved CO2 was measured as a function of temperature. The highest Fe containing carbonates (e.g., Fe(0.99)X(0.01)-CO3) yielded CO2 peak temperatures between 466-487 C, which is consistent with the high temperature RN CO2 release. The lower Fe-bearing carbonates (e.g., Fe(0.66)X(0.34)CO3) did not have peak CO2 release temperatures that matched the RN peak CO2 temperatures; however, their entire CO2 releases did occur within RN temperature range of the high temperature CO2 release. Results from this laboratory analog analysis demonstrate that the high temperature RN CO2 release is consistent with Fe-rich carbonate (approx.0.7 to 1 wt.% FeCO3). The similar RN geochemistry with other materials in Gale Crater and elsewhere on Mars (e.g., Gusev Crater, Meridiani) suggests that up to 1 wt. % Fe-rich carbonate may occur throughout the Gale Crater region and could be widespread on Mars. The Rocknest Fe-carbonate may have formed from the interaction of reduced Fe phases (e.g., Fe2+ bearing olivine) with atmospheric CO2 and transient water. Alternatively, the Rocknest Fe-carbonate could be derived by eolian processes that have eroded distally exposed deep crustal material that possesses Fe-carbonate that may have formed through metamorphic and/or metasomatic processes.

Sutter, B.↗

NASA NTRS2015

The Investigation of Perchlorate/Iron Phase Mixtures as A Possible Source of Oxygen Detected by the Sample Analysis at Mars (SAM) Instrument in Gale Crater, Mars

The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover detected 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 individual per-chlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. These detections along with the detection of perchlorate (ClO4-) by the Mars Phoenix Lander's Wet Chemistry Laboratory suggested perchlorate is a possible candidate for evolved O2 and chlorine species. Laboratory thermal analysis of pure perchlorates has yet to provide an unequivocal temperature match to the SAM O2 and HCl release data. Analog laboratory analysis of iron mineralogy detected in Gale materials that was physically mixed with Ca- and Mg-perchlorate has been shown to catalyze lower O2 release temperatures and approach some SAM O2 release data. Instead of physical mixtures used in previous work, the work presented here utilized perchlorate solutions added to Fe phases. This technique allowed for perchlorate to come in closer contact with the Fe-phase and may more closely mimic Mars conditions where humidity can increase enough to cause deliquescence of the highly hygroscopic perchlorate phases. The objective of this work is to: 1) Utilize a laboratory SAM analog instrument to evaluate the O2 release temperatures from Mg- and Ca-perchlorates solutions applied to Fephases detetected in Gale Crate; and 2) Determine if perchlorate solutions can provide improved matches with the SAM O2 temperature release profiles.

Sutter, B.↗

NASA NTRS2015

Update on the Chemical Composition Of Crystalline, Smectite, and Amorphous Components for Rocknest Soil and John Klein and Cumberland Mudstone Drill Fines at Gale Crater, Mars

We have previously calculated the chemical compositions of the X-ray-diffraction (XRD) amorphous component of three solid samples (Rocknest (RN) soil, John Klein (JK) drill fines, and Cumberland (CB) drill fines) using major-element chemistry (APXS), volatile-element chemistry (SAM), and crystalline- phase mineralogy (CheMin) obtained by the Curiosity rover as a part of the ongoing Mars Science Laboratory mission in Gale Crater. According to CheMin analysis, the RN and the JK and CB samples are mineralogically distinct in that RN has no detectable clay minerals and both JK and CB have significant concentrations of high-Fe saponite. The chemical composition of the XRD amorphous component is the composition remaining after mathematical removal of the compositions of crystalline components, including phyllosilicates if present. Subsequent to, we have improved the unit cell parameters for Fe-forsterite, augite, and pigeonite, resulting in revised chemical compositions for the XRD-derived crystalline component (excluding clay minerals). We update here the calculated compositions of amorphous components using these revised mineral compositions.

Morris, R. V.↗

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 NTRS2014

The Imprint of Atmospheric Evolution in the D/H of Hesperian Clay Minerals on Mars

The deuterium-to-hydrogen (D/H) ratio in strongly bound water or hydroxyl groups in ancient Martian clays retains the imprint of the water of formation of these minerals. Curiosity's Sample Analysis at Mars (SAM) experiment measured thermally evolved water and hydrogen gas released between 550 degrees Centigrade and 950 degrees Centigrade from samples of Hesperian-era Gale crater smectite to determine this isotope ratio. The D/H value is 3.0 (plus or minus 0.2) times the ratio in standard mean ocean water. The D/H ratio in this approximately 3-billion-year-old mudstone, which is half that of the present Martian atmosphere but substantially higher than that expected in very early Mars, indicates an extended history of hydrogen escape and desiccation of the planet.

Deuterium↗

NASA NTRS2014

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.↗

NASA NTRS2014

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.↗

NASA NTRS2014

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.↗

NASA NTRS2014

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.↗

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 NTRS2014

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

Stern, J. C.↗

NASA NTRS2014

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

Sutter, B.↗

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

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↗

NASA NTRS2014

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↗

NASA NTRS2013

Carbon Isotopic Composition of CO2, Evolved During Perchlorate-Induced Reactions in Mars Analog Materials: Interpreting SAM/MSL Rocknest Data

The Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL) Rover Curiosity made its first solid sample evolved gas analysis of unconsolidated material at aeolian bedform Rocknest in Gale Crater. The magnitude of O2 evolved in each run as well as the chlorinated hydrocarbons detected by SAM gas chromatograph/ mass spectrometer (GCMS) [1] suggest a chlorinated oxidant such as perchlorate in Rocknest materials [2]. Perchlorate induced combustion of organics present in the sample would contribute to the CO2 volatile inventory, possibly overlapping with CO2 from inorganic sources. The resulting carbon and oxygen isotopic composition of CO2 sent to the Tunable Laser Spectrometer (TLS) for analysis would represent mixed sources. This work was undertaken to better understand a) how well the carbon isotopic composition ( 13C) of CO2 from partially combusted products represents their source and b) how the 13C of combusted products can be deconvolved from other carbon sources such as thermal decomposition of carbonate.

Stern, J. C.↗