Engineering topics

Archer, P. D., Jr.

Publications and source records attributed to Archer, P. D., Jr..

At least 19 records

NASA NTRS2020

X-Ray Diffraction and Reflectance Spectroscopy of Murchison Powders (CM2) After Thermal Analysis Under Reducing Conditions to Final Temperatures Between 300 and 1300°c

The asteroids Ryugu and Bennu have spectral characteristics in common with CI/CM type carbonaceous chondrites and are target bodies for JAXA’s Hayabusa2 and NASA’s OSIRIS-Rex missions, respectively. Analog studies, based primarily on the Murchison CM2 chondrite, provide a pathway to separate spectral properties resulting space weathering from those inherent to parent-body, mineralogy, chemistry, and processes. Ryugu shares spectral properties with thermally metamorphosed and partly dehydrated CI/CM chondrites. We have undertaken a multidisciplinary study of the thermal decomposition of Murchison powder samples as an analog to metamorphic process that may have occurred on Ryugu. Bulk analyses include thermal And evolved gas analysis, X-ray diffraction (XRD), and VIS-NIR and Mössbauer spectroscopy; micro- to nanoscale analyses included scanning and transmission electron microscopy and electron probe micro analysisWe report here XRD and VIS-NIR analyses of pre- and post-heated Murchison powders, and in a companion paper report results from multiple electron beam techniques.

Morris, R. V.↗

NASA NTRS2019

Oxychlorine Detection in Gale Crater, Mars and Implications for Past Environmental Conditions

The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity has analyzed 3 scooped samples and 15 drilled samples since landing in 2012. Oxychlorine compounds (perchlorate/chlorate) were detected in the first 9 drilled samples but have not been detected in the last 6, starting with the Oudam sample in the Hartmann’s Valley member of the Murray formation (Table 1). Scooped samples have all contained detectable oxychlorine. These results suggest that oxychlorine formation and preservation spans the geologic record on Mars but has not been uniform spatially or temporally.

Archer, P. D., Jr.↗

NASA NTRS2018

Can Silicon-Smelting Contribute to the Low O/Si Ratio on the Surface of Mercury?

The MErcury Surface, Space ENvironment, GEochemistry, and Ranging (MESSENGER) spacecraft collected data that provided important insights into the structure, chemical makeup, and compositional diversity of Mercury. Among the many discoveries about Mercury made by MESSENGER, several surprising compositional characteristics of the surface were observed. These discoveries include elevated sulfur abundances (up to 4 wt.%), elevated abundances of graphitic carbon (0-4.1 wt.% across the surface with an additional 1-3 wt.% graphite above the global average in low reflectance materials), low iron abundances (less than 2 wt.%), and low oxygen abundances (O/Si weight ratio of 1.20+/-0.1). These exotic characteristics likely have important implications for the thermochemical evolution of Mercury and point to a planet that formed under highly reducing conditions. In the present study, we focus specifically on the low O/Si ratio of Mercury, which is anomalous compared to all other planetary materials. A recent study that considered the geochemical implications of the low O/Si ratio reported that 12-20% of the surface materials on Mercury are composed of Si-rich, Si-Fe alloys. They further postulated that the origin of the metal is best explained by a combination of space weathering and graphite-induced smelting that was facilitated by interaction of graphite with boninitic and komatiitic parental liquids. The goal of the present study is to assess the plausibility of smelting on Mercury through experiments run at the conditions that McCubbin et al. indicated would be favorable for Si-smelting.

McCubbin, F. M.↗

NASA NTRS2017

Effects of Martian Surface Materials on the Thermal Decomposition of Hydrogen Peroxide

While hydrogen peroxide (H2O2) has been detected in the martian atmosphere, it has not been detected in surface materials. Since the Viking lander mission, we have sent instruments to Mars with the capability to detect H2O2. The Sample Analysis at Mars (SAM) instrument onboard the Curiosity Rover and Thermal and Evolved Gas Analyzer (TEGA) instrument on the Phoenix lander both detected water and oxygen releases from analyzed sediments but whether or not peroxide could be the source of these gases has not been investigated. We are investigating the possible presence of H2O2 in martian materials by analyzing Mars-relevant minerals that have been mixed with hydrogen peroxide using lab instruments configured as analogs to Mars mission instruments. The object of this research is to use lab instruments to find the effects of Mars analog minerals on hydrogen peroxide gas release temperatures, specifically gas releases of water and oxygen and also determine the effect of the peroxide on the minerals. Data that we get from the lab can then be compared to the data collected from Mars. The minerals hematite, siderite, San Carlos olivine, magnetite and nontronite were chosen as our Mars analog minerals. ~20 mg of analog Mars minerals with 5μl of 50% H2O2, and were either run immediately or placed in a sealed tube for 2, 4, or 9 days to look for changes over time with two reps being done at each time step to determine repeatability. Each sample was heated from -60 degC to 500 degC at 20 degC/min and the evolved gases were monitored with a mass spectrometer. Each sample was also analyzed with an X-ray diffraction instrument to look for changes in mineralogy. Preliminary results show three potential outcomes: 1) peroxide has no effect on the sample (e.g., hematite), 2) the mineral is unaffected but catalyzes peroxide decomposition (magnetite, siderite), or 3) peroxide alters the mineral (pyrrhotite, San Carlos olivine).

Archer, P. D., Jr.↗

NASA NTRS2017

Effect of Solution pH and Chloride Concentration on Akaganeite Precipitation: Implications for Akaganeite Formation on Mars

Akaganeite (Beta-FeOOH, chloride-containing Fe(III) (hydr)oxide) has been recently discovered on the surface of Mars by the Mars Science Laboratory Curiosity rover in Yellowknife Bay, Gale Crater, Mars [1] and from orbit by the Mars Reconnaissance Orbiter in Robert Sharp crater and Antoniadi basin [2]. However, the mechanism and aqueous environmental conditions of akaganeite formation (e.g., pH and chloride concentration) remain unknown. We have investigated formation of akaganeite through Fe(III) hydrolysis at variable initial pH and chloride concentrations. The formed Fe(III) precipitates were characterized by instruments similar to instruments on Mars robotic spacecraft. Syntheses were performed through hydrolysis of Fe(III) perchlorate with addition of Na cloride (Fe/Cl ratio between 0.5 and 5) and at initial pH of 1.5, 2, 4, 6 and 8 at 90degC. X-ray diffraction analysis revealed formation of akaganeite alone or in mixture with goethite, hematite and ferrihydrite at all initial pHs and Fe/Cl ratio between 0.5 and 2 while akaganeite precipitated only at pH 1.5 and Fe/Cl greater than2. Chloride content of akaganeite was affected by initial pH and decreased from 20-60 mg/g at pH 1.5 to less than 0.1 mg/g at pH 8. The synthesized akaganeite samples were also characterized by Mössbauer and infrared spectroscopy and volatiles were analysed by thermal and evolved gas analysis. The obtained characterization data will be compared to published data from rover and orbital missions [1-3] to determine martian akaganeite composition, crystallinity and formation conditions.

Peretyazhko, T. A.↗

NASA NTRS2017

Bulk Hydrogen Content OF High-Silica Rocks in Gale Crater With the Active Dynamic Albedo of Neutrons Experiment

The Mars Science Laboratory (MSL) Curiosity rover recently traversed over plateaus of mafic aeolian sandstones (the 'Stimson' formation) that overlie mudstones (the 'Murray' formation). Within the Stimson formation we observed many lighter-toned, halo-forming features, that are potentially indicative of fluid alteration (see Fig. 1). These halo features extend for tens of meters laterally and are approx.1 meter wide. The halo features were characterized by Curiosity's geochemical instruments: Alpha Proton X-Ray Spectrometer (APXS), Chemin, Chemcam and Sample Analysis at Mars (SAM). With respect to the host (unaltered) Stimson rocks, fracture halos were significantly enriched in silicon and low in iron [1]. Changes in hydrogen abundance (due to its large neutron scattering cross section) greatly influence the magnitude of the thermal neutron response from the Dynamic Albedo of Neutrons (DAN) instrument [2]. There are also some elemental species, e.g. chlorine, iron, and nickel, that have significant microscopic neutron absorption cross sections. These elements can be abundant and variable results provide a useful estimate of the lower bound for bulk hydrogen content (assuming a homogeneous distribution).

Gabriel, T. S. J.↗

NASA NTRS2016

First Detection of Non-Chlorinated Organic Molecules Indigenous to a Martian Sample

The Sample Analysis at Mars (SAM) instrument onboard Curiosity can perform pyrolysis of martian solid samples, and analyze the volatiles by direct mass spectrometry in evolved gas analysis (EGA) mode, or separate the components in the GCMS mode (coupling the gas chromatograph and the mass spectrometer instruments). In addition, SAM has a wet chemistry laboratory designed for the extraction and identification of complex and refractory organic molecules in the solid samples. The chemical derivatization agent used, N-methyl-N-tert-butyldimethylsilyl- trifluoroacetamide (MTBSTFA), was sealed inside seven Inconel metal cups present in SAM. Although none of these foil-capped derivatization cups have been punctured on Mars for a full wet chemistry experiment, an MTBSTFA leak was detected and the resultant MTBSTFA vapor inside the instrument has been used for a multi-sol MTBSTFA derivatization (MD) procedure instead of direct exposure to MTBSTFA liquid by dropping a solid sample directly into a punctured wet chemistry cup. Pyr-EGA, Pyr-GCMS and Der-GCMS experiments each led to the detection and identification of a variety of organic molecules in diverse formations of Gale Crater.

Freissinet, C.↗

NASA NTRS2016

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.↗

NASA NTRS2016

Reactions Involving Calcium and Magnesium Sulfates as Potential Sources of Sulfur Dioxide During MSL SAM Evolved Gas Analyses

The Sample Analysis at Mars (SAM) and Chemistry and Mineralogy (CheMin) instruments on the Mars Science Laboratory (MSL) have analyzed several subsamples of <150 micron fines from ten 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. Four were drilled from sites Confidence Hills (CH), Mojave (MJ), Telegraph Peak (TP) and Buckskin (BK) of the Murray Formation at the base of Mt. Sharp. Two were drilled from sandstones of the Stimson formation targeting relatively unaltered (Big Sky, BY) and then altered (Greenhorn, GH) material associated with a light colored fracture zone. CheMin analyses provided quantitative sample mineralogy. SAM's evolved gas analysis mass spectrometry (EGA-MS) detected H2O, CO2, O2, H2, SO2, H2S, HCl, NO, and other trace gases. This contribution will focus on evolved SO2. All samples evolved SO2 above 500 C. The shapes of the SO2 evolution traces with temperature vary between samples but most have at least two "peaks' within the wide high temperature evolution, from approx. 500-700 and approx. 700-860 C (Fig. 1). In many cases, the only sulfur minerals detected with CheMin were Ca sulfates (e.g., RN and GH), which should thermally decompose at temperatures above those obtainable by SAM (>860 C). Sulfides or Fe sulfates were detected by CheMin (e.g., CB, MJ, BK) and could contribute to the high temperature SO2 evolution, but in most cases they are not present in enough abundance to account for all of the SO2. This additional SO2 could be largely associated with x-ray amorphous material, which comprises a significant portion of all samples. It can also be attributed to trace S phases present below the CheMin detection limit, or to reactions which lower the temperatures of SO2 evolution from sulfates that are typically expected to thermally decompose at temperatures outside the SAM temperature range (e.g., Ca and Mg sulfates). Here we discuss the results of SAM-like laboratory analyses targeted at understanding this last possibility, focused on understanding if reactions of HCl or an HCl evolving phase (oxychlorine phases, chlorides, etc.) and Ca and Mg sulfates can result in SO2 evolution in the SAM temperature range.

McAdam, A. C.↗

NASA NTRS2015

An Exploration Zone in Cerberus Containing Young and Old Terrains, Including Fossae/Faults and Sher-Gottite Distal Ejecta

No abstract available

Wright, S. P.↗

NASA NTRS2015

The Nitrate/Perchlorate Ratio on Mars as an Indicator for Habitability

Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and the potential development of a nitrogen cycle at some point in martian history. The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected evolved nitric oxide (NO) gas during pyrolysis of scooped aeolian sediments and drilled mudstone acquired in Gale Crater. The detection of NO suggests an indigenous source of fixed N, and may indicate a mineralogical sink for atmospheric N2 in the form of nitrate. The ratio of nitrate to oxychlorine species (e.g. perchlorate) may provide insight into the extent of development of a nitrogen cycle on Mars.

Stern, J. C.↗

NASA NTRS2015

Transmission X-ray Diffraction (XRD) Patterns Relevant to the MSL Chemin Amorphous Component: Sulfates And Silicates

The Mars Science Laboratory (MSL) CheMin instrument on the Curiosity rover is a transmission X-ray diffractometer (Co-Kalpha radiation source and a approx.5deg to approx.52deg 2theta range) where the analyzed powder samples are constrained to have discrete particle diameters <150 microns by a sieve. To date, diffraction patterns have been obtained for one basaltic soil (Rocknest (RN)) and four drill fines of coherent rock (John Klein (JK), Cumberland (CB), Windjana (WJ), and Confidence Hills (CH)). The CheMin instrument has detected and quantified the abundance of both primary igneous (e.g., feldspar, olivine, and pyroxene) and secondary (e.g., Ca-sulfates, hematite, akaganeite, and Fe-saponite) minerals. The diffraction patterns of all CheMin samples are also characterized by a broad diffraction band centered near 30deg 2theta and by increasing diffraction intensity (scattering continuum) from approx.15deg to approx.5deg, the 2theta minimum. Both the broad band and the scattering continuum are attributed to the presence of an XRD amorphous component. Estimates of amorphous component abundance, based on the XRD data itself and on mass-balance calculations using APXS data crystalline component chemistry derived from XRD data, martian meteorites, and/or stoichiometry [e.g., 6-9], range from approx.20 wt.% to approx.50 wt.% of bulk sample. The APXSbased calculations show that the amorphous component is rich in volatile elements (esp. SO3) and is not simply primary basaltic glass, which was used as a surrogate to model the broad band in the RN CheMin pattern. For RN, the entire volatile inventory (except minor anhydrite) is assigned to the amorphous component because no volatile-bearing crystalline phases were reported within detection limits [2]. For JK and CB, Fesaponite, basanite, and akaganeite are volatile-bearing crystalline components. Here we report transmission XRD patterns for sulfate and silicate phases relevant to interpretation of MSL-CheMin XRD amorphous components.

Morris, R. V.↗

NASA NTRS2015

Recognizing Sulfate and Phosphate Complexes Adsorbed onto Nanophase Weathering Products on Mars

Nanophase weathering products (i.e., secondary phases that lack long-range atomic order) have been recognized on the martian surface via orbital observations and in-situ measurements from landed missions. Allophane, a poorly crystalline, hydrated aluminosilicate, has been identified at the regional scale in models of thermal-infrared (TIR) data from the Thermal Emission Spectrometer (TES) and at the local scale from visible/near-IR (VNIR) data from the Compact Reconnaissance Impact Spectrometer for Mars (CRISM) instrument and phase calculations of Alpha Particle X-ray Spectrometer (APXS) data of rocks encountered by the Mars Exploration Rovers (MER) Spirit and Opportunity. Nanophase iron oxides (npOx) have been recognized in rocks and soils measured by the Mössbauer Spectrometer on Spirit and Opportunity. Furthermore, analyses of X-ray diffraction data measured by the CheMin instrument onboard the Mars Science Laboratory rover Curiosity indicate rock and soil samples are comprised of approx. 20-50 wt.% X-ray amorphous materials. Chemical measurements by landed missions indicate the presence of sulfur and phosphorus in martian rocks in soils, and APXS data from Gusev crater demonstrate abundances of up to approx. 5 wt.% P2O5 and approx. 30 wt.% SO3. However, the speciation of phosphorus and sulfur is not always evident. On Earth, phosphate and sulfate anions can be chemisorbed onto the surfaces of nanophase weathering products. This process may also occur on Mars, and calculations of the composition of the amorphous component at Gale crater using CheMin mineral models and APXS data show that amorphous material is enriched in volatiles, including S. Here, we examine the ability to detect chemisorbed sulfate and phosphate complexes by analyzing sulfate- and phosphate-adsorbed nanophase weathering products using instruments similar to those on landed and orbital missions.

Rampe, E. B.↗

NASA NTRS2015

Oxychlorine Species on Mars: The Gale Crater Story

Comparing data from the Alpha- Particle X-Ray Spectrometer (APXS) and the Sample Analysis at Mars (SAM) instruments on MSL reveals a strong linear correlation between chlorine and oxygen, further demonstrating the presence of oxychlorine species in Gale Crater and, very likely, globally on Mars. Perchlorate was first discovered on Mars by the Microscopy, Electrochemistry, and Conductivity Analyzer (MECA) instrument on the Phoenix lander in 2008. Current hypotheses suggest that the formation of oxychlorine species such as perchlorate or chlorate is a global process and that these species should be globally distributed on Mars [e.g. 2-4]. To date, the SAM and Chemistry and Mineralogy (CheMin) instruments on MSL have analyzed one scooped sample of aeolian material (Rocknest [RN]), and four drilled samples (John Klein [JK], Cumberland [CB], Windjana [WJ], and Confidence Hills [CH]). The APXS instrument has also investigated the same or very similar samples. Although not definitively identified, oxychlorine species have been proposed to explain releases of O2, HCl, and chlorinated hydrocarbon species detected by evolved gas analysis (EGA) with the SAM instrument. We report a strong linear correlation between wt. % Cl detected by APXS and moles O2 detected by SAM during pyrolysis, indicating the presence of oxychlorine species in Gale Crater.

Archer, P. D., Jr.↗

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

The Nitrate/Perchlorate Ratio on Mars as an Indicator for Habitability

Mars↗

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.↗