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Niles, P. B.

Publications and source records attributed to Niles, P. B..

At least 55 records · Page 3

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.↗

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.↗

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.↗

Evidence for a Noachian-Aged Ephemeral Lake in Gusev Crater, Mars

Gusev crater was selected as the landing site for the Spirit rover because of the likelihood that it contained an ancient lake. Although outcrops rich in Mg-Fe carbonate dubbed Comanche were discovered in the Noachian-aged Columbia Hills, they were inferred to result from volcanic hydrothermal activity. Spirit encountered other mineral and chemical indicators of aqueous activity, but none was recognized as definitive evidence for a former lake in part because none was associated with obvious lacustrine sedimentary deposits. However, water discharge into Martian crater basins like Gusev may have been episodic, producing only small amounts of sediment and shallow ephemeral lakes. Evaporative precipitation from such water bodies has been suggested as a way of producing the Mg- and Fe-rich carbonates found in ALH84001 and carbonates and salts in some nakhlites a hypothesis we examine for the Comanche carbonate.

Ruff, S. W.↗

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↗

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.↗

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.↗

Hydrogen Isotopic Composition of Water in the Martian Atmosphere and Released from Rocknest Fines

The Mars Science Laboratory Curiosity rover sampled the aeolian bedform called Rocknest as its first solid samples to be analyzed by the analytical instruments CheMin and SAM. The instruments ingested aliquots from a sieved sample of less than 150 micrometer grains. As discussed in other reports at this conference [e.g., 1], CheMin discovered many crystalline phases, almost all of which are igneous minerals, plus some 10s of percent of x-ray amorphous material. The SAM instrument is focused on understanding volatiles and possible organics in the fines, performing evolved gas analysis (EGA) with the SAM quadrapole mass spectrometer (QMS), isotope measurements using both the QMS and the tunable laser spectrometer (TLS), which is sensitive to CO2, water and methane, and organics with the gas chromatograph mass spectrometer (GCMS). As discussed in the abstract by Franz et al. [2] and others, EGA of Rocknest fines revealed the presence of significant amounts of H2O as well as O-, C- and S-bearing materials. SAM has also tasted the martian atmosphere several times, analyzing the volatiles in both the TLS and QMS [e.g., 3,4]. This abstract will focus on presentation of initial hydrogen isotopic data from the TLS for Rocknest soils and the atmosphere, and their interpretation. Data for CO2 isotopes and O isotopes in water are still being reduced, but should be available by at the conference.

Leshin, L. A.↗

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

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

Franz, H. B.↗

Multiple Smaller Missions as a Direct Pathway to Mars Sample Return

Recent discoveries by the Mars Exploration Rovers, Mars Express, Mars Odyssey, and Mars Reconnaissance Orbiter spacecraft include multiple, tantalizing astrobiological targets representing both past and present environments on Mars. The most desirable path to Mars Sample Return (MSR) would be to collect and return samples from that site which provides the clearest examples of the variety of rock types considered a high priority for sample return (pristine igneous, sedimentary, and hydrothermal). Here we propose an MSR architecture in which the next steps (potentially launched in 2018) would entail a series of smaller missions, including caching, to multiple landing sites to verify the presence of high priority sample return targets through in situ analyses. This alternative architecture to one flagship-class sample caching mission to a single site would preserve a direct path to MSR as stipulated by the Planetary Decadal Survey, while permitting investigation of diverse deposit types and providing comparison of the site of returned samples to other aqueous environments on early Mars

Niles, P. B.↗

The Carbonates in ALH 84001 Record the Evolution of the Martian Atmosphere Through Multiple Formation Events

Current Martian conditions restrict the presence of liquid water due to low temperatures (approx 210K), a thin atmosphere (approx 7mb), and intense UV radiation. However, past conditions on Mars may have been different with the possibility that the ancient Martian climate was warm and wet with a dense CO2 atmosphere. The cycling of carbon on Mars through atmospheric CO2 and carbonate minerals is critical for deciphering its climate history. In particular stable isotopes contained in carbonates can provide information of their origin and formation environment as well as possibly hinting at the composition of global reservoirs such as atmospheric CO2. Martian meteorite ALH 84001 contains widely studied carbonate rosettes that have been dated to approx. 3.9 Ga and have been used to interpret climatic conditions present at that time. However, there is mount-ing evidence for multiple episodes of carbonate formation in ALH 84001 with potentially distinct isotopic compositions. This study seeks to tease out these different carbonate assemblages using stepped phosphoric acid dissolution and analysis of carbon and triple oxygen stable isotopes. In addition, we report SIMS analyses of the delta O-18 several petrographically unusual carbonate phases in the meteorite.

Shaheen, R.↗

The Alteration History of Clovis Class Rocks in Gusev Crater as Determined by Ti-Normalzed Mass Balance Analysis

The West Spur Clovis class rocks in Gusev Crater are some of the most altered rocks in Gusev Crater and likely contain a mixed sulfate and phyllosilicate mineralogy [1,2]. The high S and Cl content of the Clovis rocks suggests that acidic vapors or fluids of H2SO4 and HCl reacted with the Clovis parent rock to form Ca, Mg,- sulfates, iron-oxyhydroxides and secondary aluminosilicates (approx.60 wt.%) of a poorly crystalline nature (e.g., allophane) [1]. Up to 14-17 wt.% phyllosilicates (e.g., kaolinite, chlorite, serpentine) are hypothesized to exist in the Clovis materials suggesting that Clovis parent materials while possibly exposed to acidic pHs were likely neutralized by basalt dissolution which resulted in mildly acidic pHs (4-6) [1, 2]. This work proposes that subsequent to the alteration of the Clovis rocks, alteration fluids became concentrated in ions resulting in the addition of silicate and salts. The objective of this work is to utilize Ti-normalized mass balance analysis to evaluate (1) mineral gains and losses and (2) elemental gains and losses in the Clovis rocks. Results of this work will be used evaluate the nature of geochemical conditions that affect phyllosilicate and sulfate formation at Gusev crater.

Sutter, Brat↗

Dissolution of Olivine, Siderite, and Basalt at 80 Deg C in 0.1 M H2SO4 in a Flow Through Process: Insights into Acidic Weathering on Mars

The occurrence of jarosite, other sulfates (e.g., Mg-and Ca-sulfates), and hematite along with silicic-lastic materials in outcrops of sedimentary materials at Meridiani Planum (MP) and detection of silica rich deposits in Gusev crater, Mars, are strong indicators of local acidic aqueous processes [1,2,3,4,5]. The formation of sediments at Meridiani Planum may have involved the evaporation of fluids derived from acid weathering of Martian basalts and subsequent diagenesis [6,7]. Also, our previous work on acid weathering of basaltic materials in a closed hydro-thermal system was focused on the mineralogy of the acid weathering products including the formation of jarosite and gray hematite spherules [8,9,10]. The object of this re-search is to extend our earlier qualitative work on acidic weathering of rocks to determine acidic dissolution rates of Mars analog basaltic materials at 80 C using a flow-thru reactor. We also characterized residual phases, including poorly crystalline or amorphous phases and precipitates, that remained after the treatments of olivine, siderite, and basalt which represent likely MP source rocks. This study is a stepping stone for a future simulation of the formation of MP rocks under a range of T and P.

Golden, D. C.↗

A Possible Organic Contribution to the Low Temperature CO2 Release Seen in Mars Phoenix Thermal and Evolved Gas Analyzer Data

Two of the most important discoveries of the Phoenix Mars Lander were the discovery of approx.0.6% perchlorate [1] and 3-5% carbonate [2] in the soils at the landing site in the martian northern plains. The Thermal and Evolved Gas Analyzer (TEGA) instrument was one of the tools that made this discovery. After soil samples were delivered to TEGA and transferred into small ovens, the samples could be heated up to approx.1000 C and the gases that evolved during heating were monitored by a mass spectrometer. A CO2 signal was detected at high temperature (approx.750 C) that has been attributed to calcium carbonate decomposition. In addition to this CO2 release, a lower temperature signal was seen. This lower temperature CO2 release was postulated to be one of three things: 1) desorption of CO2, 2) decomposition of a different carbonate mineral, or 3) CO2 released due to organic combustion. Cannon et al. [3] present another novel hypothesis involving the interaction of decomposition products of a perchlorate salt and calcium carbonate.

Archer, P. D. Jr.↗

Thermal and Evolved Gas Analysis of "Nanophase" Carbonates: Implications for Thermal and Evolved Gas Analysis on Mars Missions

Data collected by the Mars Phoenix Lander's Thermal and Evolved Gas Analyzer (TEGA) suggested the presence of calcium-rich carbonates as indicated by a high temperature CO2 release while a low temperature (approx.400-680 C) CO2 release suggested possible Mg- and/or Fe-carbonates [1,2]. Interpretations of the data collected by Mars remote instruments is done by comparing the mission data to a database on the thermal properties of well-characterized Martian analog materials collected under reduced and Earth ambient pressures [3,4]. We are proposing that "nano-phase" carbonates may also be contributing to the low temperature CO2 release. The objectives of this paper is to (1) characterize the thermal and evolved gas proper-ties of carbonates of varying particle size, (2) evaluate the CO2 releases from CO2 treated CaO samples and (3) examine the secondary CO2 release from reheated calcite of varying particle size.

Lauer, Howard V., Jr.↗