Engineering topics

Szopa, Cyril

Publications and source records attributed to Szopa, Cyril.

9 records

NASA NTRS2020

First Detections of Dichlorobenzene Isomers and Trichloromethylpropane from Organic Matter Indigenous to Mars Mudstone in Gale Crater, Mars: Results from the Sample Analysis at Mars Instrument Onboard the Curiosity Rover

Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5–17 ppbw range relative to the sample mass. We also report the first detection of trichloromethylpropane and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (<300 ppbw) indigenous to the same mudstone highlight that organics can be preserved from the harsh surface conditions even at shallow depth. The detection of new chlorohydrocarbons with SAM confirms that organic molecules should have been available in an environment favorable to life forms, strengthening the habitability aspect of Gale crater. Key Words: Mars—Chlorinated organic molecules—In situ measurements—Sample Analysis at Mars— Mudstone—Gale crater. Astrobiology 20, 292–306.

Szopa, Cyril↗

NASA NTRS2019

Investigating the Effects of Gamma Radiation on Selected Chemicals for Use in Biosignature Detection Instruments on the Surface of Jupiter's Moon Europa

Jupiter's moon Europa is a prime target for the search for potential signs of life in the solar system. The Europa Lander Science Definition Team Report outlined investigations and measurement requirements on a future Europa Lander and has led us to consider application of powerful techniques such as pyrolysis and derivatization gas chromatography mass spectrometry (GC-MS) and laser desorption mass spectrometry (LD-MS) to elucidate the organic composition of near-surface ice and minerals. Definitive identification of chemical biosignatures using such techniques is strongly enabled by the use of various chemicals, such as perfluorotributylamine (PFTBA) for the MS calibration, α-cyano-hydroxycinnamic acid (CHCA) for matrix-assisted laser desorption and ionization (MALDI) and N,N-dimethylformamide dimethyl acetal (DMF-DMA), N-tert-butyldimethylsilyl-N-methyltrifluoroacetamide (MTBSTFA) and tetramethylammonium hydroxide (TMAH) for wet chemistry GC-MS protocols. The jovian radiation environment is known to represent a uniquely challenging risk to mission performance and lifetime, principally due to high radiation levels. To assess the potential ionizing radiation damage to these important chemicals, we tested their effectiveness following gamma radiation exposure doses up to the anticipated Europa Lander rating requirement of 300 krad(Si). The chemicals were sealed in glass ampules under vacuum (<10 mTorr), to reduce trapped oxygen gas, as the oxidation by O2 may be enhanced in the presence of radiation. We report that all five chemicals exposed to total ionizing doses of 0, 150 and 300 krad(Si) maintained their full effectiveness, and no significant degradation was observed.

Radiation↗

NASA NTRS2018

Organic Matter Preserved in 3-Billion-Year-Old Mudstones at Gale Crater, Mars

Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500Â° to 820Â°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatographyâ€“mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.

Eigenbrode, Jennifer L.↗

NASA NTRS2014

The Search for Organic Compounds of Martian Origin in Gale Crater by the Sample Analysis at Mars (SAM) Instrument on Curiosity

One of the key objectives of the Mars Science Laboratory rover and the Sample Analysis at Mars (SAM) instrument suite is to determine the inventory of organic and inorganic volatiles in the atmosphere and surface regolith and rocks to help assess the habitability potential of Gale Crater. The SAM instrument on the Curiosity rover can detect volatile organic compounds thermally evolved from solid samples using a combination of evolved gas analysis (EGA) and gas chromatography mass spectrometry (GCMS) (Mahaffy et al. 2012). The first solid samples analyzed by SAM, a scoop of windblown dust and sand at Rocknest, revealed several chloromethanes and a C4-chlorinated hydrocarbon derived primarily from reactions between a martian oxychlorine phase (e.g. perchlorate) and terrestrial carbon from N-methyl-N-(tertbutyldimethylsilyl)- trifluoroacetamide (MTBSTFA) vapor present in the SAM instrument background (Glavin et al. 2013). After the analyses at Rocknest, Curiosity traveled to Yellowknife Bay and drilled two separate holes in a fluvio-lacustrine sediment (the Sheepbed unit) designated John Klein and Cumberland. Analyses of the drilled materials by both SAM and the CheMin X-Ray Diffraction instrument revealed a mudstone consisting of ~20 wt% smectite clays (Ming et al. 2013; Vaniman et al. 2013), which on Earth are known to aid the concentration and preservation of organic matter. Oxychlorine compounds were also detected in the Sheepbed mudstone during pyrolysis; however, in contrast to Rocknest, much higher levels of chloromethanes were released from the Sheepbed materials, suggesting an additional, possibly martian source of organic carbon (Ming et al. 2013). In addition, elevated abundances of chlorobenzene and a more diverse suite of chlorinated alkanes including dichloropropane and dichlorobutane detected in Cumberland compared to Rocknest suggest that martian or meteoritic organic carbon sources may be preserved in the mudstone (Freissinet et al. 2013). Chloromethane and dichloromethane were also identified after thermal volatilization of the surface soils by the GCMS instruments at the Viking landing sites, although no other chlorinated hydrocarbons were reported (Biemann et al. 1977). Here we focus on the origin of the chlorinated hydrocarbons detected in the Sheepbed mudstone by SAM and the implications for the preservation of organic matter in near-surface materials on Mars.

Mars Curiosity Rover↗

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 Sampl;e 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 from the three sites at Gale Crater. Preliminary detections of nitrogen species include No, HCN, ClCN, and TFMA ((trifluoro-N-methyl-acetamide), Confirmation of indigenous Martian nitrogen-bearing compounds requires quantifying N contribution from the terrestrial derivatization reagents 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.

Stern, Jennifer C.↗

NASA NTRS2013

Detection and Quantification of Nitrogen Compounds in Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite

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 from three sites at Gale Crater. Preliminary detections of nitrogen species include NO, HCN, ClCN, CH3CN, and TFMA (trifluoro-Nmethyl-acetamide). On Earth, nitrogen is a crucial bio-element, and nitrogen availability controls productivity in many environments. Nitrogen has also recently been detected in the form of CN in inclusions in the Martian meteorite Tissint, and isotopically heavy nitrogen (delta N-15 approx +100per mille) has been measured during stepped combustion experiments in several SNC meteorites. The detection of nitrogen-bearing compounds in Martian regolith would have important implications for the habitability of ancient Mars. However, confirmation of indigenous Martian nitrogen bearing compounds will require ruling out their formation from the terrestrial derivatization reagents (e.g. N-methyl-N-tert-butyldimethylsilyl-trifluoroacetamide, MTBSTFA and dimethylformamide, DMF) carried for SAM's wet chemistry experiment that contribute to the SAM background. The nitrogen species we detect 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. However, this does not preclude a Martian origin for some of these compounds, which are present in nanomolar concentrations in SAM evolved gas analyses. Analysis of SAM data and laboratory breadboard tests are underway to determine whether nitrogen species are present at higher concentrations than can be accounted for by maximum estimates of nitrogen contribution from MTBSTFA and DMF. In addition, methods are currently being developed to use GC Column 6, (functionally similar to a commercial Q-Bond column), to separate and identify unretained compounds such as NO, N2O, and NO2, which are difficult to detect by EGA-MS due to mass interferences at 30, 44 and 46, respectively. Here we present evolved gas analysis-mass spectrometry (EGA-MS) and gas chromatography mass spectrometry (GC-MS) data on the identification and quantification of these nitrogen-bearing compounds, and suggestions for their origins

Stern, Jennifer C.↗

NASA NTRS2013

The Search for Nitrates on Mars by the Sample Analysis at Mars (SAM) Instrument

Planetary models suggest that nitrogen was abundant in the early Martian atmosphere as N2 but it was lost by sputtering and photochemical loss to space, impact erosion, and chemical oxidation to nitrates. A nitrogen cycle may exist on Mars where nitrates, produced early in Mars' history, may have been later decomposed back into N2 by the current impact flux. Nitrates are a fundamental source of nitrogen for terrestrial microorganisms, and they have evolved metabolic pathways to perform both oxidation and reduction to drive a complete biological nitrogen cycle. Therefore, the characterization of nitrogen in Martian soils is important to assess habitability of the Martian environment, particularly with respect to the presence of nitrates. The only previous mission that was designed to search for soil nitrates was the Phoenix mission but N-containing species were not detected by TEGA or the MECA WCL. Nitrates have been tentatively identified in Nakhla meteorites, and if nitrogen was oxidized on Mars, this has important implications for the habitability potential of Mars. Here we report the results from the Sample Analysis at Mars (SAM) instrument suite aboard the Curiosity rover during the first year of surface operations in Gale Crater. Samples from the Rocknest aeolian deposit and sedimentary rocks (John Klein) were heated to approx 835degC under helium flow and the evolved gases were analyzed by MS and GC-MS. Two and possibly three peaks may be associated with the release of m/z 30 at temperatures ranging from 180degC to 500degC. M/z 30 has been tentatively identified as NO; other plausible contributions include CH2O and an isotopologue of CO, 12C18O. NO, CH2O, and CO may be reaction products of reagents (MTBSTFA/DMF) carried from Earth for the wet chemical derivatization experiments with SAM and/or derived from indigenous soil nitrogenated organics. Laboratory analyses indicate that it is also possible that <550degC evolved NO is produced via reaction of HCl with nitrates arising from the decomposition of perchlorates. All sources of m/z 30 whether it be martian or terrestrial will be considered and their implications for Mars will be discussed.

Navarro-Gonzalez, Rafael↗

NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

A single scoop of the Rocknest aeolian deposit was sieved (less than 150 micrometers), and four separate sample portions, each with a mass of approximately 50 mg, were delivered to individual cups inside the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of approximately 0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N-(tert-butyldimethylsilyl)-trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine-bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6-diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.

sample analysis at mars↗

NASA NTRS2013

Evidence for Perchlorates and the Origin of Chlorinated Hydrocarbons Detected by SAM at the Rocknest Aeolian Deposit in Gale Crater

Four individual sample portions from a single scoop of the Rocknest aeolian deposit were sieved ( 150 m) and delivered to the Sample Analysis at Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatography mass spectrometry analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of 0.01 to 2.3 nanomole.The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N-methyl-N- (tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA), a chemical that leaked from a derivatization cup inside SAM.The best candidate for the oxychloride phase in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated species measured by SAM, although other chlorine bearing phases are being considered. Laboratory pyrolysis experiments suggest that reaction of martian chlorine with organic carbon from MTBSTFA can explain the presence of the chloromethanes and a chloromethylpropene also detected by SAM.However, we cannot exclude the possibility that traces of organic carbon of either martian or exogenous origin contributed to some of the chloromethanes measured by SAM. Although the alteration history and exposure age of the Rocknest deposit is unknown, it is possible that oxidative degradation of complex organic matter by ionizing radiation or other chemical processes in Rocknest has occurred.

Mars Rover↗