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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 NTRS2022

Measurement report: Closure Analysis of Aerosol–cloud Composition in Tropical Maritime Warm Convection

Cloud droplet chemical composition is a key observable property that can aid understanding of how aerosols and clouds interact. As part of the Clouds, Aerosols and Monsoon Processes – Philippines Experiment (CAMP2Ex), three case studies were analyzed involving collocated airborne sampling of relevant clear and cloudy air masses associated with maritime warm convection. Two of the cases represented a polluted marine background, with signatures of transported East Asian regional pollution, aged over water for several days, while the third case comprised a major smoke transport event from Kalimantan fires. Sea salt was a dominant component of cloud droplet composition, in spite of fine particulate enhancement from regional anthropogenic sources. Furthermore, the proportion of sea salt was enhanced relative to sulfate in rainwater and may indicate both a propensity for sea salt to aid warm rain production and an increased collection efficiency of large sea salt particles by rain in subsaturated environments. Amongst cases, as precipitation became more significant, so too did the variability in the sea salt to (non-sea salt) sulfate ratio. Across cases, nitrate and ammonium were fractionally greater in cloud water than fine-mode aerosol particles; however, a strong covariability in cloud water nitrate and sea salt was suggestive of prior uptake of nitrate on large salt particles. A mass-based closure analysis of non-sea salt sulfate compared the cloud water air-equivalent mass concentration to the concentration of aerosol particles serving as cloud condensation nuclei for droplet activation. While sulfate found in cloud was generally constrained by the sub-cloud aerosol concentration, there was significant intra-cloud variability that was attributed to entrainment – causing evaporation of sulfate-containing droplets –and losses due to precipitation. In addition, precipitation tended to promote mesoscale variability in the sub-cloud aerosol through a combination of removal, convective downdrafts, and dynamically driven convergence. Physical mechanisms exerted such strong control over the cloud water compositional budget that it was not possible to isolate any signature of chemical production/loss using in-cloud observations. The cloud-free environment surrounding the non-precipitating smoke case indicated sulfate enhancement compared to convective mixing quantified by a stable gas tracer; however, this was not observed in the cloud water (either through use of ratios or the mass closure), perhaps implying that the warm convective cloud timescale was too short for chemical production to be a leading-order budgetary term and because precursors had already been predominantly exhausted. Closure of other species was truncated by incomplete characterization of coarse aerosol (e.g., it was found that only 10 %–50% of sea salt mass found in cloud was captured during clear-air sampling) and unmeasured gasphase abundances affecting closure of semi-volatile aerosol species (e.g., ammonium, nitrate and organic) and soluble volatile organic compound contributions to total organic carbon in cloud water.

Ewan Crosbie↗
NASA NTRS2023

Two Air Quality Regimes in Total Column NO2 over the Gulf of Mexico in May 2019: Shipboard and Satellite Views

The Satellite Coastal and Oceanic Atmospheric Pollution Experiment (SCOAPE) cruise in the Gulf of Mexico was conducted in May 2019 by NASA and the Bureau of Ocean Energy Management to determine the feasibility of using satellite data to measure air quality in a region of concentrated oil and natural gas (ONG) operations. SCOAPE addressed both technological and scientific issues related to measuring NO2 columns over the Outer Continental Shelf. Featured were nitrogen dioxide (NO 2 ) instruments (Pandora, Teledyne API analyzer) at Cocodrie, LA (29.26°, -90.66°), and on the Research Vessel Point Sur operating off the Louisiana coast with measurements of ozone, carbon monoxide and volatile organic compounds (VOC). The findings: (1) All NO 2 observations revealed two atmospheric regimes over the Gulf, the first influenced by tropical air in 10-14 May, the second influenced by flow from urban areas on 15-17 May; (2) Comparisons of OMI v4 and TROPOMI v1.3 TC (total column) NO 2 data with shipboard Pandora NO 2 column observations averaged 13% agreement with the largest difference during 15-17 May (~20%). At Cocodrie, the satellite-Pandora agreement was ~5%. (3) Three new-model Pandora instruments displayed a TC NO 2 precision of 0.01 Dobson Units (~5%); (4) Regions of smaller, older natural gas operations showed high methane readings from leakage; elevated VOC were also detected. Neither satellite nor spectrometer captured the magnitude of ambient NO 2 variability near ONG platforms. Given an absence of regular air quality monitoring over the Gulf of Mexico, SCOAPE data constitute a baseline against which future observations can be compared.

Nitrogen dioxide↗
NASA NTRSDate not supplied

Tropospheric Ozone in the NASA GEOS Model: Effects of Satellite NO2 Data Assimilation and Improvements in Background NOx Chemistry

Tropospheric ozone is a major atmospheric oxidant, the primary source of the hydroxyl radical, and a greenhouse gas. In the troposphere, it is produced from the oxidation of carbon monoxide and volatile organic compounds in the presence of nitrogen oxides (NOx=NO+NO2) or has its origins in the stratosphere. The tropospheric ozone burdens in global atmospheric chemistry models disagree by a factor of 1.5, indicating an incomplete understanding of ozone sources and sinks. Here we examine the tropospheric ozone simulation in NASA Global Modeling and Assimilation Office’s (GMAO’s) GEOS model with the GEOS-Chem chemistry mechanism (version 14.2), using observations from satellites, aircraft, ozonesondes, and surface sites. This modeling framework is used to produce GMAO’s GEOS Composition Forecasts (GEOS-CF), and it has been updated extensively with new emission inventories, improved model physics, satellite data assimilation capability, and an up-to-date chemical mechanism that includes tropospheric halogen chemistry and NOx recycling from particulate nitrate. Earlier versions of the model using GEOS-Chem version 12.0 showed an underestimate in tropospheric ozone in the northern hemisphere. We evaluate the ozone simulation in the updated model, focusing on the effects of assimilating satellite NO2 data from the Ozone Monitoring Instrument (OMI), constraining stratospheric ozone to satellite data, and updates to the NOx chemistry. We will examine changes in the vertical profiles of tropospheric ozone over the US in support of the Tropospheric Emissions: Monitoring of Pollution (TEMPO), and discuss implications for the tropospheric ozone budget.

V. Shah↗
NASA NTRSDate not supplied

Tropospheric Ozone in the NASA GEOS Model: Effects of Satellite Data Assimilation and Improvements in Background NO x Chemistry

Tropospheric ozone is a major atmospheric oxidant, the primary source of the hydroxyl radical, and a greenhouse gas. In the troposphere, it is produced from the oxidation of carbon monoxide and volatile organic compounds in the presence of nitrogen oxides (NO x =NO+NO 2 ) or has its origins in the stratosphere. The tropospheric ozone burdens in global atmospheric chemistry models disagree by a factor of 1.5, indicating an incomplete understanding of ozone sources and sinks. Here we examine the tropospheric ozone simulation in NASA Global Modeling and Assimilation Office’s (GMAO’s) GEOS model with the GEOS-Chem chemistry mechanism (version 14.2), using observations from satellites, aircraft, ozonesondes, and surface sites. This modeling framework is used to produce GMAO’s GEOS Composition Forecasts (GEOS-CF), and it has been updated extensively with new emission inventories, improved model physics, satellite data assimilation capability, and an up-to-date chemical mechanism that includes tropospheric halogen chemistry and NOx recycling from particulate nitrate. Earlier versions of the model using GEOS-Chem version 12.0 showed an underestimate in tropospheric ozone in the northern hemisphere. We evaluate the ozone simulation in the updated model, focusing on the effects of assimilating satellite NO 2 data from the Ozone Monitoring Instrument (OMI), constraining stratospheric ozone to satellite data, and updates to the NOx chemistry. We will examine changes in the vertical profiles of tropospheric ozone over the US in support of the Tropospheric Emissions: Monitoring of Pollution (TEMPO), and discuss implications for the tropospheric ozone budget.

Viral Shah↗
NASA NTRS2021

Analytical Methods and Testbeds for Characterizing Adsorbents and Catalysts for Atmosphere Revitalization of Crewed Spacecraft

Spacecraft environmental control and life support systems (ECLSS) include a number of air revitalization (AR) technologies to provide breathable air and a comfortable living environment to the crew. Crew health and comfort is ensured by controlling human produced CO2 (1 kg person-1 day-1) and water vapor (~2 kg person-1 day-1), and by removing trace contaminants (TCs) from cabin air. These life support functions on-board the International Space Station (ISS) are carried out by the Carbon Dioxide Removal Assembly (CDRA), the Water Processor Assembly (WPA), and the trace contaminant control system (TCCS). During the development of the TCCS, new analytical and theoretical methods were developed in the 1970s for characterizing adsorption and desorption characteristics of activated carbons for the purpose of designing suitable AR technologies required for controlling airborne trace contaminants within spacecraft cabins during long exploration missions. The TCCS removes harmful volatile organic compounds and other trace contaminants from the circulating air. It consists of a granular activated carbon (GAC) bed for the removal of high molecular weight contaminants and ammonia followed by a heated catalytic bed for low molecular weight hydrocarbons. The high temperature catalytic oxidizer (HTCO) of the TCCS, which operates at 400°C and requires 120W average power, removes low molecular weight compounds such as carbon monoxide (CO), formaldehyde (CH2O), and methane (CH4), that pass through the GAC bed. The Air Revitalization Laboratory at the Kennedy Space Center (KSC) was established to develop new analytical methods for evaluating emerging ECLSS technologies for use in future AR architectures. General properties of adsorbents and catalysts are required for trace contaminant control system design calculations and vendor-supplied data are seldom available at relevant process conditions of interest to spacecraft cabin applications. To address this shortcoming, appropriate testbeds were developed to measure the desired properties of AR technologies being considered for use in ECLS architectures. Generally, the testbeds developed at KSC challenge the test media (activated carbon, impregnated activated carbon, catalysts, zeolites, solid amines, or pleated filters) with simulated spacecraft gas streams containing representative mixtures of trace contaminants (volatile organic compounds, ammonia, CO, CO2, or siloxanes) at the flow rates, temperatures, and relative humidity that will be encountered within manned spacecraft. Work performed at KSC funded by NASA’s Advanced Exploration (AES) Program has included: Identifying candidate sorbents to replace commercially obsolete impregnated carbons for NH3 control within the TCCS, characterizing their adsorptive capacities using simulated spacecraft gas streams, and ranking their appropriateness in various AR applications; evaluating novel low temperature catalysts for controlling CO and formaldehyde by traditional and photocatalytic methods for trace contaminant control; development of analytical methods to assess regenerable solid amine performance for CO2 control via pressure swing adsorption. The Air Revitalization lab was also funded to study trace contaminant control by other NASA programs. These include: screening of candidate sorbents for the design of new Charcoal HEPA Integrated Particle Scrubber (CHIPS) filters for removing siloxanes from cabin air; characterizing the performance of an impregnated activated carbon at low humidity for use in ORION ECLS; screening of sorbents for protecting the Sabatier 2.0 catalyst from DMSO2, siloxanes, NH3, and solid amine byproducts.

Monje, Oscar↗
NASA NTRS2006

Thermal Conductivity of Ultem(TradeMark)/Carbon Nanofiller Blends

In an effort to improve polymer thermal conductivity (TC), Ultem(TradeMark) 1000 was compounded with nano-fillers of carbon allotropes. Ultem(TradeMark) 1000 was selected since it is both solution and melt processable. As-received and modified multiwalled carbon nanotubes (MWCNTs), vapor grown carbon nanofibers (CNF) and expanded graphite (EG) were investigated. MWCNTs were modified by functionalizing the surface through oxidization with concentrated acids, mixing with an alkyl bromide, and addition of alkyl and phosphorus compounds after initial treatment with n-butyl lithium. Functionalization was performed to improve the TC compatibility between the resin and MWCNTs. It was postulated that this may provide an improved interface between the MWCNT and the polymer which would result in enhanced TC. The nano-fillers were mixed with Ultem(TradeMark) 1000 in the melt and in solution at concentrations ranging from 5 to 40 wt%. Ribbons were extruded from the blends to form samples where the nano-fillers were aligned to some degree in the extrusion direction. Samples were also fabricated by compression molding resulting in random orientation of the nano-fillers. Thermal properties of the samples were evaluated by Differential Scanning Calorimetry (DSC) and Thermal Gravimetric Analyzer (TGA). Tensile properties of aligned samples were determined at room temperature. The specimens were cut from the ribbons in the extrusion direction; hence the nano-fillers are somewhat aligned in the direction of stress. Typically it was observed that melt mixed samples exhibited superior mechanical properties compared to solution mixed samples. As expected, increased filler loading led to increased modulus and decreased elongation with respect to the neat polymer. The degree of dispersion and alignment of the nano-fillers was determined by high-resolution scanning electron microscopy (HRSEM). HRSEM of the ribbons revealed that the MWCNTs and CNFs were predominantly aligned in the flow direction. The TC of the samples was measured using a Nanoflash(TradeMark) instrument. Since the MWCNTs and CNF are anisotropic, the TC was expected to be different in the longitudinal (parallel to the nanotube and fiber axis) and transverse (perpendicular to the nanotube and fiber axis) directions. The extruded ribbons provided samples for transverse TC measurements. However, to determine the TC in the longitudinal direction, the ribbons needed to be stacked and molded under 1.7 MPa and 270 C. Samples were then obtained by cutting the molded block with a diamond saw. The largest TC improvement was achieved for aligned samples when the measurement was performed in the direction of MWCNT and CNF alignment (i.e. longitudinal axis). Unaligned samples also showed a significant improvement in TC and may be potentially useful in applications when it is not possible to align the nano-filler. The results of this study will be presented.

Ghose, S.↗
NASA NTRS2001

Thiols in Hydrothermal Solution: Standard Partial Molal Properties and Their Role in the Organic Geochemistry of Hydrothermal Environments

Modern seafloor hydrothermal systems are locations where great varieties of geochemistry occur due to the enormous disequilibrium between vent fluids and seawater. The disequilibrium geochemistry has been hypothesized to include reactions to synthesize organic compounds. Despite the incomplete understanding of the carbon budget in hydrothermal systems, the organic geochemistry of these sites has received little attention. Experimental simulations of these environments, however, indicate that organic compounds may have difficulty forming in a purely aqueous environment. On the other hand, thiols, thioesters and disulfides have been implicated as reaction intermediates between CO or CO2 in experiments of carbon reduction in hydrothermal environments, as well as in a variety of biological processes and other abiotic reactions. The reduction of CO2 to thesis, for example, is observed using the FeS-H2S/FeS2 couple to provide the reducing power. We have used recent advances in theoretical geochemistry to estimate the standard partial moral thermodynamic properties and parameters for the revised Helgeson-Kirkham-Flowers equation of state for aqueous straight-chain alkyl thesis. With these data and parameters we have evaluated the role that organic sulfur compounds may play as reaction intermediates during organic compound synthesis. We conclude that organic sulfur compounds may hold the key to the organic chemistry leading to the origin of life in hydrothermal settings. These results may also explain the presence of sulfur in a number of biomolecules present in ancient thermophilic microorganisms.

Schulte, Mitchell D.↗
NASA NTRS1981

Organic compounds in meteorites and their origins

The current investigation represents an extensively updated version of a review conducted by Anders et al. (1973). The investigation takes into account the literature through mid-1980. It is pointed out that Type 1 carbonaceous chondrites (C1) contain 6% of their cosmic complement of carbon, mainly in the form of organic matter. Most authors now agree that this material represents primitive prebiotic matter. The principal questions remaining are what abiotic processes formed the organic matter, and to what extent these processes took place in locales other than the solar nebula, such as interstellar clouds or meteorite parent bodes. The problem is approached in three stages. It is attempted to reconstruct the physical conditions during condensation from the clues contained in the inorganic matrix of the meteorite. The condensation behavior of carbon under these conditions is determined on the basis of thermodynamic calculations. Model experiments on the condensation of carbon are performed, and the synthesized compounds are compared with those actually found in meteorites.

Hayatsu, R.↗
NASA NTRS2006

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Smart, Marshall↗
NASA NTRS2003

Method of synthesizing metal doped diamond-like carbon films

A method of synthesizing metal doped carbon films by placing a substrate in a chamber with a selected amount of a metalorganic compound. An electron cyclotron resonance is applied to the chamber in order to vaporize the metalorganic compound. The resonance is applied to the chamber until a metal doped carbon film is formed. The metalorganic compound is preferably selected from the group consisting of an organic salt of ruthenium, palladium, gold or platinum.

Ueno, Mayumi↗
NASA NTRS1994

Contamination Analyzer

Measurement of the total organic carbon content in water is important in assessing contamination levels in high purity water for power generation, pharmaceutical production and electronics manufacture. Even trace levels of organic compounds can cause defects in manufactured products. The Sievers Model 800 Total Organic Carbon (TOC) Analyzer, based on technology developed for the Space Station, uses a strong chemical oxidizing agent and ultraviolet light to convert organic compounds in water to carbon dioxide. After ionizing the carbon dioxide, the amount of ions is determined by measuring the conductivity of the deionized water. The new technique is highly sensitive, does not require compressed gas, and maintenance is minimal.

Source record↗
NASA NTRS2002

Hydrothermal Origin for Carbonate Globules in Martian Meteorite ALH84001: A Terrestrial Analogue from Spitsbergen (Norway)

Carbonate minerals in the ancient Martian meteorite ALH84001 are the only known solid phases that bear witness to the processing of volatile and biologically critical compounds (CO2, H2O) on early Mars. Similar carbonates have been found in xenoliths and their host basalts from Quaternary volcanic centers in northern Spitsbergen (Norway). These carbonates were deposited by hot (i.e., hydrothermal) waters associated with the volcanic activity. By analogy with the Spitsbergen carbonates, the ALH84001 carbonates were probably also deposited by hot water. Hydrothermal activity was probably common and widespread on Early Mars, which featured abundant basaltic rocks, water as ice or liquid, and heat from volcanos and asteroid impacts. On Earth, descendants of the earliest life forms still prefer hydrothermal environments, which are now shown to have been present on early Mars.

Treiman, Allan H.↗
NASA NTRS2006

Isotope Variations in Terrestrial Carbonates and Thermal Springs as Biomarkers: Analogs for Martian Processes

Stable isotope measurements of carbonate minerals contained within ALH84001 [1] suggest that fluids were present at 3.9 Gy on Mars [2, 3, 4, 5]. Both oxygen and carbon isotopes provide independent means of deciphering paleoenvironmental conditions at the time of carbonate mineral precipitation. In terrestrial carbonate rocks oxygen isotopes not only indicate the paleotemperature of the precipitating fluid, but also provide clues to environmental conditions that affected the fluid chemistry. Carbon isotopes, on the other hand, can indicate the presence or absence of organic compounds during precipitation (i.e. biogenically vs. thermogenically-generated methane), thus serving as a potential biomarker. We have undertaken a study of micro scale stable isotope variations measured in some terrestrial carbonates and the influence of organic compounds associated with the formation of these carbonates. Preliminary results indicate that isotope variations occur within narrow and discrete intervals, providing clues to paleoenvironmental conditions that include both biological and non-biological activity. These results carry implications for deciphering Martian isotope data and therefore potential biological prospecting on the planet Mars. Recently, Fourier Transform Spectrometer observations have detected methane occurring in the Martian atmosphere [6] that could be attributed to a possible biogenic source. Indeed, Mars Express has detected the presence of methane in the Martian atmosphere [7], with evidence indicating that methane abundances are greatest above those basins with high water concentrations.

Socki, Richard A.↗
NASA NTRS1993

A combustion products analyzer for contingency use during thermodegradation events on spacecraft

The Toxicology Laboratory at JSC and Exidyne Instrumentation Technologies (EIT) have developed a prototype Combustion Products Analyzer (CPA) to monitor, in real time, combustion products from a thermodegradation event on board spacecraft. The CPA monitors the four gases that are the most hazardous compounds (based on the toxicity potential and quantity produced) likely to be released during thermodegradation of synthetic materials: hydrogen fluoride (HF), hydrogen chloride (HCl), hydrogen cyanide (HCN), and carbon monoxide (CO). The levels of these compounds serve as markers to assist toxicologists in determining when the cabin atmosphere is safe for the crew to breathe following the contingency event. The CPA is a hand-held, battery-operated instrument containing four electrochemical sensors, one for each target gas, and a pump for drawing air across the sensors. The sensors are unique in their small size and zero-g compatibility. The immobilized electrolytes in each sensor permit the instrument to function in space and eliminate the possibility of electrolye leaks. The sample inlet system is equipped with a particulate filter that prevents clogging from airborne particulate matter. The CPA has a large digital display for gas concentrations and warming signals for low flow and low battery conditions. The CPA has flown on 13 missions beginning with STS 41 in Oct. 1990. Current efforts include the development of a microprocessor, an improved carbon monoxide sensor, and a ground-based test program to evaluate the CPA during actual thermodegradation of selected materials.

Wilson, Steve↗
NASA NTRS2016

Perchlorate and Volatiles of the Brine of Lake Vida (Antarctica): Implication for the in Situ Analysis of Mars Sediments

The cold (-13.4 C), cryoencapsulated, anoxic, interstitial brine of the 27 m-thick ice of Lake Vida (Victoria Valley, Antarctica) contains 49 microgram L-1 of perchlorate and 11 microgram L-1 of chlorate. Lake Vida brine (LVBr) may provide an analog for potential oxychlorine-rich subsurface brine on Mars. LVBr volatiles were analyzed by solid-phase microextraction (SPME) gas chromatography-mass spectrometry (GC-MS) with two different SPME fibers. With the exception of volatile organic sulfur compounds, most other volatiles observed were artifacts produced in the GC injector when the thermal decomposition products of oxychlorines reacted with reduced carbon derived from LVBr and the SPME fiber phases. Analysis of MilliQ water with perchlorate (40 microgram L-1) showed low level of organic artifacts, reflecting carbon limitation. In order to observe sample-derived organic compounds, both in analog samples and on Mars, the molar abundance of reduced carbon in a sample must exceed those of O2 and Cl2 produced during decomposition of oxychlorines. This suggests that the abundance of compounds observed by the Sample Analysis at Mars (SAM) instruments in Sheepbed samples (CB-3, CB5, and CB6) may be controlled by an increase in the reduced-carbon/oxychlorine ratio of these samples. To increase chances of in situ detection of Martian organics during pyrolysis-GC-MS, we propose that the derivatization agents stored on SAM may be used as an external source of reduced carbon, increasing artificially the reduced-carbon to perchlorate ratio during pyrolysis, allowing the expression of more abundant and perhaps more diverse Martian organic matter.

Mars analog experiment↗