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Detection of Sub-Surface Water on Mars by Controlled and Natural Source Electromagnetic Induction

Detection of subsurface liquid water on Mars is a leading scientific objective for Mars exploration in this decade. We describe electromagnetic induction (EM) methods that are both uniquely well suited for detection of subsurface liquid water on Mars and practical within the context of a Mars exploration program. EM induction methods are ideal for detection of more highly conducting (liquid water bearing) soils and rock beneath a more resistive overburden. A combined natural source and controlled source method offers an efficient and unambiguous characterization of the depth to liquid water and the extent of the aqueous region. The controlled source method employs an ac vertical dipole source (horizontal loop) to probe the depth to the conductor and a natural source method (gradient sounding) to characterize its conductivity-thickness product. These methods are proven in geophysical exploration and can be tailored to cope with any reasonable Mars crustal electrical conductivity. We describe a practical experiment and discuss experiment optimization to address the range of material properties likely encountered in the Mars crust.

Connerney, J. E. P.↗

Attempt of Serendipitous Science During the Mojave Volatile Prospector Field Expedition

On 23 October a partial solar eclipse occurred across parts of the southwest United States between approximately 21:09 and 23:40 (UT), with maximum obscuration, 36%, occurring at 22:29 (UT). During 21-26 October 2014 the Mojave Volatile Prospector (MVP) field expedition deployed and operated the NASA Ames Krex2 rover in the Mojave desert west of Baker, California (Fig. 1, bottom). The MVP field expedition primary goal was to characterize the surface and sub-surface soil moisture properties within desert alluvial fans, and as a secondary goal to provide mission operations simulations of the Resource Prospector (RP) mission to a Lunar pole. The partial solar eclipse provided an opportunity during MVP operations to address serendipitous science. Science instruments on Krex2 included a neutron spectrometer, a near-infrared spectrometer with associated imaging camera, and an independent camera coupled with software to characterize the surface textures of the areas encountered. All of these devices are focused upon the surface and as a result are downward looking. In addition to these science instruments, two hazard cameras are mounted on Krex2. The chief device used to monitor the partial solar eclipse was the engineering development unit of the Near-Infrared Volatile Spectrometer System (NIRVSS) near-infrared spectrometer. This device uses two separate fiber optic fed Hadamard transform spectrometers. The short-wave and long-wave spectrometers measure the 1600-2400 and 2300-3400 nm wavelength regions with resolutions of 10 and 13 nm, respectively. Data are obtained approximately every 8 seconds. The NIRVSS stares in the opposite direction as the front Krex2.

soil moisture properties↗

Spacecraft Induced Molecular Return Flux Considerations for Icy Moon Missions Targeting Detection of Organics with Mass Spectrometers

Science missions targeting the detection of organics from jet plumes originating from icy moons (i.e. Europa and Enceladus) will employ next-generation, state-of-the-art mass spectrometers to measure the composition of icy moon plume effluents and exospheres. During fly-bys, as mass spectrometers make their scientific measurements, molecular emissions from the spacecraft can interact with the local exosphere and associated jet plumes from the sub-surface oceans of the icy moons. Spacecraft-induced molecular effluents collide with molecules from the ambient exosphere, and a fraction of the spacecraft emissions are returned to the spacecraft and its complement of science instruments. The rate at which emitted molecules are returned to the spacecraft by collisions with other molecules (e.g. in Europa’s exosphere) is the return flux. The return flux of molecular emission from spacecraft sources is a major contributor to contaminant deposition onto the complement of contamination-sensitive instruments. Characterization of return flux is critical to the definition of requirements for materials outgassing for the spacecraft and its instruments, and for the definition of thruster operations.

Soares, C. E.↗

The Mars Reconnaissance Orbiter Mission: 2018 Status

The Mars Reconnaissance Orbiter (MRO) continues its dual-mode mission of scientific exploration and programmatic support. Now in its 13th year of flight (and its 12th year in its low-altitude, sun-synchronous orbit around Mars), the spacecraft continues in its normal flight mode and its science instruments continue to acquire a treasure trove of data which is being used to study the Martian environment (surface, sub-surface, and atmosphere). To date (July 2018), more than 333 TB of scientific data have been returned to Earth. Building onto the 2017 IAC paper: “The Mars Reconnaissance Orbiter Mission: Continuing a Record of Exploration from Mars Orbit,” [1] this paper provides a 2018 status update on the MRO Mission. A signature event since the 2017 writing is the onset and evolution of a planet-encircling dust event (PEDE), the first such event since 2007. Additional recent science highlights for MRO include the discovery of mid-latitude ice cliffs, polar cap characterization, daily global mapping of the 2018 PEDE dust activity and the atmospheric thermal response, further characterization of the tantalizing recurring slope lineae (RSL), and continued detection of surface changes. Programmatically, UHF relay support for the Mars Science Laboratory (MSL) rover Curiosity and the Mars Exploration Rover (MER) rover Opportunity continues at a pace that provides the engineers and scientists operating those surface vehicles timely information to support their mission planning and science analysis. Most of the landing site characterization requests for the NASA Mars 2020 rover and the ESA ExoMars Rover/Surface Platform (RSP) missions have been completed, with final acquisitions delayed due to the obscuring dust haze from the current PEDE. In parallel, the flight team has faced new engineering challenges as the spacecraft has aged. The team has developed and is implementing actions that are aimed at stretching spacecraft battery life. A new all-stellar capability using the spacecraft’s star trackers now allows for normal spacecraft operations without IMUs. In addition to its current relay duties, MRO will be synchronized to provide critical communications support for the InSight Entry, Descent, and Landing (EDL) event on November 26, 2018, and will be readied to support InSight’s critical commissioning phase with UHF relay support and environmental characterization. A new split-pass relay capability has been developed which will allow MRO to relay with two surface vehicles in “close proximity” on the same overflight, i.e. the InSight lander and the Curiosity rover. Extended for another year of operations by NASA, this paper will highlight recent scientific progress and describe actions that will extend MRO’s life well into the 2020’s as a key element of the Mars Exploration Program.

Zurek, Richard W.↗

VIPER Mission Traverse Planning – Design, Strategies, and Dynamics

The Volatiles Investigation Polar Exploration Rover (VIPER) is a lunar polar volatiles prospecting mission developed through NASA’s Science Mission Directorate (SMD) Planetary Science Di-vision[1].VIPER is scheduled to land on Mons Mouton near the lunar South Pole in late 2024. VIPER’s primary mission goal is to characterize the distribution of water and volatiles across a range of thermal environments. This characterization aims to assist in understanding the origin of lunar polar volatiles and also help evaluate the In-Situ Resource Utilization (ISRU) potential of the lunar poles. The VIPER rover is a four-wheeled robotic vehicle weighing ~450 kg. It is solar-powered and teleoperated from Earth over a line-of-sight radio link. The rover can move at up to 20 cm/s on flat terrain. Accounting for commanding, localization, navigation, and obstacle-avoidance delays, however, the effective speed is closer to 1 cm/s. This effective speed is known as “Speed Made Good” (SMG), adopted from maritime culture, and kept as a key performance metric for VIPER oper-ations planning, execution, and evaluation. The mission duration is anticipated to be more than 90 Earth days and involves up to 20 km of driving. VIPER’s prospecting payload consists of spectrometers to detect volatiles and assess concentrations, context imagers, and a drill for sub-surface measurements down to one meter depth [2]. Mobility, combined with the prospecting and drill instrument suite, makes VIPER an analytically powerful resource mapper.

Volatiles Investigation Polar Exploration Rover (V↗

On the Determination of Local Sites for Shallow Ground Water Prospection Using Low Frequency Sounding Radars on Mars

Low frequency sounding radars should be able to probe the Martian subsurface layers down to varying depths, depending on the geo-electrical properties of the sounded sites. We present in this work four frequency dependent geo-electrical models of the Martian subsurface in the 1-20 MHz frequency band, based on laboratory electromagnetic characterization of Martian soil analogues. Those models correspond to local Martian sites, where we considered particular interest for the search of water using mainly the Ground Penetrating Radar (GPR) instrument of the Netlander mission. Results and discussion are also valid for both sounding experiments MARSIS and SHARAD. The four models of the Martian subsurface are designed to represent terrains where recent fluvial like features suggest the presence of near subsurface ground ice and probably liquid water. We performed measurements on volcanic and sedimentary materials that may be present on these sites under the appropriate geophysical conditions that may exist in those terrains. We then simulated the backscattered radar echo arising from each site in the 2 MHz frequency band, using the Finite Difference Time Domain (FDTD) algorithm, in order to evaluate the instrument performances to probe the subsurface stratigraphy of each site. Our results confirm that the near subsurface rich iron oxide mineralogy controls the instrument performances in terms of penetration depth and signal to noise ratio in the 2 MHz frequency band. We also discuss the geophysical and geo-electrical sounding conditions that could lead to an ambiguous detection of shallow subsurface water on Mars for the Netlander GPR. Finally we hope to present by the conference time a terrestrial test analogue site selected according to those creteria where deep sub-surface water have been detected 600 m deep using a prototype of the 2 MHz Netlander GPR in a field survey performed last febrary in the eastern part of the Egyptian desert.

Heggy, E.↗

3D Time-Lapse Electrical Resistivity Imaging of Rock Damage Patterns and Gas Flow Paths Resulting from Two Underground Chemical Explosions

Abstract Rock damage from underground nuclear explosions (UNEs) has a strong influence on sub-surface gas movement and on seismic waveform characteristics, both of which are used to detect UNEs. Although advanced numerical simulation capabilities exist to predict rock damage patterns and corresponding detection signals, those predictions are dependent on (generally) unknown properties of the host rock. For example, the effects of in-situ mechanical heterogeneities on the explosively generated damage/fractures that provide gas flow pathways to the surface are not well understood, due largely to the difficulty in accessing and characterizing the near-source region. In this paper we demonstrate the emerging use of electrical resistivity tomography (ERT) for imaging rock damage and gas flow patterns resulting from two relatively small-scale underground chemical explosions. Pre-explosion ERT and crosshole seismic imaging revealed a natural fracture zone within the test bed. Post-explosion imaging revealed that the damage zone was non-symmetric and was focused primarily within the pre-existing fracture zone, located 10 m above the first explosion and 5 m above the second explosion. Time-lapse ERT imaging of heated air injected into the detonation borehole revealed the primary gas flow paths to be within the upper margin of the same primary damage zone. These results point to the utility of ERT imaging for understanding rock damage and gas flow patterns under experimental conditions, and to the importance of understanding the effects of geologic heterogeneity on UNE detection signals, particularly gas surface breakthrough times.

58 GEOSCIENCES↗

Nano-Plasticity of an Electrified Ionic Liquid/Electrode Interface: Uncovering Hard–Soft Structuring via Controlled Metal Fill Factor

Here, ionic liquids (ILs) nanostructuring at electrified interfaces is of both fundamental and practical interest as these materials are increasingly gaining prominence in energy storage and conversion processes. However, much remains unresolved about IL potential-controlled (re)organization under highly polarized interfaces, mostly due to the difficulty of selectively probing both the distal and proximal surface layers of adsorbed ions. In this work, the structural dynamics of the innermost layer (<10 nm from the surface) were independently interrogated from that of the ionic layers in the sub-surface region (>100 nm from the surface), using an infrared (IR) spectroscopy approach. By tuning the metal fill factor of gold films deposited on conductive metal oxide-modified IR internal reflection elements, the charge-driven (re)structuring of the inner and distal layers of 1-butyl-1-methylpyrrolidinium trifluoromethanesulfonate is unveiled. Within a relatively wide potential region (~±1 V) bounding the potential of zero charges, the ionic liquid is shown to undergo a reversible (i.e., soft) reorganization whereby the innermost layer of anions (cations) is exchanged by a layer of cations (anions). Kinetically unhindered changes in the number density of constituent cations and anions largely follow electrostatic expectations in the subsurface region, whereas the innermost layer exhibits a pronounced hysteresis and very slow relaxation. Under larger negative potential bias, IL restructuring is characterized by a highly irreversible (i.e., hard) and intense interfacial densification of the BMPy + cations, consistent with the formation of nanoscale segregated liquids. The outcomes of this work reveal a plastic IL nanostructuring under a strong electric field.

36 MATERIALS SCIENCE↗

Formation of the oxyl’s potential energy surface by the spectral kinetics of a vibrational mode

One of the most reactive intermediates for oxidative reactions is the oxyl radical, an electron-deficient oxygen atom. The discovery of a new vibration upon photoexcitation of the oxygen evolution catalysis detected the oxyl radical at the SrTiO3 surface. The vibration was assigned to a motion of the sub-surface oxygen underneath the titanium oxyl (Ti–O●−) created upon hole transfer to (or electron extraction from) a hydroxylated surface site. Evidence for such an interfacial mode is derived from its spectral shape, which exhibited a Fano resonance—a coupling of a sharp normal mode to continuum excitations. Here, this Fano resonance is utilized to derive precise formation kinetics of the oxyl radical and its associated potential energy surface (PES). From the Fano lineshape, the formation kinetics are obtained from the anti-resonance (the kinetics of the coupling factor), the resonance (the kinetics of the coupled continuum excitations), and the frequency integrated spectrum (the kinetics of the normal mode’s cross-section). All three perspectives yield logistic function growth with a half-rise of 2.3 ± 0.3 ps and a time constant of 0.48 ± 0.09 ps. A non-equilibrium transient associated with photoexcitation is separated from the rise of the equilibrated PES. The logistic function characterizes the oxyl coverage at the very initial stages (t ∼ 0) to have an exponential growth rate that quickly decreases toward zero as a limiting coverage is reached. Such time-dependent reaction kinetics identify a dynamic activation barrier associated with the formation of a PES and quantify it for oxyl radical coverage.

Chemistry↗

In-situ Characterizations of Microstructural Degradation of Perovskite Solar Cells

Rapid progress has been achieved in perovskite solar cells (PSCs), and their efficiencies have improved from 3.8 % to 24.2 % in less than a decade. With low-cost processing, PSCs have shown exciting photovoltaic (PV) properties, such as effective optical absorption, a long carrier lifetime, and unique defect tolerance. While recent studies demonstrated improved stability up to 100 days, PSC technology is still challenged to meet the stringent industry requirements for commercialization. Despite considerable efforts, the underlying physical mechanisms for the inferior stability of PSCs are not well understood. One reason for this divergence is that many established measurement techniques (e.g., quantum efficiency, photoluminescence) probe the properties on length scales far greater than that of electronic and/or structural inhomogeneity (i.e., < 1 μm near grain boundaries) and therefore characterize convoluted and/or averaged properties. Ion/electron beam-based techniques have been extensively used to access the microstructures of PSCs, enabling atomic/nanoscale structural, chemical, optical, and electrical characterizations. For example, focused ion beam (FIB) milling produces an atomically smooth surface that minimizes the artifacts attributed to the surface roughness. FIB techniques can also create a well-defined cross-section of PSCs without mechanical damage in a physical cleaving sample preparation. While powerful, there are some concerns about possible beam damage of inorganic-organic perovskites via chemical-bond breakage and local heating. This project aims to comprehensively understand how the microstructural/interfacial properties of PSCs (e.g., Methylammonium Lead Iodide [MAPbI 3 ]) are modified under the irradiating ion beams. Specifically, we investigate the sub-surface properties of PSCs before and after Ar-ion beam injections. Kelvin probe force microscopy (KPFM) measures the contact potential differences (CPDs). Photoluminescence (PL) microscopy in conjunction with Finite-Difference Time-Domain (FDTD) simulations infers the formation of a “dead layer” (< 15 nm) on the subsurface of MAPbI 3 during Ar+ milling processes while preserving the initial bulk properties. The x-ray photoemission spectroscopy (XPS) confirms this modified surface is a lead-rich and iodine-deficient surface. We initiate customizing in-situ measurement setup while measuring the local optical and electrical properties of PSC under thermal (cooling, heating) and light stressors. Our results provide in-depth knowledge of the ion-beam impact on metal-halide perovskites and how this modified sub-surface impacts their properties under accelerated stressors of light and heat. Intensive Monte Carlo simulations of an electron beam interacting with PSCs provide the beam energy distribution in PSCs, proposing possible measurement conditions of using e-beam with minimizing beam damage. Our in-situ measurement platform can accommodate the diverse architecture of PSC devices for studying deterioration mechanisms under mixed environmental stressors.

14 SOLAR ENERGY↗

Rational Selection of Transition-Metal Oxide Electrocatalysts from Structure Electronic Structure-Activity Relations: The Role of Defects, Strain, and Sub-Surface Layering

This BES research investigates the physicochemical properties of metal oxides and how they affect electrocatalytic functionalities. The goal is to develop a predictive framework for realizing top-performing electrocatalytic materials for energy-critical reactions. The hypothesis is that well-defined thin films allow detailed mapping of structural-activity relationships because flat surfaces are more straightforward to characterize. Furthermore, the well-defined nature of thin-film metal oxides allows precise tuning of structural and chemical variables for structure-activity-relationship mapping. The proposed research has two technical objectives. The first is to experimentally assess whether the binding energies of surface oxygen can serve as an activity descriptor for oxygen electrocatalysis on metal oxides and then how to control them by tuning the structure and chemical variables. The second is to find the rate-limiting process in oxygen electrocatalysis and other small-molecule reactions. Similar mechanistic insights have been developed on well-defined platinum surfaces but not yet on oxides. This research addresses this gap and uses electrochemistry and X-ray photoemission spectroscopy to study oxide surface chemistry. The obtained insights are collectively analyzed to reveal how the oxides’ structural and chemical variables affect kinetics and can be used to design more active electrocatalysts for energy-critical reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of electrical discharges on Teflon dielectrics used as spacecraft thermal control

The dual effects of system degradation and reduced life of synchronous-orbit satellites as a result of differential spacecraft charging underscore the need for a clearer understanding of the prevailing electrical discharge phenomena. In a laboratory simulation, the electrical discharge current, surface voltage, emitted particle fluxes, and photo-emission associated with discharge events on electron beam irradiated silver-backed Teflon samples were measured. Sample surface damage was examined with optical and electron beam microscopes. The results are suggestive of a model in which the entire sample surface is discharged by lateral sub-surface currents flowing from a charge deposition layer through a localized discharge channel to the back surface of the sample. The associated return current pulse appears to have a duration which may be a signature by which different discharge processes may be characterized.

Yadlowsky, E. J.↗

The Use of CASES-97 Observations to Assess and Parameterize the Impact of Land-Surface Heterogeneity on Area-Average Surface Heat Fluxes for Large-Scale Coupled Atmosphere-Hydrology Models

To understand the effects of land-surface heterogeneity and the interactions between the land-surface and the planetary boundary layer at different scales, we develop a multiscale data set. This data set, based on the Cooperative Atmosphere-Surface Exchange Study (CASES97) observations, includes atmospheric, surface, and sub-surface observations obtained from a dense observation network covering a large region on the order of 100 km. We use this data set to drive three land-surface models (LSMs) to generate multi-scale (with three resolutions of 1, 5, and 10 kilometers) gridded surface heat flux maps for the CASES area. Upon validating these flux maps with measurements from surface station and aircraft, we utilize them to investigate several approaches for estimating the area-integrated surface heat flux for the CASES97 domain of 71x74 square kilometers, which is crucial for land surface model development/validation and area water and energy budget studies. This research is aimed at understanding the relative contribution of random turbulence versus organized mesoscale circulations to the area-integrated surface flux at the scale of 100 kilometers, and identifying the most important effective parameters for characterizing the subgrid-scale variability for large-scale atmosphere-hydrology models.

Chen, Fei↗

Starting Conditions for Hydrothermal Systems Underneath Martian Craters: Hydrocode Modeling

Mars is the most Earth-like of the Solar System s planets, and the first place to look for any sign of present or past extraterrestrial life. Its surface shows many features indicative of the presence of surface and sub-surface water, while impact cratering and volcanism have provided temporary and local surface heat sources throughout Mars geologic history. Impact craters are widely used ubiquitous indicators for the presence of sub-surface water or ice on Mars. In particular, the presence of significant amounts of ground ice or water would cause impact-induced hydrothermal alteration at Martian impact sites. The realization that hydrothermal systems are possible sites for the origin and early evolution of life on Earth has given rise to the hypothesis that hydrothermal systems may have had the same role on Mars. Rough estimates of the heat generated in impact events have been based on scaling relations, or thermal data based on terrestrial impacts on crystalline basements. Preliminary studies also suggest that melt sheets and target uplift are equally important heat sources for the development of a hydrothermal system, while its lifetime depends on the volume and cooling rate of the heat source, as well as the permeability of the host rocks. We present initial results of two-dimensional (2D) and three-dimensional (3D) simulations of impacts on Mars aimed at constraining the initial conditions for modeling the onset and evolution of a hydrothermal system on the red planet. Simulations of the early stages of impact cratering provide an estimate of the amount of shock melting and the pressure-temperature distribution in the target caused by various impacts on the Martian surface. Modeling of the late stage of crater collapse is necessary to characterize the final thermal state of the target, including crater uplift, and distribution of the heated target material (including the melt pool) and hot ejecta around the crater.

Pierazzo, E.↗

Mission Design Overview for the Phoenix Mars Scout Mission

The Phoenix mission "follows the water" by landing in a region where NASA's Mars Odyssey orbiter has discovered evidence of ice-rich soil very near the Martian surface. For three months after landing, the fixed Lander will perform in-situ and remote sensing investigations that will characterize the chemistry of the materials at the local surface, sub-surface, and atmosphere, and will identify potential provenance of key indicator elements of significance to the biological potential of Mars, including potential organics and any accessible water ice. The Lander will employ a robotic arm to dig to the ice layer, and will analyze the acquired samples using a suite of deck-mounted, science instruments. The development of the baseline strategy to achieve the objectives of this mission involves the integration of a variety of elements into a coherent mission plan.

Phoenix↗

The Telesupervised Adaptive Ocean Sensor Fleet (TAOSF) Architecture: Coordination of Multiple Oceanic Robot Boats

Earth science research must bridge the gap between the atmosphere and the ocean to foster understanding of Earth s climate and ecology. Ocean sensing is typically done with satellites, buoys, and crewed research ships. The limitations of these systems include the fact that satellites are often blocked by cloud cover, and buoys and ships have spatial coverage limitations. This paper describes a multi-robot science exploration software architecture and system called the Telesupervised Adaptive Ocean Sensor Fleet (TAOSF). TAOSF supervises and coordinates a group of robotic boats, the OASIS platforms, to enable in-situ study of phenomena in the ocean/atmosphere interface, as well as on the ocean surface and sub-surface. The OASIS platforms are extended deployment autonomous ocean surface vehicles, whose development is funded separately by the National Oceanic and Atmospheric Administration (NOAA). TAOSF allows a human operator to effectively supervise and coordinate multiple robotic assets using a sliding autonomy control architecture, where the operating mode of the vessels ranges from autonomous control to teleoperated human control. TAOSF increases data-gathering effectiveness and science return while reducing demands on scientists for robotic asset tasking, control, and monitoring. The first field application chosen for TAOSF is the characterization of Harmful Algal Blooms (HABs). We discuss the overall TAOSF architecture, describe field tests conducted under controlled conditions using rhodamine dye as a HAB simulant, present initial results from these tests, and outline the next steps in the development of TAOSF.

sensor web↗

Indigenous Carbonaceous Matter in the Nakhla Mars Meteorite

Detailed microanalysis of the Martian meteorite Nakhla has shown there are morphologically distinct carbonaceous features spatially associated with low-T aqueous alteration phases including salts and id-dingsite. A comprehensive suite of analytical instrumentation including optical microscopy, field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX) spectroscopy, focused ion beam (FIB) microscopy, transmission electron microscopy (TEM), two-step laser mass spectrometry (mu-L(sup 2)MS), laser mu-Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), and nanoscale secondary ion mass spectrometry (NanoSIMS) are being used to characterize the carbonaceous matter and host mineralogy. The search for carbonaceous matter on Mars has proved challenging. Viking Landers failed to unambiguously detect simple organics at either of the two landing sites although the Martian surface is estimated to have acquired at least 10(exp15) kg of C as a consequence of meteoritic accretion over the last several Ga. The dearth of organics at the Martian surface has been attributed to various oxidative processes including UV photolysis and peroxide activity. Consequently, investigations of Martian organics need to be focused on the sub-surface regolith where such surface processes are either severely attenuated or absent. Fortuitously since Martian meteorites are derived from buried regolith materials they provide a unique opportunity to study Martian organic geochemistry.

Clemett, S. J.↗

Analysis of Mixed Aryl/Alkyl Esters by Pyrolysis Gas Chromatography-Mass Spectrometry in the Presence of Perchlorate

Mars is an important target for Astrobiology. A key goal of the MSL mission was to determine whether Mars was habitable in the past, a que-tion that has now been definitely determined to be yes. Another key goal for Mars exploration is to understand the origin and distribution of organic material on Mars; this question is being addressed by the SAM instrument on MSL, and will also be informed by two upcoming Mars exploration missions, ExoMars and Mars 2020. These latter two missions have instrumentation capable of detecting and characterize organic molecules. Over the next decade, these missions will analyze organics in surface, near-surface and sub-surface samples. Each mission has the capability to analyze organics by different methods (pyrolysis gas chromatography-mass spectrometry [py-GC-MS]; laser desorption and thermal volatilization GC-MS; and Raman spectroscopy). Plausibly extraterrestrial organics were recently discovered by the Mars Science Laboratory (MSL), providing an important first step towards understanding the organic inventory on Mars [1]. The compounds detected were chlorobenzenes and chloroalkanes, but it was argued that chlorination of these compounds occurred during pyrolysis of samples containing unchlorinated organics in the presence of perchlorate. A recent report analyzed a suite of aromatic (benzene, toluene, benzoic acid, phthalic acid, and mellitic acid) and aliphatic (acetic acid, propane, propanol, and hexane) by pyrolysis under SAM-like conditions in the presence of perchlorate to attempt to constrain possible precursor molecules for the organic molecules detected on Mars. For aromatic compounds, the aromatic acids all readily produced SAM-relevant chlorobenzes, whereas benzene and toluene did not. This observation suggests that the chlorobenzene detected on Mars could have derived from compounds like mellitic acid, consistent with the previous hypothesis by Benner et al. [3]. Among the aliphatic molecules, it was shown that pyrolysis of alkanes and alcohols in the presence of perchlorates produced polychlorine containing chloro-alkanes similar to what was observed on Mars. Surpris-ingly, however, similar treatment of acetic acid pro-duced chloroketones, instead, and no chloroalkanes were reported. This suggests that the chloroalkanes detected in the Sheepbed mudstone were not derived from aliphatic carboxylic acids, but instead were from more reduced alcohols or even alkanes, or perhaps were degradation products of more complicated organic material. Because organics analyses on mars will rely heavily on py-GC-MS of perchlorate-containing samples over the next decade, it is important to understand the fate of organic molecules of biotic and abiotic origin under such conditions. In this work we begin a series of experiments to improve our understanding of products generated during py-GC-MS of increasingly complex organic molecules (esters, amides, peptides, nucleic acids, fatty acids) in the presence of perchlorate.

Burton, A. S.↗