In 1976, the Viking landers carried out the most comprehensive search for organics and microbial life in the martian regolith. Their results indicate that Mars' surface is lifeless and, surprisingly, ...depleted in organics at part-per-billion levels. Several biology experiments on the Viking landers gave controversial results that have since been explained by the presence of oxidizing agents on the surface of Mars. These oxidants may degrade abiotic or biological organics, resulting in their nondetection in the regolith. As several exploration missions currently focus on the detection of organics on Mars (or will do so in the near future), knowledge of the oxidative state of the surface is fundamental. It will allow for determination of the capability of organics to survive on a geological timescale, the most favorable places to seek them, and the best methods to process the samples collected at the surface. With this aim, we review the main oxidants assumed to be present on Mars, their possible formation pathways, and those laboratory studies in which their reactivity with organics under Mars-like conditions has been evaluated. Among the oxidants assumed to be present on Mars, only four have been detected so far: perchlorate ions (ClO
) in salts, hydrogen peroxide (H
O
) in the atmosphere, and clays and metal oxides composing surface minerals. Clays have been suggested as catalysts for the oxidation of organics but are treated as oxidants in the following to keep the structure of this article straightforward. This work provides an insight into the oxidizing potential of the surface of Mars and an estimate of the stability of organic matter in an oxidizing environment. Key Words: Mars surface-Astrobiology-Oxidant-Chemical reactions. Astrobiology 16, 977-996.
In this paper, we present the results obtained by the general circulation model developed at the Laboratoire de Météorologie Dynamique which has been used to simulate the Martian hydrological cycle. ...Our model, which employs a simplified cloud scheme, reproduces the observed Martian water cycle with unprecedented agreement. The modeled seasonal evolution of cloudiness, which also compares well with data, is described in terms of the meteorological phenomena that control the Martian cloud distribution. Whereas cloud formation in the tropical region results from seasonal changes in the overturning circulation, Polar Hood clouds are mostly driven by variations of atmospheric wave activity. A sensitivity study allows us to quantify the effects of the transport of water ice clouds on the seasonal evolution of the water cycle. The residence time of cloud particles is long enough to allow cloud advection over great distances (typically thousands of kilometers). Despite the relatively low proportion of clouds (∼10%) in the total atmospheric inventory of water, their ability to be transported over large distances generally acts at the expense of the north polar cap and generates a water cycle globally wetter by a factor of 2 than a cycle produced by a model neglecting cloud transport. Around aphelion season, clouds modulate the north to south migration of water in a significant fashion and participate just as much as vapor in the cross‐equatorial transport of total water. Most of the year, atmospheric waves generate an equatorward motion of water ice clouds near the polar vortex boundaries, partially balancing the opposite poleward flux of water vapor. The combination of both effects delays the return of water to the north polar cap and allows water to build up in the Martian tropics.
The Sample Analysis at Mars (SAM) instrument on board the Mars Science Laboratory Curiosity rover is designed to conduct inorganic and organic chemical analyses of the atmosphere and the surface ...regolith and rocks to help evaluate the past and present habitability potential of Mars at Gale Crater. Central to this task is the development of an inventory of any organic molecules present to elucidate processes associated with their origin, diagenesis, concentration, and long‐term preservation. This will guide the future search for biosignatures. Here we report the definitive identification of chlorobenzene (150–300 parts per billion by weight (ppbw)) and C2 to C4 dichloroalkanes (up to 70 ppbw) with the SAM gas chromatograph mass spectrometer (GCMS) and detection of chlorobenzene in the direct evolved gas analysis (EGA) mode, in multiple portions of the fines from the Cumberland drill hole in the Sheepbed mudstone at Yellowknife Bay. When combined with GCMS and EGA data from multiple scooped and drilled samples, blank runs, and supporting laboratory analog studies, the elevated levels of chlorobenzene and the dichloroalkanes cannot be solely explained by instrument background sources known to be present in SAM. We conclude that these chlorinated hydrocarbons are the reaction products of Martian chlorine and organic carbon derived from Martian sources (e.g., igneous, hydrothermal, atmospheric, or biological) or exogenous sources such as meteorites, comets, or interplanetary dust particles.
Key Points
First in situ evidence of nonterrestrial organics in Martian surface sediments
Chlorinated hydrocarbons identified in the Sheepbed mudstone by SAM
Organics preserved in sample exposed to ionizing radiation and oxidative condition
•Laboratory experiments in simulated flight conditions for the analysis of chlorohydrocarons on Mars.•Separation and identification of chlorohydrocarbons with the SAM instrument onboard NASA’s ...Curiosity rover.•Elution of chlorohydrocarbons with various stationary phases.
The Sample Analysis at Mars (SAM) instrument is a gas chromatograph-mass spectrometer onboard the NASA Curiosity rover, currently operating on the surface of Mars. Organic compounds are of major importance with regard to questions of habitability and the potential presence of life on Mars, and one of the mission’s main objectives is to analyze the organic content of soil and rock samples. In SAM’s first chromatographic measurements, however, unexpected chlorine-bearing organic molecules were detected. These molecules have different origins but the presence of perchlorates and chlorates detected at the surface of Mars suggests that reactivity between organic molecules and thermal decomposition products from oxychlorines is one of the major sources of the chlorinated organic molecules. Here we perform a comprehensive and systematic study of the separation of volatile chlorohydrocarbons with the chromatographic columns used in the SAM instrument. Despite the constrained operating conditions of the flight instrument, we demonstrate that SAM’s capillary chromatographic columns allow for effective separation and identification of a wide range of chlorine-bearing species. We also show that instrumental limitations prevent the detection of certain molecules, obscuring our ability to make definitive conclusions about the origin of these organic materials.
Aerosols in Titan's atmosphere play an important role in determining its thermal structure. They also serve as sinks for organic vapours and can act as condensation nuclei for the formation of ...clouds, where the condensation efficiency will depend on the chemical composition of the aerosols. So far, however, no direct information has been available on the chemical composition of these particles. Here we report an in situ chemical analysis of Titan's aerosols by pyrolysis at 600 °C. Ammonia (NH3) and hydrogen cyanide (HCN) have been identified as the main pyrolysis products. This clearly shows that the aerosol particles include a solid organic refractory core. NH3 and HCN are gaseous chemical fingerprints of the complex organics that constitute this core, and their presence demonstrates that carbon and nitrogen are in the aerosols.
Venus has thick clouds of H2SO4 aerosol particles extending from altitudes of 40 to 60 km. The 60-100 km region (the mesosphere) is a transition region between the 4 day retrograde superrotation at ...the top of the thick clouds and the solar-antisolar circulation in the thermosphere (above 100 km), which has upwelling over the subsolar point and transport to the nightside. The mesosphere has a light haze of variable optical thickness, with CO, SO2, HCl, HF, H2O and HDO as the most important minor gaseous constituents, but the vertical distribution of the haze and molecules is poorly known because previous descent probes began their measurements at or below 60 km. Here we report the detection of an extensive layer of warm air at altitudes 90-120 km on the night side that we interpret as the result of adiabatic heating during air subsidence. Such a strong temperature inversion was not expected, because the night side of Venus was otherwise so cold that it was named the 'cryosphere' above 100 km. We also measured the mesospheric distributions of HF, HCl, H2O and HDO. HCl is less abundant than reported 40 years ago. HDO/H2O is enhanced by a factor of approximately 2.5 with respect to the lower atmosphere, and there is a general depletion of H2O around 80-90 km for which we have no explanation.
The first results obtained by the ACP experiment onboard Huygens probe revealed that the main products obtained after thermolysis of Titan's collected aerosols, were ammonia (NH3) and hydrogen ...cyanide (HCN). Titan's aerosols, and their laboratory analogues named tholins, have been the subject of experimental or theoretical studies during the last four decades. These studies have been mainly devoted to understanding their origin and formation mechanisms, their physical, chemical and optical properties, and their role in the radiative equilibrium of the satellite. Before the arrival of the Cassini–Huygens mission, the dense layer of aerosols hid many aspects of the satellite's surface and precious information about its composition.
If Titan's aerosols have been in the eye and mind of planetary scientists during such a long time, it is not surprising that a literature survey displays a good quantity of papers on aerosol analogues. With aerosol analogues we mean any material produced in a terrestrial laboratory under conditions that try to represent those of Titan's atmosphere. We present here a study aimed to understand the particularities of aerosol analogues synthesized in different laboratories around the world in order to determine some of their most representative chemical fingerprints and in some cases, to perform a direct comparison of the volatiles produced after a thermal treatment done in conditions similar to the ones used by the ACP experiment. From the information collected, we propose a broad classification of aerosol analogues highlighting the materials that can be more representative of Titan's aerosols in terms of their content of organic volatiles. We identify the laboratory analogs that best suit the ACP results; such identification is of prime importance to correctly predict the optical properties of Titan's aerosol and to accurately estimate their contribution in radiative equilibrium models and/or to assess their role in chemical reactions of astrobiological importance at Titan's surface.
► Final exploitation of Huygens mission Data. ► Intercomparison between in situ results and laboratory investigations. ► Titan's chemistry complexity confirmed. ► Orientation of future laboratory simulations of Titan's gas/particulate chemistry.
In preparation for the Russian Luna-Resurs mission we combined our compact time-of-flight mass spectrometer (TOF-MS) with a chemical pre-separation of the species by gas chromatography (GC). Coupled ...measurements with both instruments were successfully performed with the prototype of the mass spectrometer and a flight-like gas chromatograph. The system was tested with two test gas mixtures, a mixture of hydrocarbons and a mixture of noble gases. Due to its capability to record mass spectra over the full mass range at once with high sensitivity and a dynamic range of up to 106 within 1s, the TOF-MS system is a valuable extension of the GC analytical system. Based on the measurements with calibration gases performed with the combined GC–MS prototype and under assumption of mean characteristics for the Moon's regolith, the detection limit for volatile species in a soil sample is estimated to 2·10−10 by mass for hydrocarbons and 2·10−9 by mass for noble gases.
•Development of a sensitive GC-MS instrument for in situ measurements on the Moon.•GC-MS coupling with a time-of-flight type mass spectrometer.•Prototype measurements with noble gases and hydrocarbons.
The Sample Analysis at Mars (SAM) instrument onboard the Curiosity rover, is specifically designed for in situ molecular and isotopic analyses of martian surface materials and atmosphere. It ...contributes to the Mars Science Laboratory (MSL) missions primary scientific goal to characterize the potential past, present or future habitability of Mars. In all of the analyses of solid samples delivered to SAM so far, chlorinated organic compounds have been detected above instrument background levels and identified by gas chromatography coupled to mass spectrometry (GC–MS) (Freissinet et al., 2015; Glavin et al., 2013). While some of these may originate from reactions between oxychlorines and terrestrial organic carbon present in the instrument background (Glavin et al., 2013), others have been demonstrated to originate from indigenous organic carbon present in samples (Freissinet et al., 2015).
We present here laboratory calibrations that focused on the analyses performed with the MXT-CLP GC column (SAM GC-5 channel) used for nearly all of the GC–MS analyses of the martian soil samples carried out with SAM to date. Complementary to the mass spectrometric data, gas chromatography allows us to separate and identify the species analyzable in a nominal SAM-GC run time of about 21min. To characterize the analytical capabilities of this channel within the SAM Flight Model (FM) operating conditions on Mars, and their implications on the detection of organic matter, it is required to perform laboratory experimental tests and calibrations on spare model components. This work assesses the SAM flight GC-5 column efficiency, confirms the identification of the molecules based on their retention time, and enables a better understanding of the behavior of the SAM injection trap (IT) and its release of organic molecules. This work will enable further optimization of the SAM-GC runs for additional samples to be analyzed during the MSL mission.
•Laboratory analyses to reproduce the SAM GC–MS measurements.•Identification of organic molecules on Mars with SAM.•Performances of the SAM GC5 channel for organic molecules analysis.
Spectroscopy for the investigation of the characteristics of the atmosphere of Venus (SPICAV) is a suite of three spectrometers in the UV and IR range with a total mass of 13.9
kg flying on the Venus ...Express (VEX) orbiter, dedicated to the study of the atmosphere of Venus from ground level to the outermost hydrogen corona at more than 40,000
km. It is derived from the SPICAM instrument already flying on board Mars Express (MEX) with great success, with the addition of a new IR high-resolution spectrometer, solar occultation IR (SOIR), working in the solar occultation mode. The instrument consists of three spectrometers and a simple data processing unit providing the interface of these channels with the spacecraft.
A UV spectrometer (118–320
nm, resolution 1.5
nm) is identical to the MEX version. It is dedicated to nadir viewing, limb viewing and vertical profiling by stellar and solar occultation. In nadir orientation, SPICAV UV will analyse the albedo spectrum (solar light scattered back from the clouds) to retrieve SO
2, and the distribution of the UV-blue absorber (of still unknown origin) on the dayside with implications for cloud structure and atmospheric dynamics. On the nightside, γ and δ bands of NO will be studied, as well as emissions produced by electron precipitations. In the stellar occultation mode the UV sensor will measure the vertical profiles of CO
2, temperature, SO
2, SO, clouds and aerosols. The density/temperature profiles obtained with SPICAV will constrain and aid in the development of dynamical atmospheric models, from cloud top (∼60
km) to 160
km in the atmosphere. This is essential for future missions that would rely on aerocapture and aerobraking. UV observations of the upper atmosphere will allow studies of the ionosphere through the emissions of CO, CO
+, and CO
2
+, and its direct interaction with the solar wind. It will study the H corona, with its two different scale heights, and it will allow a better understanding of escape mechanisms and estimates of their magnitude, crucial for insight into the long-term evolution of the atmosphere.
The SPICAV VIS-IR sensor (0.7–1.7
μm, resolution 0.5–1.2
nm) employs a pioneering technology: an acousto-optical tunable filter (AOTF). On the nightside, it will study the thermal emission peeping through the clouds, complementing the observations of both VIRTIS and Planetary Fourier Spectrometer (PFS) on VEX. In solar occultation mode this channel will study the vertical structure of H
2O, CO
2, and aerosols.
The SOIR spectrometer is a new solar occultation IR spectrometer in the range
λ=2.2–4.3
μm, with a spectral resolution
λ/Δ
λ>15,000, the highest on board VEX. This new concept includes a combination of an echelle grating and an AOTF crystal to sort out one order at a time. The main objective is to measure HDO and H
2O in solar occultation, in order to characterize the escape of D atoms from the upper atmosphere and give more insight about the evolution of water on Venus. It will also study isotopes of CO
2 and minor species, and provides a sensitive search for new species in the upper atmosphere of Venus. It will attempt to measure also the nightside emission, which would allow a sensitive measurement of HDO in the lower atmosphere, to be compared to the ratio in the upper atmosphere, and possibly discover new minor atmospheric constituents.
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