Amino acid photostability on the Martian surface

Abstract— In the framework of international planetary exploration programs, several space missions are planned to search for organics and bio‐signatures on Mars. Previous attempts have not detected any organic compounds in the Martian regolith. It is therefore critical to investigate the processes that may affect organic molecules on and below the planet's surface. Laboratory simulations can provide useful data about the reaction pathways of organic material at Mars' surface. We have studied the stability of amino acid thin films against ultraviolet (UV) irradiation and use those data to predict the survival time of these compounds on and in the Martian regolith. We show that thin films of glycine and D‐alanine are expected to have half‐lives of 22 ± 5 hr and of 3 ± 1 hr, respectively, when irradiated with Mars‐like UV flux levels. Modelling shows that the half‐lives of the amino acids are extended to the order of 10⁷ years when embedded in regolith. These data suggest that subsurface sampling must be a key component of future missions to Mars dedicated to organic detection.     

TOF‐SIMS analysis of polycyclic aromatic hydrocarbons in Allan Hills 84001

Abstract— The presence of polycyclic aromatic hydrocarbons (PAHs) in the Martian meteorite Allan Hills 84001 (ALH 84001) was considered to be a major sign of ancient biogenic activity on planet Mars (McKay et al. 1996). An asserted spatial association of PAHs with carbonates, carriers of so‐called nanofossils, was crucial for their suggested connection to early life forms. Although both observations can be explained individually without employing living organisms, a lateral correlation of PAHs and carbonates would suggest a genetic link between PAHs and the microstructures, favoring a biogenic explanation. On the other hand, without such a correlation, a biogenic or even a Martian origin of the PAHs cannot be inferred. Here we show that there is no correlation of PAHs and carbonates in ALH 84001. Furthermore, a general trend of high PAH concentrations at locations where terrestrial lead is present obviously suggests a terrestrial origin for PAHs in ALH 84001.     

Ultraviolet Photoprocessing of Interstellar Dust Mantles as a Source of Polycyclic Aromatic Hydrocarbons and Other Conjugated Molecules

By co-depositing a gas mixture of simple carbon- and nitrogen-containing molecules with water on a 10 K surface and exposing it to ultraviolet radiation, we were able to form a residue. This residue was then placed aboard the EURECA satellite behind a magnesium fluoride window and exposed to solar radiation for 4 months before it was returned and analyzed. The resulting residue is believed to simulate the photoprocessing of organic dust mantles in the interstellar medium. Mass spectrometry indicated that the photoprocessing created a rich mixture of polycyclic aromatic hydrocarbons (PAHs) and other conjugated organic molecules, which may explain how PAHs are replenished in space.     

Assessment of Raman spectroscopy as a tool for the non-destructive identification of organic minerals and biomolecules for Mars studies

Several characteristic geological features found on the surface of Mars by planetary rovers suggest that a possible extinct biosphere could exist based on similar sources of energy as occurred on Earth. For this reason, analytical instrumental protocols for the detection of biomarkers in suitable geological matrices unequivocally have to be elaborated for future unmanned explorations including the forthcoming ESA ExoMars mission. As part of the Pasteur suite of analytical instrumentation on ExoMars, the Raman/LIBS instrument will seek elemental and molecular information about geological, biological and biogeological markers in the Martian record. A key series of experiments on terrestrial Mars analogues, of which this paper addresses a particularly important series of compounds, is required to obtain the Raman spectra of key molecules and crystals, which are characteristic for each biomarker. Here, we present Raman spectra of several examples of organic compounds which have been recorded non-destructively—higher n-alkanes, polycyclic aromatic hydrocarbons, carotenoids, salts of organic acids, pure crystalline terpenes as well as oxygen-containing organic compounds. In addition, the lower limit of β-carotene detection in sulphate matrices using Raman microspectroscopy was estimated.     

The evolution of polycyclic aromatic hydrocarbons under simulated inner asteroid conditions

Large polycyclic aromatic hydrocarbons (PAHs) are an important component of the interstellar medium. PAHs have been identified in the soluble and insoluble matter of carbonaceous chondrites (CCs). Here, we study the evolution of PAHs under conditions relevant to the interiors of asteroids and compare our results to PAHs observed in CCs. We have performed long‐term and short‐term hydrothermal experiments, in which we exposed PAH‐mineral mixture analogs of meteorites to temperature conditions representative of those predicted for asteroids interiors. Our results show that small PAHs with melting points within the aqueous alteration temperature of CCs form carbonaceous spherules in the presence of water. In this work, we describe the microstructure and morphology of these spherules. We discuss the similarities and differences compared to globules isolated from CCs.     

Analysis and survival of amino acids in Martian regolith analogs

Abstract— We have investigated the native amino acid composition of two analogs of Martian soil, JSC Mars‐1 and Salten Skov. A Mars simulation chamber has been built and used to expose samples of these analogs to temperature and lighting conditions similar to those found at low latitudes on the Martian surface. The effects of the simulated conditions have been examined using high‐performance liquid chromatography (HPLC). Exposure to energetic ultraviolet (UV) light in vacuum appears to cause a modest increase in the concentration of certain amino acids within the materials, which is interpreted as resulting from the degradation of microorganisms. The influence of low temperatures shows that the accretion of condensed water on the soils leads to the destruction of amino acids, supporting the idea that reactive chemical processes involving H₂O are at work within the Martian soil. We discuss the influence of UV radiation, low temperatures, and gaseous CO₂ on the intrinsic amino acid composition of Martian soil analogs and describe, with the help of a simple model, how these studies fit within the framework of life detection on Mars and the practical tasks of choosing and using Martian regolith analogs in planetary research.     

Assessment of the interstellar processes leading to deuterium enrichment in meteoritic organics

Abstract— The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low‐temperature gas phase ion‐molecule reactions, low‐temperature gas‐grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D‐enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, O, and N in the same compounds.     

Atmospheric entry heating of micrometeorites at Earth and Mars: Implications for the survival of organics

The atmospheric entry heating of micrometeorites (MMs) can significantly alter their pre‐existing mineralogy, texture, and organic material. The degree of heating depends predominantly on the gravity and atmospheric density of the planet on which they fall. For particles falling on Earth, the alteration can be significant, leading to the destruction of much of the pre‐entry organics; however, the weaker gravity and thinner atmosphere of Mars enhance the survival of MMs and increase the fraction of particles that preserve organic material. This paper investigates the entry heating of MMs on the Earth and Mars in order to examine the MM population on each planet and give insights into the survival of extraterrestrial organic material. The results show that particles reaching the surface of Mars experience a lower peak temperature compared to Earth and, therefore, experience less evaporative mass loss. Of the particles which reach the surface, 68.2% remain unmelted on Mars compared to only 22.8% on Earth. Due to evaporative mass loss, unmelted particles that reach the surface of Earth are restricted to sizes <70 μm whereas particles >475 μm survive unmelted on Mars. Approximately 10% of particles experience temperatures below ~800 K, that is, the sublimation temperature of refractory organics found in MMs. On Earth, this fraction is significantly lower with less than 1% expected to remain below this temperature. Lower peak temperatures coupled with the larger sizes of particles surviving without significant heating on Mars suggest a much higher fraction of organic material surviving to the Martian surface.     

The effects of Martian near surface conditions on the photochemistry of amino acids

In order to understand the complex multi-parameter system of destruction of organic material on the surface of Mars, step-by-step laboratory simulations of processes occurring on the surface of Mars are necessary. This paper describes the measured effects of two parameters, a CO₂ atmosphere and low temperature, on the destruction rate of amino acids when irradiated with Mars-like ultraviolet light (UV). The results show that the presence of a 7 mbar CO₂ atmosphere does not affect the destruction rate of glycine, and that cooling the sample to 210 K (average Mars temperature) lowers the destruction rate by a factor of 7. The decrease in the destruction rate of glycine by cooling the sample is thought to be predominantly caused by the slower reaction kinetics. When these results are scaled to Martian lighting conditions, cold thin films of glycine are assumed to have half-lives of 250 h under noontime peak illumination. It has been hypothesised that the absence of detectable native organic material in the Martian regolith points to the presence of oxidising agents. Some of these agents might form via the interaction of UV with compounds in the atmosphere. Water, although a trace component of Mars’ atmosphere, is suggested to be a significant source of oxidising species. However, gaseous CO₂ or adsorbed H₂O layers do not influence the photodestruction of amino acids significantly in the absence of reactive soil. Other mechanisms such as chemical processes in the Martian regolith need to be effective for rapid organic destruction.     

Could organic matter have been preserved on Mars for 3.5 billion years?

3.5 billion years (byr) ago, when it is thought that Mars and Earth had similar climates, biological evolution on Earth had made considerable progress, such that life was abundant. It is therefore surmised that prior to this time period the advent of chemical evolution and subsequent origin of life occurred on Earth and may have occurred on Mars. Analysis for organic compounds in the soil buried beneath the Martian surface may yield useful information regarding the occurrence of chemical evolution and possibly biological evolution. Calculations based on the stability of amino acids lead to the conclusion that remnants of these compounds, if they existed on Mars 3.5 byr ago, might have been preserved buried beneath the surface oxidizing layer. For example, if phenylalanine, an amino acid of average stability, existed on Mars 3.5 byr ago, then 1.6% would remain buried today, or 25 pg-2.5 ng of C g-1 Martian soil may exist from remnants of meteoritic and cometary bombardment, assuming that 1% of the organics survived impact.     

The provenance,formation, and implications of reduced carbon phases in Martian meteorites

This review is intended to summarize the current observations of reduced carbon in Martian meteorites, differentiating between terrestrial contamination and carbon that is indigenous to Mars. Indeed, the identification of Martian organic matter is among the highest priority targets for robotic spacecraft missions in the next decade, including the Mars Science Laboratory and Mars 2020. Organic carbon compounds are essential building blocks of terrestrial life, so the occurrence and origin (biotic or abiotic) of organic compounds on Mars is of great significance; however, not all forms of reduced carbon are conducive to biological systems. This paper discusses the significance of reduced organic carbon (including methane) in Martian geological and astrobiological systems. Specifically, it summarizes current thinking on the nature, sources, and sinks of Martian organic carbon, a key component to Martian habitability. Based on this compilation, reduced organic carbon on Mars, including detections of methane in the Martian atmosphere, is best described through a combination of abiotic organic synthesis on Mars and infall of extraterrestrial carbonaceous material. Although conclusive signs of Martian life have yet to be revealed, we have developed a strategy for life detection on Mars that can be utilized in future life‐detection studies.     

Surface modifications of comet‐exposed aerogel from the Stardust cometary collector

Abstract– Keystones removed from the Stardust cometary collector show varying degrees of visible fluorescence when exposed to UV light, with the brightest fluorescence associated with the space‐exposed surface. We investigated the spatial characteristics of this phenomenon further by using fluorescence microscopy, confocal Raman microscopy, and synchrotron Fourier transform infrared (FTIR) spectromicroscopy. Twenty‐four keystones, extracted from the Stardust cometary collector, were analyzed. Fluorescence measurements show two distributions with different excitation characteristics, indicating the presence of at least two distinct fluorophores. The first distribution is confined to within about 10 μm of the space‐exposed surface, whereas the second distribution is much broader with a maximum that is typically about 30–50 μm below the surface. Confocal Raman measurements did not reveal any changes associated with the surface; however, only features associated with aliphatic hydrocarbons were strong enough to be observed. FTIR measurements, on the other hand, show two distinct distributions at the space‐exposed surface: (1) a narrow, surface‐confined distribution originating from ?O₃SiH groups and (2) a broader, sub‐surface distribution originating from ?O₂SiH₂ groups. These functional groups were not observed in keystones extracted from the cometary flight spare or from the Stardust interstellar collector, indicating that they may result at least partially from cometary exposure. The presence of O₃SiH and O₂SiH₂ groups at the comet‐exposed surface suggests that the enhanced surface fluorescence is caused by defects in the O‐Si‐O network and not by organic contamination.     

The ORGANICS experiment on BIOPAN V: UV and space exposure of aromatic compounds

We studied the stability of aromatic compounds in low Earth orbit environment and describe the scientific results and successful flight of the ORGANICS experiment on-board the BIOPAN V space exposure facility. This experiment investigated the photo stability of large organic molecules in low Earth orbit. Thin films of selected organic molecules, such as polycyclic aromatic hydrocarbons (PAHs) and the fullerene C₆₀ were subjected to the low Earth orbit environment and the samples were monitored before and after flight. PAHs and fullerenes have been proposed as carriers for a number of astronomical absorption and emission features and are also identified in meteorites. Our experiment on BIOPAN V was exposed to a total fluence of 602.45 kJ m⁻² for photons in the range 170–280 nm. The experiment was also intended as a hardware test-flight for a long-term exposure experiment (Survival of organics in space) on the EXPOSE facility on the International Space Station (ISS). For the small fluence that was collected during the BIOPAN V experiment we found little evidence of photo-destruction. The results confirm that PAH molecules are very stable compounds in space. The small differences in destruction rates that are expected to arise among the PAH samples as a function of molecular size and structure will only show after the longer irradiation fluences that are expected in the exposure experiment on the ISS.     

Why exobiology on Mars?

Processing of organic molecules by liquid water was probably an essential requirement towards the emergence of terrestrial primitive life. According to Oparin's hypothesis, organic building blocks required for early life were produced from simple organic molecules formed in a primitive reducing atmosphere. Geochemists favour now a less reducing atmosphere dominated by carbon dioxide. In such an atmosphere, very few building blocks are formed. Import of extraterrestrial organic molecules may represent an alternative supply. Experimental support for such an alternative scenario is examined in comets, meteorites and micrometeorites. The early histories of Mars and Earth clearly show similarities. Liquid water was once stable on the surface of Mars attesting the presence of an atmosphere capable of decelerating C-rich micro-meteorites. Therefore, primitive life may have developed on Mars, as well. Liquid water disappeared from the surface of Mars very early, about 3.8 Ga ago. The Viking missions did not find, at the surface of the Martian soil, any organic molecules or clear-cut evidence for microbial activities such as photosynthesis, respiration or nutrition. The results can be explained referring to an active photochemistry of Martian soil driven by the high influx of solar UV. These experiments do not exclude the existence of organic molecules and fossils of micro-organisms which developed on early Mars until liquid water disappeared. Mars may store below its surface some well preserved clues of a still hypothetical primitive life.     

Methane and related trace species on Mars: Origin,loss, implications for life,and habitability

One of the most puzzling aspects of Mars is that organics have not yet been found on the surface. The simplest of organic molecules, methane, was detected in the Martian atmosphere for the first time in 2003. The existence and behavior of methane on Mars is of great significance, as methane is a potential biomarker. In this paper we review our current understanding of possible sources and sinks of methane on Mars. We also investigate the role of other trace species in the maintenance and removal of methane from the atmosphere, as well as of other organic material from the surface. In particular, we examine the exogenous, hydrogeochemical—especially serpentinization—and biological sources, for supplying methane to Mars. We suggest that comets and meteorites are the least likely, whereas low-temperature serpentinization is the most plausible of all candidates to explain the methane observations. Nevertheless, it is premature to rule out the role of biology in producing methane on Mars, in view of available data. It is important to note that the loss of methane to surface must also be factored into any “source” scenarios for methane. Ordinary heterogeneous loss process to surface tends to be very slow. On the other hand, a reactive surface could potentially accelerate the destruction of methane. If correct, it would imply that a larger source of methane is present than currently estimated on the basis of photochemical loss alone. A reactive surface can also explain why no organic material has ever been detected on the Martian surface. The surface could become reactive if some oxidizer were present. We suggest that vast quantities of a powerful oxidant, hydrogen peroxide, can be produced in electrochemistry triggered by electrostatic fields generated in the Martian dust devils and dust storms, and in normal saltation process close to the surface. Finally, current observations are inadequate to prove or disprove the existence of life on Mars, now or in the past. The question of extraterrestrial life is a fundamental one, and it should be addressed meticulously on future missions to Mars. Measurements planned on the Mars Science Laboratory (MSL), especially carbon isotopes and chirality, will go a long way in meeting this goal. A brief overview of the MSL Mission and measurements relevant to the question of life and habitability of Mars is also presented in this paper.     

NanoSIMS analysis of organic carbon from the Tissint Martian meteorite: Evidence for the past existence of subsurface organic‐bearing fluids on Mars

Two petrographic settings of carbonaceous components, mainly filling open fractures and occasionally enclosed in shock‐melt veins, were found in the recently fallen Tissint Martian meteorite. The presence in shock‐melt veins and the deuterium enrichments (δD up to +1183‰) of these components clearly indicate a pristine Martian origin. The carbonaceous components are kerogen‐like, based on micro‐Raman spectra and multielemental ratios, and were probably deposited from fluids in shock‐induced fractures in the parent rock of Tissint. After precipitation of the organic matter, the rock experienced another severe shock event, producing the melt veins that encapsulated a part of the organic matter. The C isotopic compositions of the organic matter (δ¹³C = ?12.8 to ?33.1‰) are significantly lighter than Martian atmospheric CO₂ and carbonate, providing a tantalizing hint for a possible biotic process. Alternatively, the organic matter could be derived from carbonaceous chondrites, as insoluble organic matter from the latter has similar chemical and isotopic compositions. The presence of organic‐rich fluids that infiltrated rocks near the surface of Mars has significant implications for the study of Martian paleoenvironment and perhaps to search for possible ancient biological activities on Mars.     

A search for amino acids and nucleobases in the Martian meteorite Roberts Massif 04262 using liquid chromatography‐mass spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography‐mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot‐water extracts with high relative abundances of β‐alanine and γ‐amino‐n‐butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight‐chained amine‐terminal n‐ω‐amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites (Burton et al. 2012; Chan et al. 2012). A carbon isotope ratio of ?24‰ ± 6‰ for β‐alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of n‐ω‐amino acids may be due to a high temperature Fischer‐Tropsch‐type synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.     

Ultraviolet irradiation of naphthalene in H2O ice: Implications for meteorites and biogenesis

Abstract— The polycyclic aromatic hydrocarbon (PAH) naphthalene was exposed to ultraviolet radiation in H₂O ice under astrophysical conditions, and the products were analyzed using infrared spectroscopy and high‐performance liquid chromatography. As we found in our earlier studies on the photoprocessing of coronene in H₂O ice, aromatic alcohols and ketones (quinones) were formed. The regiochemistry of the reactions is described and leads to specific predictions of the relative abundances of various oxidized naphthalenes that should exist in meteorites if interstellar ice photochemistry influenced their aromatic inventory. Since oxidized PAHs are present in carbon‐rich meteorites and interplanetary dust particles (IDPs), and ubiquitous in and fundamental to biochemistry, the delivery of such extraterrestrial molecules to the early Earth may have played a role in the origin and evolution of life.     

UIR Bands in Carbon Star Spectra

Unidentified infrared emission bands (UIR bands) have been attributed to polycyclic aromatic hydrocarbons (PAHs), which are believed to require ultraviolet radiation in order for the UIR bands to be excited. If, in addition to amorphous carbon and hydrogenated amorphous carbon (HAC) particles, PAHs are able to form in the outflows of cool carbon-rich stars (Cherchneff et al. 1991), then the weak UV radiation field from such stars would be unlikely to be able to excite the UIR bands and so the PAH species could remain undetected in the spectra of C-stars. However, cool carbon stars with hot companions might be exposed to strong enough UV radiation fields for UIR-band emission to be excited from PAHs. Buss et al. (1991) reported the detection of the 8 μm UIR-band (C-C stretch) in the IRAS LRS spectrum of HD 38218 (TU Tau), a carbon star with a hotter A2III companion. To investigate the phenomenon further, we have therefore obtained UKIRT CGS3 10 μm spectra of three carbon stars with hot companions, TU Tau, UV Aur and CS776. It was found that TU Tau showed the 11.25 μm and 8.6 μm UIR-bands (both attributed to C-H bend modes) at good contrast, while UV Aur clearly exhibited the 11.25 μm UIR band. No narrow UIR-band emission was detected in the spectrum of CS776. We have fitted these 10 μm region spectra using a χ²-minimization program equipped to fit stellar and dust emission continua together with the broad SiC feature and the narrow UIR-bands. The features seen in the spectra of TU Tau and UV Aur can be well fitted by a narrow 11.25 μm UIR-band sitting on top of a broad, self-absorbed 11.3 μm silicon carbide feature. Our results therefore provide strong support for the supposition that PAHs can form in carbon star outflows. This revised version was published online in September 2006 with corrections to the Cover Date.     

Alteration of five organic compounds by glow discharge plasma and UV light under simulated Mars conditions

The Viking missions to Mars failed to detect any organic material in regolith samples. Since then, several removal mechanisms of organic material have been proposed. Two of these proposed methods are removal due to exposure to plasmas created in dust devils and exposure to UV irradiation. The experiments presented here were performed to identify similarities between the two potential removal mechanisms and to identify any compounds produced from these mechanisms that would have been difficult for the Viking instruments to detect. Five organic compounds, phenanthrene, octadecane, octadecanoic acid, decanophenone and benzoic acid, were exposed to a glow discharge plasma created in simulated martian atmospheres as might be present in dust devils, and to UV irradiation similar to that found at the surface of Mars. Glow discharge exposure was carried out in a chamber with 6.9 mbar pressure of a Mars like gas composed mostly of carbon dioxide. The plasma was characterized using emission spectroscopy and found to contain cations and excited neutral species including carbon dioxide, carbon monoxide, and nitrogen. UV irradiation experiments were performed in a Mars chamber which simulates the temperature, pressure, atmospheric composition, and UV fluence rates of equatorial Mars. The non-volatile residues left after each exposure were characterized by mass loss, infrared spectroscopy and high resolution mass spectrometry. Oxidized, higher molecular weight versions of the parent compounds containing carbonyl, hydroxyl and alkenyl functional groups were identified. The presence of these oxidized compounds suggests that searches for organic material in soils on Mars use instrumentation suitable for detection of compounds which contain the above functional groups. Discussions of possible reaction mechanisms are given.