Establishing the presence and state of organic matter, including its possible biosignatures, in martian materials has been an elusive quest, despite limited reports of the existence of organic matter ...on Mars. We report the in situ detection of organic matter preserved in lacustrine mudstones at the base of the ~3.5-billion-year-old Murray formation at Pahrump Hills, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. Diverse pyrolysis products, including thiophenic, aromatic, and aliphatic compounds released at high temperatures (500° to 820°C), were directly detected by evolved gas analysis. Thiophenes were also observed by gas chromatography–mass spectrometry. Their presence suggests that sulfurization aided organic matter preservation. At least 50 nanomoles of organic carbon persists, probably as macromolecules containing 5% carbon as organic sulfur molecules.
Obtaining carbon isotopic information for organic carbon from Martian sediments has long been a goal of planetary science, as it has the potential to elucidate the origin of such carbon and aspects ...of Martian carbon cycling. Carbon isotopic values (δ
C
) of the methane released during pyrolysis of 24 powder samples at Gale crater, Mars, show a high degree of variation (-137 ± 8‰ to +22 ± 10‰) when measured by the tunable laser spectrometer portion of the Sample Analysis at Mars instrument suite during evolved gas analysis. Included in these data are 10 measured δ
C values less than -70‰ found for six different sampling locations, all potentially associated with a possible paleosurface. There are multiple plausible explanations for the anomalously depleted
C observed in evolved methane, but no single explanation can be accepted without further research. Three possible explanations are the photolysis of biological methane released from the subsurface, photoreduction of atmospheric CO
, and deposition of cosmic dust during passage through a galactic molecular cloud. All three of these scenarios are unconventional, unlike processes common on Earth.
A single scoop of the Rocknest aeolian deposit was sieved (< 150 µm), and four separate sample portions, each with a mass of ~50 mg, were delivered to individual cups inside the Sample Analysis at ...Mars (SAM) instrument by the Mars Science Laboratory rover's sample acquisition system. The samples were analyzed separately by the SAM pyrolysis evolved gas and gas chromatograph mass spectrometer analysis modes. Several chlorinated hydrocarbons including chloromethane, dichloromethane, trichloromethane, a chloromethylpropene, and chlorobenzene were identified by SAM above background levels with abundances of ~0.01 to 2.3 nmol. The evolution of the chloromethanes observed during pyrolysis is coincident with the increase in O2 released from the Rocknest sample and the decomposition of a product of N‐methyl‐N‐(tert‐butyldimethylsilyl)‐trifluoroacetamide (MTBSTFA), a chemical whose vapors were released from a derivatization cup inside SAM. The best candidate for the oxychlorine compounds in Rocknest is a hydrated calcium perchlorate (Ca(ClO4)2·nH2O), based on the temperature release of O2 that correlates with the release of the chlorinated hydrocarbons measured by SAM, although other chlorine‐bearing phases are being considered. Laboratory analog experiments suggest that the reaction of Martian chlorine from perchlorate decomposition with terrestrial organic carbon from MTBSTFA during pyrolysis can explain the presence of three chloromethanes and a chloromethylpropene detected by SAM. Chlorobenzene may be attributed to reactions of Martian chlorine released during pyrolysis with terrestrial benzene or toluene derived from 2,6‐diphenylphenylene oxide (Tenax) on the SAM hydrocarbon trap. At this time we do not have definitive evidence to support a nonterrestrial carbon source for these chlorinated hydrocarbons, nor do we exclude the possibility that future SAM analyses will reveal the presence of organic compounds native to the Martian regolith.
Key Points
Perchlorates and chlorinated hydrocarbons detected by SAM at Rocknest
Chlorohydrocarbons produced from terrestrial organic carbon and Martian chlorine
No definitive evidence of Martian organic carbon at Rocknest
Late Archean Rise of Aerobic Microbial Ecosystems Eigenbrode, Jennifer L.; Freeman, Katherine H.
Proceedings of the National Academy of Sciences - PNAS,
10/2006, Letnik:
103, Številka:
43
Journal Article
Recenzirano
Odprti dostop
We report the$^{13}C$content of preserved organic carbon for a 150 million-year section of late Archean shallow and deepwater sediments of the Hamersley Province in Western Australia. We find ...a$^{13}C$enrichment of ≈10‰ in organic carbon of post-2.7-billion-year-old shallow-water carbonate rocks relative to deepwater sediments. The shallow-water organic-carbon$^{13}C$content has a 29‰ range in values (-57 to -28‰), and it contrasts with the less variable but strongly$^{13}C-depleted $(-40 to -45‰) organic carbon in deepwater sediments. The$^{13}C$enrichment likely represents microbial habitats not as strongly influenced by assimilation of methane or other$^{13}C-depleted$substrates. We propose that continued oxidation of shallow settings favored the expansion of aerobic ecosystems and respiring organisms, and, as a result, isotopic signatures of preserved organic carbon in shallow settings approached that of photosynthetic biomass. Facies analysis of published carbon-isotopic records indicates that the Hamersley shallow-water signal may be representative of a late Archean global signature and that it preceded a similar, but delayed,$^{13}C$enrichment of deepwater deposits. The data suggest that a globalscale expansion of oxygenated habitats accompanied the progression away from anaerobic ecosystems toward respiring microbial communities fueled by oxygenic photosynthesis before the oxygenation of the atmosphere after 2.45 billion years ago.
The Sample Analysis at Mars instrument stepped combustion experiment on a Yellowknife Bay mudstone at Gale crater, Mars revealed the presence of organic carbon of Martian and meteoritic origins. The ...combustion experiment was designed to access refractory organic carbon in Mars surface sediments by heating samples in the presence of oxygen to combust carbon to CO
2
. Four steps were performed, two at low temperatures (less than ∼550 °C) and two at high temperatures (up to ∼870 °C). More than 950 μg C/g was released at low temperatures (with an isotopic composition of δ
13
C = +1.5 ± 3.8‰) representing a minimum of 431 μg C/g indigenous organic and inorganic Martian carbon components. Above 550 °C, 273 ± 30 μg C/g was evolved as CO
2
and CO (with estimated δ
13
C = −32.9‰ to −10.1‰ for organic carbon). The source of high temperature organic carbon cannot be definitively confirmed by isotopic composition, which is consistent with macromolecular organic carbon of igneous origin, meteoritic infall, or diagenetically altered biomass, or a combination of these. If from allochthonous deposition, organic carbon could have supported both prebiotic organic chemistry and heterotrophic metabolism at Gale crater, Mars, at ∼3.5 Ga.
The Great Oxidation Event (GOE) represents a crucial juncture in Earth history, signifying the rise in atmospheric oxygen from parts per million to percent levels at ∼2.45–2.32 billion-years-ago ...(Ga). Although planetary oxygenation undoubtedly led to the inception of the contemporary Earth system, the trigger(s) and mechanism(s) controlling this chemical reorganisation remain elusive. Quantitative estimates of the atmosphere's composition in the prelude to the GOE are central to understanding this oxygenation event. Previous analyses of 2.65–2.5 Ga sediments from the Griqualand Basin (South Africa) invoke a tantalising picture of an unusual Earth environment, alluding to an atmosphere periodically dominated by a layer of organic particles (“haze”) formed from methane photolysis. However, as yet this hypothesis has remained untested. Here we present four new coupled carbon and quadruple sulphur isotope records from distal, time equivalent (2.7–2.5 Ga), sedimentary successions from South Africa and Western Australia. These extended records reveal similar chemostratigraphic trends, supporting a dynamic terminal-Neoarchaean atmosphere, oscillating between a hazy state at elevated methane concentrations, and a haze-free anoxic background state. We suggest these atmospheric aberrations were related to heightened biogenic methane fluxes fuelled by enhanced nutrient delivery from climatically or weathering induced feedbacks. These data question the canonical view of a simple, unidirectional planetary oxygenation and signify that the overture to the GOE was governed by complex feedbacks within the Earth–biosphere system.
•We present four ∼2.7–2.5 Ga coupled carbon and quadruple sulphur isotope records.•These data depict a biospheric overhaul of atmospheric chemistry at ∼2.7 Ga.•Post-2.7 Ga atmospheres were dynamic, switching between haze-free and hazy states.•We suggest that amplified biogenic CH4 fluxes drove these atmospheric aberrations.•Biology apparently regimented atmosphere chemistry in the prelude to the GOE.
Mars methane detection and variability at Gale crater Webster, Christopher R.; Mahaffy, Paul R.; Atreya, Sushil K. ...
Science (American Association for the Advancement of Science),
01/2015, Letnik:
347, Številka:
6220
Journal Article
Recenzirano
Odprti dostop
Reports of plumes or patches of methane in the martian atmosphere that vary over monthly time scales have defied explanation to date. From in situ measurements made over a 20-month period by the ...tunable laser spectrometer of the Sample Analysis at Mars instrument suite on Curiosity at Gale crater, we report detection of background levels of atmospheric methane of mean value 0.69 ± 0.25 parts per billion by volume (ppbv) at the 95% confidence interval (CI). This abundance is lower than model estimates of ultraviolet degradation of accreted interplanetary dust particles or carbonaceous chondrite material. Additionally, in four sequential measurements spanning a 60-sol period (where 1 sol is a martian day), we observed elevated levels of methane of 7.2 ± 2.1 ppbv (95% CI), implying that Mars is episodically producing methane from an additional unknown source.
Enceladus’s long-lived plume of ice grains and water vapor makes accessing oceanic material readily achievable from orbit (around Saturn or Enceladus) and from the moon’s surface. In preparation for ...the National Academies of Sciences, Engineering and Medicine 2023–2032 Planetary Science and Astrobiology Decadal Survey, we investigated four architectures capable of collecting and analyzing plume material from orbit and/or on the surface to address the most pressing questions at Enceladus: Is the subsurface ocean inhabited? Why, or why not? Trades specific to these four architectures were studied to allow an evaluation of the science return with respect to investment. The team found that Orbilander, a mission concept that would first orbit and then land on Enceladus, represented the best balance. Orbilander was thus studied at a higher fidelity, including a more detailed science operations plan during both orbital and landed phases, landing site characterization and selection analyses, and landing procedures. The Orbilander mission concept demonstrates that scientifically compelling but resource-conscious Flagship-class missions can be executed in the next decade to search for life at Enceladus.
The Mars Science Laboratory (MSL) has an instrument package capable of making measurements of past and present environmental conditions. The data generated may tell us if Mars is, or ever was, able ...to support life. However, the knowledge of Mars' past history and the geological processes most likely to preserve a record of that history remain sparse and, in some instances, ambiguous. Physical, chemical, and geological processes relevant to biosignature preservation on Earth, especially under conditions early in its history when microbial life predominated, are also imperfectly known. Here, we present the report of a working group chartered by the Co-Chairs of NASA's MSL Project Science Group, John P. Grotzinger and Michael A. Meyer, to review and evaluate potential for biosignature formation and preservation on Mars. Orbital images confirm that layered rocks achieved kilometer-scale thicknesses in some regions of ancient Mars. Clearly, interplays of sedimentation and erosional processes govern present-day exposures, and our understanding of these processes is incomplete. MSL can document and evaluate patterns of stratigraphic development as well as the sources of layered materials and their subsequent diagenesis. It can also document other potential biosignature repositories such as hydrothermal environments. These capabilities offer an unprecedented opportunity to decipher key aspects of the environmental evolution of Mars' early surface and aspects of the diagenetic processes that have operated since that time. Considering the MSL instrument payload package, we identified the following classes of biosignatures as within the MSL detection window: organism morphologies (cells, body fossils, casts), biofabrics (including microbial mats), diagnostic organic molecules, isotopic signatures, evidence of biomineralization and bioalteration, spatial patterns in chemistry, and biogenic gases. Of these, biogenic organic molecules and biogenic atmospheric gases are considered the most definitive and most readily detectable by MSL.
The Sample Analysis at Mars (SAM) instrument on the Mars Science Laboratory (MSL) rover Curiosity detected evolved gases during thermal analysis of soil samples from the Rocknest aeolian deposit in ...Gale Crater. Major species detected (in order of decreasing molar abundance) were H2O, SO2, CO2, and O2, all at the µmol level, with HCl, H2S, NH3, NO, and HCN present at the tens to hundreds of nmol level. We compute weight % numbers for the major gases evolved by assuming a likely source and calculate abundances between 0.5 and 3 wt.%. The evolution of these gases implies the presence of both oxidized (perchlorates) and reduced (sulfides or H‐bearing) species as well as minerals formed under alkaline (carbonates) and possibly acidic (sulfates) conditions. Possible source phases in the Rocknest material are hydrated amorphous material, minor clay minerals, and hydrated perchlorate salts (all potential H2O sources), carbonates (CO2), perchlorates (O2 and HCl), and potential N‐bearing materials (e.g., Martian nitrates, terrestrial or Martian nitrogenated organics, ammonium salts) that evolve NH3, NO, and/or HCN. We conclude that Rocknest materials are a physical mixture in chemical disequilibrium, consistent with aeolian mixing, and that although weathering is not extensive, it may be ongoing even under current Martian surface conditions.
Key Points
Major volatiles detected by SAM were H2O, SO2, CO2, and O2
Minor volatiles include HCl, H2S, NH3, NO, and HCN
Calculating abundances from counts per second is explained
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