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.
Mars dayside thermospheric temperature and scale height trends were examined using measurements from the Neutral Gas Ion Mass Spectrometer (NGIMS) and the Imaging Ultraviolet Spectrograph (IUVS) on ...the Mars Atmosphere Volatile EvolutioN (MAVEN) spacecraft. Average scale heights (over 150–180 km for solar zenith angles ≤75°) from several different sampling periods were obtained from each instrument. NGIMS and IUVS scale height trends were found to be in good agreement, with both showing scale heights decreasing after perihelion and reaching a low value near aphelion (13.6 to 9.4 km). Between these two seasonal extremes, the temperature decreased by ∼70 K (from 240 to 170 K). These trends were also analyzed with respect to the changing solar flux reaching the planet, using the Lyman alpha irradiance measured by the Extreme Ultraviolet Monitor (EUVM) on MAVEN. Scale heights responded strongly to the changing solar flux. During this part of the MAVEN mission (October 2014 to May 2016), it was concluded that over longer timescales (at least several months), dayside thermospheric temperatures are chiefly driven by changing solar forcing, although it is the effects of changing heliocentric distance rather than changing solar activity which seem to have the greatest impact. Furthermore, effects of solar forcing were not observed on shorter timescales (less than a month), suggesting local wave effects may dominate solar forcing on these timescales. Finally, temperatures from two NGIMS sampling periods were compared to temperatures from the Mars Global Ionosphere‐Thermosphere Model (M‐GITM) and found to be in good agreement.
Plain Language Summary
The Martian dayside upper atmosphere (above 100 km) has been studied with limited datasets over several decades prior to 2014. Much controversy has resulted from analysis of this limited data such that derived temperatures plus densities and their variations were poorly constrained. In this paper, dayside temperature variations and their correlation with the solar fluxes measured explicitly at Mars are studied in great detail making use of both in‐situ and remote datasets from the recent MAVEN spacecraft mission to Mars. Results show that dayside temperatures (75 degrees solar zenith angle) over the Mars seasonal cycle vary by at least 70 K, and that variations owing to the changing solar output over its 11‐year cycle should enhance these variations further. This result is important because the dayside upper neutral atmospheric structure (temperatures and densities) and its variations control the reservoir of neutral and ion constituents that participate in the loss of the atmosphere to space over time. This loss to space is specifically being investigated by MAVEN in an effort to estimate the loss of water over time and the evolution of the climate of Mars.
Key Points
Seasonal and solar activity trends of Mars dayside upper atmosphere are revealed by MAVEN
MAVEN NGIMS and IUVS dayside thermosphere scale height trends are very similar
Long‐term variability of Mars dayside thermospheric temperatures is tied to solar‐driven thermal balances
Photochemical escape of atomic oxygen is thought to be one of the dominant channels for Martian atmospheric loss today and played a potentially major role in climate evolution. Mars Atmosphere and ...Volatile Evolution Mission (MAVEN) is the first mission capable of measuring, in situ, the relevant quantities necessary to calculate photochemical escape fluxes. We utilize 18 months of data from three MAVEN instruments: Langmuir Probe and Waves, Neutral Gas and Ion Mass Spectrometer, and SupraThermal And Thermal Ion Composition. From these data, we calculate altitude profiles of the production rate of hot oxygen atoms from the dissociative recombination of O2+ and the probability that such atoms will escape the Mars atmosphere. From this, we determine escape fluxes for 815 periapsis passes. Derived average dayside hot O escape rates range from 1.2 to 5.5 × 1025 s−1, depending on season and EUV flux, consistent with several pre‐MAVEN predictions and in broad agreement with estimates made with other MAVEN measurements. Hot O escape fluxes do not vary significantly with dayside solar zenith angle or crustal magnetic field strength but depend on CO2 photoionization frequency with a power law whose exponent is 2.6 ± 0.6, an unexpectedly high value which may be partially due to seasonal and geographic sampling. From this dependence and historical EUV measurements over 70 years, we estimate a modern‐era average escape rate of 4.3 × 1025 s−1. Extrapolating this dependence to early solar system, EUV conditions gives total losses of 13, 49, 189, and 483 mbar of oxygen over 1–3 and 3.5 Gyr, respectively, with uncertainties significantly increasing with time in the past.
Key Points
Photochemical O escape fluxes from dissociative recombination of O2+ are calculated from MAVEN in situ data
Escape rates of 1.2 to 5.5 × 1025 s−1 are derived and depend on season, solar zenith angle, and EUV flux, consistent with previous models
We find a power law exponent of 2.6 for the EUV dependence of escape rate, implying 100 s of mbar of oxygen loss over 3.5 Gyr
Variable levels of methane in the martian atmosphere have eluded explanation partly because the measurements are not repeatable in time or location. We report in situ measurements at Gale crater made ...over a 5-year period by the Tunable Laser Spectrometer on the Curiosity rover. The background levels of methane have a mean value 0.41 ± 0.16 parts per billion by volume (ppbv) (95% confidence interval) and exhibit a strong, repeatable seasonal variation (0.24 to 0.65 ppbv). This variation is greater than that predicted from either ultraviolet degradation of impact-delivered organics on the surface or from the annual surface pressure cycle. The large seasonal variation in the background and occurrences of higher temporary spikes (~7 ppbv) are consistent with small localized sources of methane released from martian surface or subsurface reservoirs.
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.
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
The Neutral Gas and Ion Mass Spectrometer (NGIMS) of the Mars Atmosphere and Volatile Evolution Mission (MAVEN) is designed to measure the composition, structure, and variability of the upper ...atmosphere of Mars. The NGIMS complements two other instrument packages on the MAVEN spacecraft designed to characterize the neutral upper atmosphere and ionosphere of Mars and the solar wind input to this region of the atmosphere. The combined measurement set is designed to quantify atmosphere escape rates and provide input to models of the evolution of the martian atmosphere. The NGIMS is designed to measure both surface reactive and inert neutral species and ambient ions along the spacecraft track over the 125–500 km altitude region utilizing a dual ion source and a quadrupole analyzer.
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 Sample Analysis at Mars (SAM) investigation of the Mars Science Laboratory (MSL) addresses the chemical and isotopic composition of the atmosphere and volatiles extracted from solid samples. The ...SAM investigation is designed to contribute substantially to the mission goal of quantitatively assessing the habitability of Mars as an essential step in the search for past or present life on Mars. SAM is a 40 kg instrument suite located in the interior of MSL’s Curiosity rover. The SAM instruments are a quadrupole mass spectrometer, a tunable laser spectrometer, and a 6-column gas chromatograph all coupled through solid and gas processing systems to provide complementary information on the same samples. The SAM suite is able to measure a suite of light isotopes and to analyze volatiles directly from the atmosphere or thermally released from solid samples. In addition to measurements of simple inorganic compounds and noble gases SAM will conduct a sensitive search for organic compounds with either thermal or chemical extraction from sieved samples delivered by the sample processing system on the Curiosity rover’s robotic arm.
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