C. A. Malespin

Mars methane detection and variability at Gale crater

Of water and methane on Mars The Curiosity rover has been collecting data for the past 2 years, since its delivery to Mars (see the Perspective by Zahnle). Many studies now suggest that many millions of years ago, Mars was warmer and wetter than it is today. But those conditions required an atmosphere that seems to have vanished. Using the Curiosity rover, Mahaffy et al. measured the ratio of deuterium to hydrogen in clays that were formed 3.0 to 3.7 billion years ago. Hydrogen escapes more readily than deuterium, so this ratio offers a snapshot measure of the ancient atmosphere that can help constrain when and how it disappeared. Most methane on Earth has a biological origin, so planetary scientists have keenly pursued its detection in the martian atmosphere as well. Now, Webster et al. have precisely confirmed the presence of methane in the martian atmosphere with the instruments aboard the Curiosity rover at Gale crater. Science, this issue p. 412, p. 415; see also p. 370 Curiosity confirms the presence and variability of atmospheric methane, implying episodic production from an unknown source. [Also see Perspective by Zahnle] 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.

In situ radiometric and exposure age dating of the martian surface.

We determined radiogenic and cosmogenic noble gases in a mudstone on the floor of Gale Crater. A K-Ar age of 4.21 ± 0.35 billion years represents a mixture of detrital and authigenic components and confirms the expected antiquity of rocks comprising the crater rim. Cosmic-ray–produced 3He, 21Ne, and 36Ar yield concordant surface exposure ages of 78 ± 30 million years. Surface exposure occurred mainly in the present geomorphic setting rather than during primary erosion and transport. Our observations are consistent with mudstone deposition shortly after the Gale impact or possibly in a later event of rapid erosion and deposition. The mudstone remained buried until recent exposure by wind-driven scarp retreat. Sedimentary rocks exposed by this mechanism may thus offer the best potential for organic biomarker preservation against destruction by cosmic radiation.

Primordial argon isotope fractionation in the atmosphere of Mars measured by the SAM instrument on Curiosity and implications for atmospheric loss.

[1] The quadrupole mass spectrometer of the Sample Analysis at Mars (SAM) instrument on Curiosity rover has made the first high-precision measurement of the nonradiogenic argon isotope ratio in the atmosphere of Mars. The resulting value of 36Ar/38Ar = 4.2 ± 0.1 is highly significant for it provides excellent evidence that “Mars” meteorites are indeed of Martian origin, and it points to a significant loss of argon of at least 50% and perhaps as high as 85–95% from the atmosphere of Mars in the past 4 billion years. Taken together with the isotopic fractionations in N, C, H, and O measured by SAM, these results imply a substantial loss of atmosphere from Mars in the posthydrodynamic escape phase.

Evolved gas analyses of sedimentary rocks and eolian sediment in Gale Crater, Mars: Results of the Curiosity rover's sample analysis at Mars instrument from Yellowknife Bay to the Namib Dune

The Sample Analysis at Mars instrument evolved gas analyzer (SAM-EGA) has detected evolved water, H2, SO2, H2S, NO, CO2, CO, O2 and HCl from two eolian sediments and nine sedimentary rocks from Gale Crater, Mars. These evolved gas detections indicate nitrates, organics, oxychlorine phase, and sulfates are widespread with phyllosilicates and carbonates occurring in select Gale Crater materials. Coevolved CO2 (160 ± 248 - 2373 ± 820 μgC(CO2)/g), and CO (11 ± 3 - 320 ± 130 μgC(CO)/g) suggest organic-C is present in Gale Crater materials. Five samples evolved CO2 at temperatures consistent with carbonate (0.32± 0.05 - 0.70± 0.1 wt.% CO3). Evolved NO amounts to 0.002 ± 0.007 - 0.06 ± 0.03 wt.% NO3. Evolution of O2 suggests oxychlorine phases (chlorate/perchlorate) (0.05 ± 0.025 - 1.05 ± 0.44wt. % ClO4) are present while SO2 evolution indicates the presence of crystalline and/or poorly crystalline Fe- and Mg-sulfate and possibly sulfide. Evolved H2O (0.9 ± 0.3 - 2.5 ± 1.6 wt.% H2O) is consistent with the presence of adsorbed water, hydrated salts, interlayer/structural water from phyllosilicates, and possible inclusion water in mineral/amorphous phases. Evolved H2 and H2S suggest reduced phases occur despite the presence of oxidized phases (nitrate, oxychlorine, sulfate, carbonate). SAM results coupled with CheMin mineralogical and APXS elemental analyses indicate that Gale Crater sedimentary rocks have experienced a complex authigenetic/diagenetic history involving fluids with varying pH, redox, and salt composition. The inferred geochemical conditions were favorable for microbial habitability and if life ever existed, there was likely sufficient organic-C to support a small microbial population.

Organic matter preserved in 3-billion-year-old mudstones at Gale crater, Mars

Measuring martian organics and methane The Curiosity rover has been sampling on Mars for the past 5 years (see the Perspective by ten Kate). Eigenbrode et al. used two instruments in the SAM (Sample Analysis at Mars) suite to catch traces of complex organics preserved in 3-billion-year-old sediments. Heating the sediments released an array of organics and volatiles reminiscent of organic-rich sedimentary rock found on Earth. Most methane on Earth is produced by biological sources, but numerous abiotic processes have been proposed to explain martian methane. Webster et al. report atmospheric measurements of methane covering 3 martian years and found that the background level varies with the local seasons. The seasonal variation provides an important clue for determining the origin of martian methane. Science, this issue p. 1096, p. 1093; see also p. 1068 Complex organic compounds may have been detected by the Curiosity rover in ancient martian sedimentary rocks. 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.

Volatile Analysis by Pyrolysis of Regolith for planetary resource exploration

The extraction and identification of volatile resources that could be utilized by humans including water, oxygen, noble gases, and hydrocarbons on the Moon, Mars, and small planetary bodies will be critical for future long-term human exploration of these objects. Vacuum pyrolysis at elevated temperatures has been shown to be an efficient way to release volatiles trapped inside solid samples. In order to maximize the extraction of volatiles, including oxygen and noble gases from the breakdown of minerals, a pyrolysis temperature of 1400°C or higher is required, which greatly exceeds the maximum temperatures of current state-of-the-art flight pyrolysis instruments. Here we report on the recent optimization and field testing results of a high temperature pyrolysis oven and sample manipulation system coupled to a mass spectrometer instrument called Volatile Analysis by Pyrolysis of Regolith (VAPoR). VAPoR is capable of heating solid samples under vacuum to temperatures above 1300°C and determining the composition of volatiles released as a function of temperature.

Background levels of methane in Mars’ atmosphere show strong seasonal variations

Measuring martian organics and methane The Curiosity rover has been sampling on Mars for the past 5 years (see the Perspective by ten Kate). Eigenbrode et al. used two instruments in the SAM (Sample Analysis at Mars) suite to catch traces of complex organics preserved in 3-billion-year-old sediments. Heating the sediments released an array of organics and volatiles reminiscent of organic-rich sedimentary rock found on Earth. Most methane on Earth is produced by biological sources, but numerous abiotic processes have been proposed to explain martian methane. Webster et al. report atmospheric measurements of methane covering 3 martian years and found that the background level varies with the local seasons. The seasonal variation provides an important clue for determining the origin of martian methane. Science, this issue p. 1096, p. 1093; see also p. 1068 The background level of methane in Mars’ atmosphere varies with season, providing a clue to its origin. 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.

Discordant K-Ar and Young Exposure Dates for the Windjana sandstone, Kimberley, Gale Crater, Mars

K-Ar and noble gas surface exposure age measurements were carried out on the Windjana sandstone, Kimberley region, Gale Crater, Mars, by using the Sample Analysis at Mars instrument on the Curiosity rover. The sandstone is unusually rich in sanidine, as determined by CheMin X-ray diffraction, contributing to the high K_2O concentration of 3.09 ± 0.20 wt % measured by Alpha-Particle X-ray Spectrometer analysis. A sandstone aliquot heated to ~915°C yielded a K-Ar age of 627 ± 50 Ma. Reheating this aliquot yielded no additional Ar. A second aliquot heated in the same way yielded a much higher K-Ar age of 1710 ± 110 Ma. These data suggest incomplete Ar extraction from a rock with a K-Ar age older than 1710 Ma. Incomplete extraction at ~900°C is not surprising for a rock with a large fraction of K carried by Ar-retentive K-feldspar. Likely, variability in the exact temperature achieved by the sample from run to run, uncertainties in sample mass estimation, and possible mineral fractionation during transport and storage prior to analysis may contribute to these discrepant data. Cosmic ray exposure ages from ^3He and ^(21)Ne in the two aliquots are minimum values given the possibility of incomplete extraction. However, the general similarity between the ^3He (57 ± 49 and 18 ± 32 Ma, mean 30 Ma) and ^(21)Ne (2 ± 32 and 83 ± 24 Ma, mean 54 Ma) exposure ages provides no evidence for underextraction. The implied erosion rate at the Kimberley location is similar to that reported at the nearby Yellowknife Bay outcrop.

A Two‐Step K‐Ar Experiment on Mars: Dating the Diagenetic Formation of Jarosite from Amazonian Groundwaters

Following K-Ar dating of a mudstone and a sandstone, a third sample has been dated by the Curiosity rover exploring Gale Crater. The Mojave 2 mudstone, which contains relatively abundant jarosite, yielded a young K-Ar bulk age of 2.57 ± 0.39 Ga (1σ precision). A two-step heating experiment was implemented in an effort to resolve the K-Ar ages of primary and secondary mineralogical components within the sample. This technique involves measurement of ^(40)Ar released in low-temperature (500°C) and high-temperature (930°C) steps, and a model of the potassium distribution within the mineralogical components of the sample. Using this method, the high-temperature step yields a K-Ar model age of 4.07 ± 0.63 Ga associated with detrital plagioclase, compatible with the age obtained on the Cumberland mudstone by Curiosity. The low-temperature step, associated with jarosite mixed with K-bearing evaporites and/or phyllosilicates, gave a youthful K-Ar model age of 2.12 ± 0.36 Ga. The interpretation of this result is complicated by the potential for argon loss after mineral formation. Comparison with the results on Cumberland and previously published constraints on argon retentivity of the individual phases likely to be present suggests that the formation age of the secondary materials, correcting for plausible extents of argon loss, is still less than 3 Ga, suggesting post-3 Ga aqueous processes occurred in the sediments in Gale Crater. Such a result is inconsistent with K-bearing mineral formation in Gale Lake and instead suggests postdepositional fluid flow at a time after surface fluvial activity on Mars is thought to have largely ceased.

Moon and Mars Analog Mission Activities for Mauna Kea 2012

Rover-based 2012 Moon and Mars Analog Mission Activities (MMAMA) scientific investigations were recently completed at Mauna Kea, Hawaii. Scientific investigations, scientific input, and science operations constraints were tested in the context of an existing project and protocols for the field activities designed to help NASA achieve the Vision for Space Exploration. Initial science operations were planned based on a model similar to the operations control of the Mars Exploration Rovers (MER). However, evolution of the operations process occurred as the analog mission progressed. We report here on the preliminary sensor data results, an applicable methodology for developing an optimum science input based on productive engineering and science trades and the science operations approach for an investigation into the valley on the upper slopes of Mauna Kea identified as “Apollo Valley.”