Highly enriched carbon and oxygen isotopes in carbonate-derived CO2 at Gale crater, Mars.

Carbonate minerals are of particular interest in paleoenvironmental research as they are an integral part of the carbon and water cycles, both of which are relevant to habitability. Given that these cycles are less constrained on Mars than they are on Earth, the identification of carbonates has been a point of emphasis for rover missions. Here, we present carbon (δ13C) and oxygen (δ18O) isotope data from four carbonates encountered by the Curiosity rover within the Gale crater. The carbon isotope values range from 72 ± 2‰ to 110 ± 3‰ Vienna Pee Dee Belemnite while the oxygen isotope values span from 59 ± 4‰ to 91 ± 4‰ Vienna Standard Mean Ocean Water (1 SE uncertainties). Notably, these values are isotopically heavy (13C- and 18O-enriched) relative to nearly every other Martian material. The extreme isotopic difference between the carbonates and other carbon- and oxygen-rich reservoirs on Mars cannot be reconciled by standard equilibrium carbonate-CO2 fractionation, thus requiring an alternative process during or prior to carbonate formation. This paper explores two processes capable of contributing to the isotopic enrichments: 1) evaporative-driven Rayleigh distillation and 2) kinetic isotope effects related to cryogenic precipitation. In isolation, each process cannot reproduce the observed carbonate isotope values; however, a combination of these processes represents the most likely source for the extreme isotopic enrichments.

Organic carbon concentrations in 3.5-billion-year-old lacustrine mudstones of Mars.

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 CO2. 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 δ13C = +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 CO2 and CO (with estimated δ13C = -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.

Low Hesperian PCO2 constrained from in situ mineralogical analysis at Gale Crater, Mars.

Carbon dioxide is an essential atmospheric component in martian climate models that attempt to reconcile a faint young sun with planetwide evidence of liquid water in the Noachian and Early Hesperian. In this study, we use mineral and contextual sedimentary environmental data measured by the Mars Science Laboratory (MSL) Rover Curiosity to estimate the atmospheric partial pressure of CO2 (PCO2) coinciding with a long-lived lake system in Gale Crater at ∼3.5 Ga. A reaction-transport model that simulates mineralogy observed within the Sheepbed member at Yellowknife Bay (YKB), by coupling mineral equilibria with carbonate precipitation kinetics and rates of sedimentation, indicates atmospheric PCO2 levels in the 10s mbar range. At such low PCO2 levels, existing climate models are unable to warm Hesperian Mars anywhere near the freezing point of water, and other gases are required to raise atmospheric pressure to prevent lake waters from being lost to the atmosphere. Thus, either lacustrine features of Gale formed in a cold environment by a mechanism yet to be determined, or the climate models still lack an essential component that would serve to elevate surface temperatures, at least locally, on Hesperian Mars. Our results also impose restrictions on the potential role of atmospheric CO2 in inferred warmer conditions and valley network formation of the late Noachian.

Evidence for indigenous nitrogen in sedimentary and aeolian deposits from the Curiosity rover investigations at Gale crater, Mars.

The Sample Analysis at Mars (SAM) investigation on the Mars Science Laboratory (MSL) Curiosity rover has detected oxidized nitrogen-bearing compounds during pyrolysis of scooped aeolian sediments and drilled sedimentary deposits within Gale crater. Total N concentrations ranged from 20 to 250 nmol N per sample. After subtraction of known N sources in SAM, our results support the equivalent of 110-300 ppm of nitrate in the Rocknest (RN) aeolian samples, and 70-260 and 330-1,100 ppm nitrate in John Klein (JK) and Cumberland (CB) mudstone deposits, respectively. Discovery of indigenous martian nitrogen in Mars surface materials has important implications for habitability and, specifically, for the potential evolution of a nitrogen cycle at some point in martian history. The detection of nitrate in both wind-drifted fines (RN) and in mudstone (JK, CB) is likely a result of N2 fixation to nitrate generated by thermal shock from impact or volcanic plume lightning on ancient Mars. Fixed nitrogen could have facilitated the development of a primitive nitrogen cycle on the surface of ancient Mars, potentially providing a biochemically accessible source of nitrogen.

The Curiosity Rover's Exploration of Glen Torridon, Gale Crater, Mars: An Overview of the Campaign and Scientific Results.

The Mars Science Laboratory rover, Curiosity, explored the clay mineral-bearing Glen Torridon region for 1 Martian year between January 2019 and January 2021, including a short campaign onto the Greenheugh pediment. The Glen Torridon campaign sought to characterize the geology of the area, seek evidence of habitable environments, and document the onset of a potentially global climatic transition during the Hesperian era. Curiosity roved 5 km in total throughout Glen Torridon, from the Vera Rubin ridge to the northern margin of the Greenheugh pediment. Curiosity acquired samples from 11 drill holes during this campaign and conducted the first Martian thermochemolytic-based organics detection experiment with the Sample Analysis at Mars instrument suite. The lowest elevations within Glen Torridon represent a continuation of lacustrine Murray formation deposits, but overlying widespread cross bedded sandstones indicate an interval of more energetic fluvial environments and prompted the definition of a new stratigraphic formation in the Mount Sharp group called the Carolyn Shoemaker formation. Glen Torridon hosts abundant phyllosilicates yet remains compositionally and mineralogically comparable to the rest of the Mount Sharp group. Glen Torridon samples have a great diversity and abundance of sulfur-bearing organic molecules, which are consistent with the presence of ancient refractory organic matter. The Glen Torridon region experienced heterogeneous diagenesis, with the most striking alteration occurring just below the Siccar Point unconformity at the Greenheugh pediment. Results from the pediment campaign show that the capping sandstone formed within the Stimson Hesperian aeolian sand sea that experienced seasonal variations in wind direction.

First Detections of Dichlorobenzene Isomers and Trichloromethylpropane from Organic Matter Indigenous to Mars Mudstone in Gale Crater, Mars: Results from the Sample Analysis at Mars Instrument Onboard the Curiosity Rover.

Chromatographic analysis of the Cumberland mudstone in Gale crater by the Sample Analysis at Mars (SAM) instrument revealed the detection of two to three isomers of dichlorobenzene. Their individual concentrations were estimated to be in the 0.5-17 ppbw range relative to the sample mass. We also report the first detection of trichloromethylpropane and the confirmation of the detection of chlorobenzene previously reported. Supporting laboratory experiments excluded the SAM internal background as the source of those compounds, thus confirming the organic carbon and chlorine of the newly detected chlorohydrocarbons are indigenous to the mudstone sample. Laboratory experiments also demonstrated that the chlorohydrocarbons were mainly produced from chemical reactions occurring in the SAM ovens between organic molecules and oxychlorines contained in the sample. The results we obtained show that meteoritic organics and tested chemical species (a polycyclic aromatic hydrocarbon, an amino acid, and a carboxylic acid) were plausible organic precursors of the chlorinated aromatic molecules detected with SAM, thus suggesting that they could be among the organic molecules present in the mudstone. Results from this study coupled with previously reported detections of chlorinated aromatics (<300 ppbw) indigenous to the same mudstone highlight that organics can be preserved from the harsh surface conditions even at shallow depth. The detection of new chlorohydrocarbons with SAM confirms that organic molecules should have been available in an environment favorable to life forms, strengthening the habitability aspect of Gale crater.

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

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.

Background levels of methane in Mars' atmosphere show strong seasonal variations.

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 atmosphere. Mars methane detection and variability at Gale crater.

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.

The MARTE VNIR imaging spectrometer experiment: design and analysis.

We report on the design, operation, and data analysis methods employed on the VNIR imaging spectrometer instrument that was part of the Mars Astrobiology Research and Technology Experiment (MARTE). The imaging spectrometer is a hyperspectral scanning pushbroom device sensitive to VNIR wavelengths from 400-1000 nm. During the MARTE project, the spectrometer was deployed to the Río Tinto region of Spain. We analyzed subsets of three cores from Río Tinto using a new band modeling technique. We found most of the MARTE drill cores to contain predominantly goethite, though spatially coherent areas of hematite were identified in Core 23. We also distinguished non Fe-bearing minerals that were subsequently analyzed by X-ray diffraction (XRD) and found to be primarily muscovite. We present drill core maps that include spectra of goethite, hematite, and non Fe-bearing minerals.

Visible-near infrared point spectrometry of drill core samples from Río Tinto, Spain: results from the 2005 Mars Astrobiology Research and Technology Experiment (MARTE) drilling exercise.

Sampling of subsurface rock may be required to detect evidence of past biological activity on Mars. The Mars Astrobiology Research and Technology Experiment (MARTE) utilized the Río Tinto region, Spain, as a Mars analog site to test dry drilling technologies specific to Mars that retrieve subsurface rock for biological analysis. This work examines the usefulness of visible-near infrared (VNIR) (450-1000 nm) point spectrometry to characterize ferric iron minerals in core material retrieved during a simulated Mars drilling mission. VNIR spectrometry can indicate the presence of aqueously precipitated ferric iron minerals and, thus, determine whether biological analysis of retrieved rock is warranted. Core spectra obtained during the mission with T1 (893-897 nm) and T2 (644-652 nm) features indicate goethite-dominated samples, while relatively lower wavelength T1 (832-880 nm) features indicate hematite. Hematite/goethite molar ratios varied from 0 to 1.4, and within the 880-898 nm range, T1 features were used to estimate hematite/goethite molar ratios. Post-mission X-ray analysis detected phyllosilicates, which indicates that examining beyond the VNIR (e.g., shortwave infrared, 1000-2500 nm) will enhance the detection of other minerals formed by aqueous processes. Despite the limited spectral range of VNIR point spectrometry utilized in the MARTE Mars drilling simulation project, ferric iron minerals could be identified in retrieved core material, and their distribution served to direct core subsampling for biological analysis.

The subsurface geology of Río Tinto: material examined during a simulated Mars drilling mission for the Mars Astrobiology Research and Technology Experiment (MARTE).

The 2005 Mars Astrobiology Research and Technology Experiment (MARTE) project conducted a simulated 1-month Mars drilling mission in the Río Tinto district, Spain. Dry robotic drilling, core sampling, and biological and geological analytical technologies were collectively tested for the first time for potential use on Mars. Drilling and subsurface sampling and analytical technologies are being explored for Mars because the subsurface is the most likely place to find life on Mars. The objectives of this work are to describe drilling, sampling, and analytical procedures; present the geological analysis of core and borehole material; and examine lessons learned from the drilling simulation. Drilling occurred at an undisclosed location, causing the science team to rely only on mission data for geological and biological interpretations. Core and borehole imaging was used for micromorphological analysis of rock, targeting rock for biological analysis, and making decisions regarding the next day's drilling operations. Drilling reached 606 cm depth into poorly consolidated gossan that allowed only 35% of core recovery and contributed to borehole wall failure during drilling. Core material containing any indication of biology was sampled and analyzed in more detail for its confirmation. Despite the poorly consolidated nature of the subsurface gossan, dry drilling was able to retrieve useful core material for geological and biological analysis. Lessons learned from this drilling simulation can guide the development of dry drilling and subsurface geological and biological analytical technologies for future Mars drilling missions.

The 2005 MARTE Robotic Drilling Experiment in Río Tinto, Spain: objectives, approach, and results of a simulated mission to search for life in the Martian subsurface.

The Mars Astrobiology Research and Technology Experiment (MARTE) simulated a robotic drilling mission to search for subsurface life on Mars. The drill site was on Peña de Hierro near the headwaters of the Río Tinto river (southwest Spain), on a deposit that includes massive sulfides and their gossanized remains that resemble some iron and sulfur minerals found on Mars. The mission used a fluidless, 10-axis, autonomous coring drill mounted on a simulated lander. Cores were faced; then instruments collected color wide-angle context images, color microscopic images, visible-near infrared point spectra, and (lower resolution) visible-near infrared hyperspectral images. Cores were then stored for further processing or ejected. A borehole inspection system collected panoramic imaging and Raman spectra of borehole walls. Life detection was performed on full cores with an adenosine triphosphate luciferin-luciferase bioluminescence assay and on crushed core sections with SOLID2, an antibody array-based instrument. Two remotely located science teams analyzed the remote sensing data and chose subsample locations. In 30 days of operation, the drill penetrated to 6 m and collected 21 cores. Biosignatures were detected in 12 of 15 samples analyzed by SOLID2. Science teams correctly interpreted the nature of the deposits drilled as compared to the ground truth. This experiment shows that drilling to search for subsurface life on Mars is technically feasible and scientifically rewarding.