Carbon with depleted d13C (down to − 25.6‰ VPDB) found in > 3.7 billion year old metamorphic sediments from the Isua Supracrustal Belt, Southwestern Greenland, has been proposed to represent the oldest remains of life on Earth. Graphitic inclusions within garnet porphyroblasts from this locality have been shown to associate with elements consistent with biogenic remains. In this report, we focus on certain liquid inclusions found in the Isua garnets, characterizing their chemical composition using atomic force microscopy, AFM-based infrared spectroscopy, optical photothermal infrared spectroscopy, Raman spectroscopy, and time-of-flight secondary ion mass spectrometry. Our results show that the liquid inclusions contain functional groups consisting of carbon, nitrogen, and oxygen in a configuration similar to amide functional groups. We suspect that the amide groups formed from N, O and C-containing volatile components that were released from the original kerogenous material enclosed in the garnets, as this was graphitized during thermal maturation. This is consistent with the observed inclusion assemblage of solid graphitic and viscous fluid inclusions alike. Our observations are compatible with the inclusions forming from biogenic precursor material, and when considered alongside previous reports on the carbonaceous material in the Isua metamorphic sediments, these and our study collectively indicate that the carbonaceous material in the Isua metasediments represents the oldest traces of life on Earth. 

The Perseverance rover has collected seven oriented samples of sedimentary rocks, all likely older than the oldest signs of widespread life on Earth, at the exposed base of the western fan in Jezero crater, Mars. The samples include a sulfate- and clay-bearing mudstone and sandstone, a fluvial sandstone from a stratigraphically low position at the fan front, and a carbonate-bearing sandstone deposited above the sulfate-bearing strata. All samples contain aqueously precipitated materials and most or all were aqueously deposited. Although the rover instruments have not confidently detected organic matter in the rocks from the fan front, the much more sensitive terrestrial instruments will still be able to search for remnants of prebiotic chemistries and past life, and study Mars’s past habitability in the samples returned to Earth. The hydrated, sulfate-bearing mudstone has the highest potential to preserve organic matter and biosignatures, whereas the carbonate-bearing sandstones can be used to constrain when and for how long Jezero crater contained liquid water. Returned sample science analyses of sulfate, carbonate, clay, phosphate and igneous minerals as well as trace metals and volatiles that are present in the samples acquired at the fan front would provide transformative insights into past habitable environments on Mars, the evolution of its magnetic field, atmosphere and climate and the past and present cycling of atmospheric and crustal water, sulfur and carbon.

In this work, we derive a simple method for calibrating Raman bandwidths for the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument onboard NASA’s Perseverance rover. Raman bandwidths and shapes reported by an instrument contain contributions from both the intrinsic Raman band (IRB) and instrumental artifacts. To directly correlate bandwidth to sample properties and to compare bandwidths across instruments, the IRB width needs to be separated from instrumental effects. Here, we use the ubiquitous bandwidth calibration method of modeling the observed Raman bands as a convolution of a Lorentzian IRB and a Gaussian instrument slit function. Using calibration target data, we calculate that SHERLOC has a slit function width of 34.1 cm–1. With a measure of the instrument slit function, we can deconvolve the IRB from the observed band, providing the width of the Raman band unobscured by instrumental artifact. We present the correlation between observed Raman bandwidth and intrinsic Raman bandwidth in table form for the quick estimation of SHERLOC Raman intrinsic bandwidths. We discuss the limitations of using this model to calibrate Raman bandwidth and derive a quantitative method for calculating the errors associated with the calibration. We demonstrate the utility of this method of bandwidth calibration by examining the intrinsic bandwidths of SHERLOC sulfate spectra and by modeling the SHERLOC spectrum of olivine. 

The Mars 2020 Perseverance rover has explored fluvio-lacustrine sedimentary rocks within Jezero crater. Prior work showed that igneous crater floor Séítah and Máaz formations have mafic mineralogy with alteration phases that indicate multiple episodes of aqueous alteration. In this work, we extend the analyses of hydration to targets in the Jezero western fan delta, using data from the SHERLOC (Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals) Raman spectrometer. Spectral features, for example, sulfate and hydration peak positions and shapes, vary within, and across the crater floor and western fan. The proportion of targets with hydration associated with sulfates was approximately equal in the crater floor and the western fan. All hydrated targets in the crater floor and upper fan showed bimodal hydration peaks at ∼3,200 and ∼3,400 cm−1. The sulfate symmetric stretch at ∼1,000 cm−1 coupled with a hydration peak at ∼3,400 cm−1 indicate that MgSO4·nH2O (2 < n ≤ 5) is a likely hydration carrier phase in all units, perhaps paired with low-hydration (n ≤ 1) amorphous Mg-sulfates, indicated by the ∼3,200 cm−1 peak. Low-hydration MgSO4·nH2O (n = 1–2) are more prevalent in the fan, and hydrated targets in the fan front only had one peak at ∼3,400 cm−1. While anhydrite co-occurs with hydrated Mg-sulfates in the crater floor and fan front, hydrated Ca-sulfates are observed instead at the top of the upper fan. Collectively, the data imply aqueous deposition of sediments with formation of salts from high ionic strength fluids and subsequent aridity to preserve the observed hydration states.

The Mars 2020 Perseverance rover has examined and sampled sulfate-rich clastic rocks from the Hogwallow Flats member at Hawksbill Gap and the Yori Pass member at Cape Nukshak. Both strata are located on the Jezero crater western fan front, are lithologically and stratigraphically similar, and have been assigned to the Shenandoah formation. In situ analyses demonstrate that these are fine-grained sandstones composed of phyllosilicates, hematite, Ca-sulfates, Fe-Mg-sulfates, ferric sulfates, and possibly chloride salts. Sulfate minerals are found both as depositional grains and diagenetic features, including intergranular cement and vein- and vug-cements. Here, we describe the possibility of various sulfate phases to preserve potential biosignatures and the record of paleoenvironmental conditions in fluid and solid inclusions, based on findings from analog sulfate-rich rocks on Earth. The samples collected from these outcrops, Hazeltop and Bearwallow from Hogwallow Flats, and Kukaklek from Yori Pass, should be examined for such potential biosignatures and environmental indicators upon return to Earth. 

The Mars 2020 Perseverance rover discovered fine-grained clastic sedimentary rocks in the “Hogwallow Flats” member of the “Shenandoah” formation at Jezero crater, Mars. The Hogwallow Flats member shows evidence of multiple phases of diagenesis including Fe/Mg-sulfate-rich (20–30 wt. %) outcrop transitioning downward into red-purple-gray mottled outcrop, Fe/Mg clay minerals and oxides, putative concretions, occasional Ca sulfate-filled fractures, and variable redox state over small (cm) spatial scales. This work uses Mastcam-Z and SuperCam instrument data to characterize and interpret the sedimentary facies, mineralogy and diagenetic features of the Hogwallow Flats member. The lateral continuity of bedrock similar in tone and morphology to Hogwallow Flats that occurs over several km within the western Jezero sedimentary fan suggests widespread deposition in a lacustrine or alluvial floodplain setting. Following deposition, sediments interacted with multiple fluids of variable redox state and salinity under habitable conditions. Three drilled sample cores were collected from this interval of the Shenandoah formation as part of the Mars Sample Return campaign. These samples have very high potential to preserve organic compounds and biosignatures. Drill cores may partially include dark-toned mottled outcrop that lies directly below light-toned, sulfate-cemented outcrop. This facies may represent some of the least oxidized material observed at this interval of the Shenandoah formation. This work reconstructs the diagenetic history of the Hogwallow Flats member and discusses implications for biosignature preservation in rock samples for possible return to Earth.

Sulfur plays a major role in martian geochemistry and sulfate minerals are important repositories of water. However, their hydration states on Mars are poorly constrained. Therefore, understanding the hydration and distribution of sulfate minerals on Mars is important for understanding its geologic, hydrologic, and atmospheric evolution as well as its habitability potential. NASA's Perseverance rover is currently exploring the Noachian-age Jezero crater, which hosts a fan-delta system associated with a paleolake. The crater floor includes two igneous units (the Séítah and Máaz formations), both of which contain evidence of later alteration by fluids including sulfate minerals. Results from the rover instruments Scanning Habitable Environments with Raman and Luminescence for Organics and Chemistry and Planetary Instrument for X-ray Lithochemistry reveal the presence of a mix of crystalline and amorphous hydrated Mg-sulfate minerals (both MgSO4·[3–5]H2O and possible MgSO4·H2O), and anhydrous Ca-sulfate minerals. The sulfate phases within each outcrop may have formed from single or multiple episodes of water activity, although several depositional events seem likely for the different units in the crater floor. Textural and chemical evidence suggest that the sulfate minerals most likely precipitated from a low temperature sulfate-rich fluid of moderate pH. The identification of approximately four waters puts a lower constraint on the hydration state of sulfate minerals in the shallow subsurface, which has implications for the martian hydrological budget. These sulfate minerals are key samples for future Mars sample return.

A major objective of the Mars 2020 mission is to sample rocks in Jezero crater that may preserve organic matter for later return to Earth. Using an UV Raman and luminescence spectrometer, the Perseverance rover detected luminescence signals with maximal intensities at 330 to 350 nm and 270 to 290 nm that were initially reported as consistent with organics Here, we test the alternative hypothesis that the 330- to 350-nm and 270- to 290-nm luminescence signals trace Ce3+ in phosphate and silicate defects, resp. By comparing the distributions of luminescence signals with the rover detections of x-ray fluorescence from P2O5 and Si-bearing materials, we show that, while an organic origin is not excluded, the observed luminescence can be explained by purely inorganic materials. These findings highlight the importance of eventual laboratory analyses to detect and characterize organic compounds in the returned samples.

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument onboard the Mars 2020 Perseverance rover detected so far some of the most intense fluorescence signals in association with sulfates analyzing abraded patches of rocks at Jezero crater, Mars. To assess the plausibility of an organic origin of these signals, it is key to understand if organics can survive exposure to ambient Martian UV after exposure by the Perseverance abrasion tool and prior to analysis by SHERLOC. In this work, we investigated the stability of organo-sulfate assemblages under Martian-like UV irradiation and we observed that the spectroscopic features of phthalic and mellitic acid embedded into hydrated magnesium sulfate do not change for UV exposures corresponding to at least 48 Martian sols and, thus, should still be detectable in fluorescence when the SHERLOC analysis takes place, thanks to the photoprotective properties of magnesium sulfate. In addition, different photoproduct bands diagnostic of the parent carboxylic acid molecules could be observed. The photoprotective behavior of hydrated magnesium sulfate corroborates the hypothesis that sulfates might have played a key role in the preservation of organics on Mars, and that the fluorescence signals detected by SHERLOC in association with sulfates could potentially arise from organic compounds. 

The Mars Sample Return mission intends to retrieve a sealed collection of rocks, regolith, and atmosphere sampled from Jezero Crater, Mars, by the NASA Perseverance rover mission. For all life-related research, it is necessary to evaluate water availability in the samples and on Mars. Within the first Martian year, Perseverance has acquired an estimated total mass of 355 g of rocks and regolith, and 38 μmoles of Martian atmospheric gas. Using in-situ observations acquired by the Perseverance rover, we show that the present-day environmental conditions at Jezero allow for the hydration of sulfates, chlorides, and perchlorates and the occasional formation of frost as well as a diurnal atmospheric-surface water exchange of 0.5–10 g water per m2 (assuming a well-mixed atmosphere). At night, when the temperature drops below 190 K, the surface water activity can exceed 0.5, the lowest limit for cell reproduction. During the day, when the temperature is above the cell replication limit of 245 K, water activity is less than 0.02. The environmental conditions at the surface of Jezero Crater, where these samples were acquired, are incompatible with the cell replication limits currently known on Earth.