Manganese-rich deposits in the lower member of the Datangpo Formation (DTP) (ca. 663–654 Ma) in South China formed in the aftermath of the Cryogenian Sturtian glaciation. The Mn in the DTP occurs dominantly as rhodochrosite and Ca-rhodochrosite. A hydrothermal origin of the Mn2+ is shown by the rare earth element distribution and significantly high Mn/Fe ratios (3–19, average = 10.1). Previous studies suggested a microbially-mediated process for controlling the DTP black-shale hosted Mn carbonate deposits. However, detailed reports on the formation mechanisms of micro-scale (<2–5 μm) ooid-like Mn carbonates in the DTP have rarely been published. Systematic petrography and geochemical analyses in this study demonstrate the coexistence of two types of micro-scale ooidal-like Mn carbonates formed through two distinct mechanisms, either dominated by microbially-mediated or physiochemically-forced pathways. The Type I Mn carbonate has relatively larger grain size of 2–5 μm and exhibits a radial-concentric microfabric that shows signs of growth banding in the form of alternating light and dark laminae, which mainly express variation in Ca and Mn concentrations. The initial precipitation phase of the Type I Mn carbonate is interpreted to be Mn oxide/hydroxide, based on positive Ce anomalies and selective enrichments of particular trace elements. Novel evidence indicates that the capture of Mn as a carbonate phase directly from the water column by primarily precipitated calcite, which is referred to as the Type II Mn carbonate, has also contributed to the DTP Mn-rich deposits. Multiple roles of organic matter in Mn carbonate formation have been established: (1) catalysed Mn-redox cycling; (2) trapping and transportation of initial mineral precipitates to sediments; (3) serving as a carbon source; (4) regulating the morphology of the Mn carbonate. As a key link for understanding Cryogenian carbon and Mn cycling, specific formation pathways for the DTP Mn-carbonates are likely to have been controlled by given atmospheric-oceanic compositions (including oxygen level, pCO2, and redox conditions) in response to major geological and biological events during the interglacial period. In turn, massive storage of inorganic carbon and phosphorous in Mn carbonate phases would have had a substantial influence on biogeochemical carbon cycling during the Cryogenian. 

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. 

Executive summary provided in lieu of abstract. © 2019 The Authors.

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 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.

The goals of NASA's Mars 2020 mission include searching for evidence of ancient life on Mars, studying the geology of Jezero crater, understanding Mars' current and past climate, and preparing for human exploration of Mars. During the mission's first science campaign, the Perseverance rover's SHERLOC deep UV Raman and fluorescence instrument collected microscale, two-dimensional Raman and fluorescence images on 10 natural (unabraded) and abraded targets on two different Jezero crater floor units: Séítah and Máaz. We report SHERLOC Raman measurements collected during the Crater Floor Campaign and discuss their implications regarding the origin and history of Séítah and Máaz. The data support the conclusion that Séítah and Máaz are mineralogically distinct igneous units with complex aqueous alteration histories and suggest that the Jezero crater floor once hosted an environment capable of supporting microbial life and preserving evidence of that life, if it existed. 

Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C (δ13C as light as -69% V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13Cdepleted carbonates ever reported, δ13C down to -125% V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

The deep biosphere is one of the least understood ecosystems on Earth. Although most microbiological studies in this system have focused on prokaryotes and neglected microeukaryotes, recent discoveries have revealed existence of fossil and active fungi in marine sediments and sub-seafloor basalts, with proposed importance for the subsurface energy cycle. However, studies of fungi in deep continental crystalline rocks are surprisingly few. Consequently, the characteristics and processes of fungi and fungus-prokaryote interactions in this vast environment remain enigmatic. Here we report the first findings of partly organically preserved and partly mineralized fungi at great depth in fractured crystalline rock (-740 m). Based on environmental parameters and mineralogy the fungi are interpreted as anaerobic. Synchrotron-based techniques and stable isotope microanalysis confirm a coupling between the fungi and sulfate reducing bacteria. The cryptoendolithic fungi have significantly weathered neighboring zeolite crystals and thus have implications for storage of toxic wastes using zeolite barriers. © 2017 The Author(s).

Fractured rocks of impact craters may be suitable hosts for deep microbial communities on Earth and potentially other terrestrial planets, yet direct evidence remains elusive. Here, we present a study of the largest crater of Europe, the Devonian Siljan structure, showing that impact structures can be important unexplored hosts for long-term deep microbial activity. Secondary carbonate minerals dated to 80 ± 5 to 22 ± 3 million years, and thus postdating the impact by more than 300 million years, have isotopic signatures revealing both microbial methanogenesis and anaerobic oxidation of methane in the bedrock. Hydrocarbons mobilized from matured shale source rocks were utilized by subsurface microorganisms, leading to accumulation of microbial methane mixed with a thermogenic and possibly a minor abiotic gas fraction beneath a sedimentary cap rock at the crater rim. These new insights into crater hosted gas accumulation and microbial activity have implications for understanding the astrobiological consequences of impacts. © 2019, The Author(s).

Laboratory simulations of Martian conditions are essential to develop quantitative models for the survival of organic biomarkers for future Mars exploration missions. In this work, we report the results of ultraviolet (UV) irradiation processing of biomarkers adsorbed on minerals under Martian-like conditions. Specifically, we prepared Mars soil analogues by doping forsterite, lizardite, antigorite, labradorite, natrolite, apatite and hematite minerals with organic compounds considered as potential biomarkers of extant terrestrial life such as the nucleotides adenosine monophosphate (AMP) and uridine monophosphate (UMP). We characterized such Mars soil analogues by means of Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS), Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) and Confocal Raman Imaging Spectroscopy (CRIS), in order to get insights into the specific molecule-mineral interactions and explore the capabilities of different techniques to reveal diagnostic features of these biomarkers. Then, we performed irradiation experiments in the mid-UV spectral region under simulated Martian conditions and under terrestrial ambient conditions for comparison, monitoring the degradation process through DRIFTS. We observed that degradation under Martian-like conditions occurs much slower than in terrestrial ambient conditions. The minerals labradorite and natrolite mainly promote photodegradation of nucleotides, hematite and forsterite exhibit an intermediate degrading effect, while apatite, lizardite and antigorite do not show any significant catalytic effect on the degradation of the target organic species.

The presence of solid carbonaceous matter in cometary dust was established by the detection of elements such as carbon, hydrogen, oxygen and nitrogen in particles from comet 1P/Halley1, 2. Such matter is generally thought to have originated in the interstellar medium3, but it might have formed in the solar nebula—the cloud of gas and dust that was left over after the Sun formed4. This solid carbonaceous material cannot be observed from Earth, so it has eluded unambiguous characterization5. Many gaseous organic molecules, however, have been observed6, 7, 8, 9; they come mostly from the sublimation of ices at the surface or in the subsurface of cometary nuclei8. These ices could have been formed from material inherited from the interstellar medium that suffered little processing in the solar nebula10. Here we report the in situ detection of solid organic matter in the dust particles emitted by comet 67P/Churyumov–Gerasimenko; the carbon in this organic material is bound in very large macromolecular compounds, analogous to the insoluble organic matter found in the carbonaceous chondrite meteorites11, 12. The organic matter in meteorites might have formed in the interstellar medium and/or the solar nebula, but was almost certainly modified in the meteorites’ parent bodies11. We conclude that the observed cometary carbonaceous solid matter could have the same origin as the meteoritic insoluble organic matter, but suffered less modification before and/or after being incorporated into the comet.

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is a robotic arm-mounted instrument onboard NASA’s Perseverance rover. SHERLOC combines imaging via two cameras with both Raman and fluorescence spectroscopy to investigate geological materials at the rover’s Jezero crater field site. SHERLOC requires in situ calibration to monitor the health and performance of the instrument. These calibration data are critically important to ensure the veracity of data interpretation, especially considering the extreme martian environmental conditions where the instrument operates. The SHERLOC Calibration Target (SCT) is located at the front of the rover and is exposed to the same atmospheric conditions as the instrument. The SCT includes 10 individual targets designed to meet all instrument calibration requirements. An additional calibration target is mounted inside the instrument’s dust cover. The targets include polymers, rock, synthetic material, and optical pattern targets. Their primary function is calibration of parameters within the SHERLOC instrument so that the data can be interpreted correctly. The SCT was also designed to take advantage of opportunities for supplemental science investigations and includes targets intended for public engagement. The exposure of materials to martian atmospheric conditions allows for opportunistic science on extravehicular suit (i.e., “spacesuit”) materials. These samples will be used in an extended study to produce direct measurements of the expected service lifetimes of these materials on the martian surface, thus helping NASA facilitate human exploration of the planet. Other targets include a martian meteorite and the first geocache target to reside on another planet, both of which increase the outreach and potential of the mission to foster interest in, and enthusiasm for, planetary exploration. During the first 200 sols (martian days) of operation on Mars, the SCT has been analyzed three times and has proven to be vital in the calibration of the instrument and in assisting the SHERLOC team with interpretation of in situ data. © 2022, The Author(s).

The Mars Organic Molecule Analyzer (MOMA) instrument onboard the ESA/Roscosmos ExoMars rover (to launch in July, 2020) will analyze volatile and refractory organic compounds in martian surface and subsurface sediments. In this study, we describe the design, current status of development, and analytical capabilities of the instrument. Data acquired on preliminary MOMA flight-like hardware and experimental setups are also presented, illustrating their contribution to the overall science return of the mission..

This paper describes strategies to search for, detect, and identify organic material on the surface and subsurface of Mars. The strategies described include those applied by landed missions in the past and those that will be applied in the future. The value and role of ESA's ExoMars rover and of her key science instrument Mars Organic Molecule Analyzer (MOMA) are critically assessed.

Comets are regarded as probably the most primitive of solar system objects, preserving a record of the materials from which the solar system aggregated. Key amongst their components are organic compounds - molecules that may trace their heritage to the interstellar medium from which the protosolar nebula eventually emerged. The most recent cometary space mission, Rosetta, carried instruments designed to characterize, in unprecedented detail, the organic species in comet 67P/Churyumov-Gerasimenko (67P). Rosetta was the first mission to match orbits with a comet and follow its evolution over time, and also the first mission to land scientific instruments on a comet surface. Results from the mission revealed a greater variety of molecules than previously identified and indicated that 67P contained both primitive and processed organic entities. 

Although hematophagy is found in ∼14,000 species of extant insects, the fossil record of blood-feeding insects is extremely poor and largely confined to specimens identified as hematophagic based on their taxonomic affinities with extant hematophagic insects; direct evidence of hematophagy is limited to four insect fossils in which trypanosomes and the malarial protozoan Plasmodium have been found. Here, we describe a blood-engorged mosquito from the Middle Eocene Kishenehn Formation in Montana. This unique specimen provided the opportunity to ask whether or not hemoglobin, or biomolecules derived from hemoglobin, were preserved in the fossilized blood meal. The abdomen of the fossil mosquito was shown to contain very high levels of iron, and mass spectrometry data provided a convincing identification of porphyrin molecules derived from the oxygen-carrying heme moiety of hemoglobin. These data confirm the existence of taphonomic conditions conducive to the preservation of biomolecules through deep time and support previous reports of the existence of heme-derived porphyrins in terrestrial fossils.

The lacustrine oil shales of the Coal Creek Member of the Kishenehn Formation in northwestern Montana comprise a relatively unstudied Middle Eocene fossil insect locality. Herein, we detail the stratigraphic position of the fossiliferous unit, describe the insect fauna of the Coal Creek locality and document its bias towards very small but remarkably preserved insects. In addition, the depositional environment is examined and the mineral constituents of the laminations that comprise the varves of the Kishenehn oil shale are defined. Fifteen orders of insects have been recorded with the majority of all insects identified as aquatic with the families Chironomidae (Diptera) and Corixidae (Hemiptera) dominant. The presence of small aquatic insects, many of which are immature, the intact nature of >90% of the fossil insects and the presence of Daphnia ephippia, all indicate that the depositional environment was the shallow margin of a large freshwater lake. The fossil insects occur within fossilized microbial mat layers that comprise the bedding planes of the oil shale. Unlike the fossiliferous shales of the Florissant and Okanagan Highlands, the mats are not a product of diatomaceous algae nor are diatom frustules a component of the sediments or the varve structure. Instead, the varves are composed of very fine eolian siliciclastic silt grains overlaid with non-diatomaceous, possibly cyanobacteria-derived microbial mats which contain distinct traces of polyaromatic hydrocarbons. A distinct third layer composed of essentially pure calcite is present in the shale of some exposures and is presumably derived from the seasonal warming-induced precipitation of carbonate from the lake’s waters. The Coal Creek locality presents a unique opportunity to study both very small Middle Eocene insects not often preserved as compression fossils in most Konservat-Lagerstätte and the processes that led to their preservation.

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. 

Martian soils are critically important for understanding the history of Mars, past potentially habitable environments, returned samples, and future human exploration. This paper examines soil crusts on the floor of Jezero crater encountered during initial phases of the Mars 2020 mission. Soil surface crusts have been observed on Mars at other locations, starting with the two Viking Lander missions. Rover observations show that soil crusts are also common across the floor of Jezero crater, revealed in 45 of 101 locations where rover wheels disturbed the soil surface, 2 out of 7 helicopter flights that crossed the wheel tracks, and 4 of 8 abrasion/drilling sites. Most soils measured by the SuperCam laser-induced breakdown spectroscopy (LIBS) instrument show high hydrogen content at the surface, and fine-grained soils also show a visible/near infrared (VISIR) 1.9 µm H2O absorption feature. The Planetary Instrument for X-ray Lithochemistry (PIXL) and SuperCam observations suggest the presence of salts at the surface of rocks and soils. The correlation of S and Cl contents with H contents in SuperCam LIBS measurements suggests that the salts present are likely hydrated. On the “Naltsos” target, magnesium and sulfur are correlated in PIXL measurements, and Mg is tightly correlated with H at the SuperCam points, suggesting hydrated Mg-sulfates. Mars Environmental Dynamics Analyzer (MEDA) observations indicate possible frost events and potential changes in the hydration of Mg-sulfate salts. Jezero crater soil crusts may therefore form by salts that are hydrated by changes in relative humidity and frost events, cementing the soil surface together.

The COmetary Secondary Ion Mass Analyser instrument on board ESA's Rosetta mission has collected dust particles in the coma of comet 67P/Churyumov-Gerasimenko. During the early-orbit phase of the Rosetta mission, particles and particle agglomerates have been imaged and analyzed in the inner coma at distances between 100 km and 10 km off the cometary nucleus and at more than 3 AU from the Sun. We identified 585 particles of more than 14 μm in size. The particles are collected at low impact speeds and constitute a sample of the dust particles in the inner coma impacting and fragmenting on the targets. The sizes of the particles range from 14 μm up to sub-millimeter sizes and the differential dust flux size distribution is fitted with a power law exponent of -3.1. After impact, the larger particles tend to stick together, spread out or consist of single or a group of clumps, and the flocculent morphology of the fragmented particles is revealed. The elemental composition of the dust particles is heterogeneous and the particles could contain typical silicates like olivine and pyroxenes, as well as iron sulfides. The sodium to iron elemental ratio is enriched with regard to abundances in CI carbonaceous chondrites by a factor from ∼1.5 to ∼15. No clear evidence for organic matter has been identified. The composition and morphology of the collected dust particles appear to be similar to that of interplanetary dust particles.

The in situ cometary dust particle instrument COSIMA (COmetary Secondary Ion Mass Analyser) onboard ESA's Rosetta mission has collected about 31 000 dust particles in the inner coma of comet 67P/Churyumov-Gerasimenko since August 2014. The particles are identified by optical microscope imaging and analysed by time-of-flight secondary ion mass spectrometry. After dust particle collection by low speed impact on metal targets, the collected particle morphology points towards four families of cometary dust particles. COSIMA is an in situ laboratory that operates remotely controlled next to the comet nucleus. The particles can be further manipulated within the instrument by mechanical and electrostatic means after their collection by impact. The particles are stored above 0°C in the instrument and the experiments are carried out on the refractory, ice-free matter of the captured cometary dust particles. An interesting particle morphology class, the compact particles, is not fragmented on impact. One of these particles was mechanically pressed and thereby crushed into large fragments. The particles are good electrical insulators and transform into rubble pile agglomerates by the application of an energetic indium ion beam during the secondary ion mass spectrometry analysis. This article is part of the themed issue 'Cometary science after Rosetta'. © 2017 The Authors.

Between Aug. 2014 and Sept. 2016, while ESA's cornerstone mission Rosetta was operating in the vicinity of the nucleus and in the coma of comet 67P/Churyumov-Gerasimenko, the COSIMA instrument collected a large number of dust particles with diameters up to a millimeter. Positive or negative ions were detected by a time-of-flight secondary ion mass spectrometer (TOF-SIMS) and the composition of selected particles was deduced. Many of the negative ion mass spectra show, besides mass peaks at the correct position, an additional, extended contribution at the lower mass side caused by partial charging of the dust. This effect, usually avoided in SIMS applications, can in our case be used to obtain information on the electrical properties of the collected cometary dust particles, such as the specific resistivity (ρr>1.2⋅1010Ωm) and the real part of the relative electrical permittivity (εr<1.2). From these values a lower limit for the porosity is derived (P>0.8).

During ESA’s Rosetta science mission, the COSIMA instrument collected dust particles in the coma of Comet 67P/Churyumov-Gerasimenko during two years near the comet’s nucleus. The largest particles are about 1 m m in size. The collection process involved a low velocity impact on porous gold-black surfaces, often resulting in breakup, from which information on structural properties has previously been derived (Langevin et al., 2016). However, some of the particles were collected with little damage, but fragmented due to charging during subsequent secondary ion mass spectrometry. This report shows that the details of this electrical fragmentation support the concept of the existence of stable units with sizes of tens of ÎŒ m within the incoming cometary dust particles prior to collection, possibly representing remnants of the early accretion processes.

Context. Because comets are part of the most primitive bodies of our solar system, establishing their chemical composition and comparing them to other astrophysical bodies gives new constraints on the formation and evolution of organic matter throughout the solar system. For two years, the time-of-flight secondary ion mass spectrometer COmetary Secondary Ion Mass Analyzer (COSIMA) on board the Rosetta orbiter performed in situ analyses of the dust particles ejected from comet 67P/Churyumov-Gerasimenko (67P). Aims. The aim is to determine the H/C elemental ratio of the refractory organic component contained in cometary particles of 67P. Methods. We analyzed terrestrial and extraterrestrial calibration samples using the COSIMA ground-reference model. Exploiting these calibration samples, we provide calibration lines in both positive and negative ion registration modes. Thus, we are now able to measure the cometary H/C elemental ratio. Results. The mean H/C value is 1.04 +/- 0.16 based on 33 different cometary particles. Consequently, the H/C atomic ratio is on average higher in cometary particles of 67P than in even the most primitive insoluble organic matter extracted from meteorites. Conclusions. These results imply that the refractory organic matter detected in dust particles of 67P is less unsaturated than the material in meteorites.

Impacts are common geologic features on the terrestrial planets throughout the solar system, and on at least Earth and Mars impacts have induced hydrothermal convection. Impact-generated hydrothermal systems have been suggested to possess the same life supporting capability as hydrothermal systems associated with volcanic activity. However, evidence of fossil microbial colonization in impact-generated hydrothermal systems is scarce in the literature. Here we report of fossilized microorganisms in association with cavity-grown hydrothermal minerals from the 458â.Ma Lockne impact structure, Sweden. Based on morphological characteristics the fossilized microorganisms are interpreted as fungi. We further infer the kerogenization of the microfossils, and thus the life span of the fungi, to be contemporaneous with the hydrothermal activity and migration of hydrocarbons in the system. Our results from the Lockne impact structure show that hydrothermal systems associated with impact structures can support colonization by microbial life.

Garnets from disparate geographical environments and origins such as oxidized soils and river sediments in Thailand host intricate systems of microsized tunnels that significantly decrease the quality and value of the garnets as gems. The origin of such tunneling has previously been attributed to abiotic processes. Here we present physical and chemical remains of endolithic microorganisms within the tunnels and discuss a probable biological origin of the tunnels. Extensive investigations with synchrotron-radiation X-ray tomographic microscopy (SRXTM) reveal morphological indications of biogenicity that further support a euendolithic interpretation. We suggest that the production of the tunnels was initiated by a combination of abiotic and biological processes, and that at later stages biological processes came to dominate. In environments such as river sediments and oxidized soils garnets are among the few remaining sources of bio-available Fe2+, thus it is likely that microbially mediated boring of the garnets has trophic reasons. Whatever the reason for garnet boring, the tunnel system represents a new endolithic habitat in a hard silicate mineral otherwise known to be resistant to abrasion and chemical attack.

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 Perseverance rover landed at Jezero crater, Mars, on 18 February 2021, with a payload of scientific instruments to examine Mars’ past habitability, look for signs of past life, and process samples for future return to Earth. The instrument payload includes the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) deep ultraviolet Raman and fluorescence imaging spectrometer designed to detect, characterize, and map the presence of organics and minerals on the Martian surface. Operation and engineering constraints sometimes result in the acquisition of spectra with features near the detection limit. It is therefore important to separate instrumental (background) spectral components and spectral components inherent to Martian surface materials. For SHERLOC, the instrumental background is assessed by collecting spectra in the stowed-arm configuration where the instrument is pointed at the Martian nighttime sky with no surface sample present in its optical path. These measurements reveal weak Raman and fluorescence background spectral signatures as well as charged-coupled device pixels prone to erroneous intensity spikes separate from cosmic rays. We quantitatively describe these features and provide a subtraction procedure to remove the spectral background from surface spectra. By identifying and accounting for the SHERLOC Raman background features within the median Raman spectra of Martian target scans, we find that the undefined silicate spectral feature interpreted to be either amorphous silicate or plagioclase feldspar is ubiquitously found in every Mars target Raman scan collected through Sol 751. 

The Committee on Space Research (COSPAR) Sample Safety Assessment Framework (SSAF) has been developed by a COSPAR appointed Working Group. The objective of the sample safety assessment would be to evaluate whether samples returned from Mars could be harmful for Earth's systems (e.g., environment, biosphere, geochemical cycles). During the Working Group's deliberations, it became clear that a comprehensive assessment to predict the effects of introducing life in new environments or ecologies is difficult and practically impossible, even for terrestrial life and certainly more so for unknown extraterrestrial life. To manage expectations, the scope of the SSAF was adjusted to evaluate only whether the presence of martian life can be excluded in samples returned from Mars. If the presence of martian life cannot be excluded, a Hold & Critical Review must be established to evaluate the risk management measures and decide on the next steps. The SSAF starts from a positive hypothesis (there is martian life in the samples), which is complementary to the null-hypothesis (there is no martian life in the samples) typically used for science. Testing the positive hypothesis includes four elements: (1) Bayesian statistics, (2) subsampling strategy, (3) test sequence, and (4) decision criteria. The test sequence capability covers self-replicating and non-self-replicating biology and biologically active molecules. Most of the investigations associated with the SSAF would need to be carried out within biological containment. The SSAF is described in sufficient detail to support planning activities for a Sample Receiving Facility (SRF) and for preparing science announcements, while at the same time acknowledging that further work is required before a detailed Sample Safety Assessment Protocol (SSAP) can be developed. The three major open issues to be addressed to optimize and implement the SSAF are (1) setting a value for the level of assurance to effectively exclude the presence of martian life in the samples, (2) carrying out an analogue test program, and (3) acquiring relevant contamination knowledge from all Mars Sample Return (MSR) flight and ground elements. Although the SSAF was developed specifically for assessing samples from Mars in the context of the currently planned NASA-ESA MSR Campaign, this framework and the basic safety approach are applicable to any other Mars sample return mission concept, with minor adjustments in the execution part related to the specific nature of the samples to be returned. The SSAF is also considered a sound basis for other COSPAR Planetary Protection Category V, restricted Earth return missions beyond Mars. It is anticipated that the SSAF will be subject to future review by the various MSR stakeholders. © Gerhard Kminek et al., 2022; 

COmetary Secondary Ion Mass Analyzer (COSIMA) is a time-of-flight secondary ion mass spectrometry (TOF-SIMS) instrument on board the Rosetta space mission. COSIMA has been designed to measure the composition of cometary dust particles. It has a mass resolution m/Δm of 1400 at mass 100 u, thus enabling the discrimination of inorganic mass peaks from organic ones in the mass spectra. We have evaluated the identification capabilities of the reference model of COSIMA for inorganic compounds using a suite of terrestrial minerals that are relevant for cometary science. Ground calibration demonstrated that the performances of the flight model were similar to that of the reference model. The list of minerals used in this study was chosen based on the mineralogy of meteorites, interplanetary dust particles and Stardust samples. It contains anhydrous and hydrous ferromagnesian silicates, refractory silicates and oxides (present in meteoritic Ca-Al-rich inclusions), carbonates, and Fe-Ni sulfides. From the analyses of these minerals, we have calculated relative sensitivity factors for a suite of major and minor elements in order to provide a basis for element quantification for the possible identification of major mineral classes present in the cometary particles.

Mid-Mesozoic kalligrammatid lacewings (Neuroptera) entered the fossil record 165 million years ago (Ma) and disappeared 45 Ma later. Extant papilionoid butterflies (Lepidoptera) probably originated 80–70 Ma, long after kalligrammatids became extinct. Although poor preservation of kalligrammatid fossils previously prevented their detailed morphological and ecological characterization, we examine new, well-preserved, kalligrammatid fossils from Middle Jurassic and Early Cretaceous sites in northeastern China to unravel a surprising array of similar morphological and ecological features in these two, unrelated clades. We used polarized light and epifluorescence photography, SEM imaging, energy dispersive spectrometry and time-of-flight secondary ion mass spectrometry to examine kalligrammatid fossils and their environment. We mapped the evolution of specific traits onto a kalligrammatid phylogeny and discovered that these extinct lacewings convergently evolved wing eyespots that possibly contained melanin, and wing scales, elongate tubular proboscides, similar feeding styles, and seed–plant associations, similar to butterflies. Long-proboscid kalligrammatid lacewings lived in ecosystems with gymnosperm–insect relationships and likely accessed bennettitalean pollination drops and pollen. This system later was replaced by mid-Cretaceous angiosperms and their insect pollinators.

Time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a surface sensitive MS technique that offers a new way of studying lipid biomarkers at the microscopic level, without the need to destroy the physical integrity of the sample by extraction. We applied ToF-SIMS to a cryosection of a microbial mat and compared the results with ToF-SIMS and gas chromatography-MS (GC-MS) analysis of extracts from the same material. A wide range of lipid biomarkers was identified with ToF-SIMS in the microbial mat cryosection. Spectra and ion images revealed that individual biomarkers, including fatty acids, mono-, di- and triacylglycerols, carotenoids and chlorophyll were localized with diatom cells identified as Planothidium lanceolatum using optical microscopy. This diatom species can thus be regarded as a major lipid source within the microbial mat system. The results underpin the idea that ToF-SIMS has the potential to become an important technique for future biomarker studies, in particular for the clear cut assignment of biomarkers to distinctive morphological structures and specific microorganisms within complex biogeochemical samples.

RATIONALE Over the last decade, the high lateral resolution and imaging capabilities of time-of-flight secondary ion mass spectrometry (ToF-SIMS) have increasingly stimulated interest in studying organic molecules in complex environmental materials. However, unlike with the established mass spectrometric techniques, the use of ToF-SIMS in the biogeosciences is still hampered by a lack of reference spectra of the relevant biomarker compounds. Here we present and interpret ToF-SIMS reference spectra of ten different cyclic lipids that are frequently used as biological tracers in ecological, organic geochemical and geobiological studies. METHODS Standard compounds of α,β,β-(20R, 24S)-24-methylcholestane, (22E)-ergosta-5,7,22-trien-3β-ol, 17α(H),21β-(H)-30-norhopane, hope-17(21)-ene, hop-22(29)-ene, 17β(H),21β(H)-bacteriohopane-32,33,34,35-tetrol, 17β(H), 21β(H)-35-aminobacteriohopane-32,33,34-triol, α-tocopherol, β,β-carotene, chlorophyll a, and cryosections of microbial mats and a fungus were analyzed using a ToF-SIMS instrument equipped with a Bi 3+ cluster ion source. RESULTS The spectra obtained from the standard compounds showed peaks in the molecular weight range (molecular ions, protonated and deprotonated molecules, adduct ions) and diagnostic fragment ion peaks in both, positive and negative ion modes. For the cyclic hydrocarbons, however, the positive ion mode spectra typically showed more and stronger characteristic peaks than the negative ion mode spectra. Using real world samples the capability of ToF-SIMS to detect and image selected compounds in complex organic matrices was tested. 17β(H),21β(H)-35- Aminobacteriohopane-32,33,34-triol, carotene and chlorophyll a were successfully identified in cryosections of microbial mats, and the distribution of ergosterol was mapped at μm resolution in a cryosection of a fungus (Tuber uncinatum). CONCLUSIONS This study further highlights the utility of ToF-SIMS for the identification and localization of lipids within environmental samples and as a technique for biomarker-related research in organic geochemistry and geobiology.

Elucidating cardiac evolution has been frustrated by lack of fossils. One celebrated enigma in cardiac evolution involves the transition from a cardiac outflow tract dominated by a Multi-Valved conus arteriosus in basal actinopterygians, to an outflow tract commanded by the Non- Valved, elastic, bulbus arteriosus in higher actinopterygians. We demonstrate that cardiac preservation is possible in the extinct fish Rhacolepis buccalis from the Brazilian Cretaceous. Using X-Ray synchrotron microtomography, we show that Rhacolepis fossils display hearts with a conus arteriosus containing at least five valve rows. This represents a transitional morphology between the primitive, multivalvar, conal condition and the derived, monovalvar, bulbar state of the outflow tract in modern actinopterygians. Our data rescue a Long-Lost cardiac phenotype (119-113 Ma) and suggest that outflow tract simplification in actinopterygians is compatible with a gradual, rather than a drastic saltation event. Overall, our results demonstrate the feasibility of studying cardiac evolution in fossils.

Solar radiation that arrives on the surface of Mars interacts with organic molecules present in the soil. The radiation can degrade or transform the organic matter and make the search for biosignatures on the planet’s surface difficult. Therefore, samples to be analyzed by instruments on board Mars probes for molecular content should be selectively chosen to have the highest organic preservation content. To support the identification of organic molecules on Mars, the behavior under UV irradiation of two organic compounds, undecanoic acid and L-phenylalanine, in the presence of vermiculite and two chloride salts, NaCl and MgCl, was studied. The degradation of the molecule’s bands was monitored through IR spectroscopy. Our results show that, while vermiculite acts as a photoprotective mineral with L-phenylalanine, it catalyzes the photodegradation of undecanoic acid molecules. On the other hand, both chloride salts studied decreased the degradation of both organic species acting as photoprotectors. While these results do not allow us to conclude on the preservation capabilities of vermiculite, they show that places where chloride salts are present could be good candidates for in situ analytic experiments on Mars due to their organic preservation capacity under UV radiation. 

The D/H ratio is a clue to the origin and evolution of hydrogen-bearing chemical species in Solar system materials. D/H has been observed in the coma of many comets, but most such measurements have been for gaseous water. We present the first in situ measurements of the D/H ratios in the organic refractory component of cometary dust particles collected at very low impact speeds in the coma of comet 67P/Churyumov-Gerasimenko (hereafter 67P) by the COSIMA instrument onboard Rosetta. The values measured by COSIMA are spatial averages over an approximately 35 × 50 µm2 area. The average D/H ratio for the 25 measured particles is (1.57 ± 0.54) × 10−3, about an order of magnitude higher than the Vienna Standard Mean Ocean Water (VSMOW), but more than an order of magnitude lower than the values measured in gas-phase organics in solar-like protostellar regions and hot cores. This relatively high averaged value suggests that refractory carbonaceous matter in comet 67P is less processed than the most primitive insoluble organic matter (IOM) in meteorites, which has a D/H ratio in the range of about 1 to 7 × 10−4. The cometary particles measured in situ also have a higher H/C ratio than the IOM. We deduce that the measured D/H in cometary refractory organics is an inheritance from the presolar molecular cloud from which the Solar system formed. The high D/H ratios observed in the cometary particles challenges models in which high D/H ratios result solely from processes that operated in the protosolar disc.

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.

We present a synthesis of PIXL elemental data and SHERLOC Raman spectra collected on two targets investigated by the Perseverance rover during the first year of its exploration of Jezero Crater, Mars. The Bellegarde target (in the Máaz formation) and Dourbes target (in the Séítah formation) exhibit distinctive mineralogies that are an ideal case study for in situ analysis by SHERLOC and PIXL. Each instrument alone produces valuable data about the chemistry and spatial distribution of mineral phases at the sub-millimeter scale. However, combining data from both instruments provides a more robust interpretation that overcomes the limitations of either instrument, for example: 1) Detection of correlated calcium and sulfur in Bellegarde by PIXL is corroborated by the co-located detection of calcium sulfate by SHERLOC. 2) Detection of sodium and chlorine in Dourbes is consistent with either chloride or oxychlorine salts, but SHERLOC does not detect perchlorate or chlorate. 3) A Raman peak at 1120 cm−1 in Dourbes could be sulfate or pyroxene, but elemental abundances from PIXL at that location are a better match to pyroxene. This study emphasizes the importance of analyzing co-located data from both instruments together, to obtain a more complete picture of sub-millimeter-scale mineralogy measured in situ in Jezero crater, Mars, by the Perseverance rover. © 2022 The Authors

The Perseverance rover landed in Jezero crater, Mars, in February 2021. We used the Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) instrument to perform deep-ultraviolet Raman and fluorescence spectroscopy of three rocks within the crater. We identify evidence for two distinct ancient aqueous environments at different times. Reactions with liquid water formed carbonates in an olivine-rich igneous rock. A sulfate-perchlorate mixture is present in the rocks, which probably formed by later modifications of the rocks by brine. Fluorescence signatures consistent with aromatic organic compounds occur throughout these rocks and are preserved in minerals related to both aqueous environments. 

Comets are composed of dust and frozen gases. The ices are mixed with the refractory material either as an icy conglomerate, or as an aggregate of pre-solar grains (grains that existed prior to the formation of the Solar System), mantled by an ice layer. The presence of water-ice grains in periodic comets is now well established. Modelling of infrared spectra obtained about ten kilometres from the nucleus of comet Hartley 2 suggests that larger dust particles are being physically decoupled from fine-grained water-ice particles that may be aggregates, which supports the icy-conglomerate model. It is known that comets build up crusts of dust that are subsequently shed as they approach perihelion. Micrometre-sized interplanetary dust particles collected in the Earth's stratosphere and certain micrometeorites are assumed to be of cometary origin. Here we report that grains collected from the Jupiter-family comet 67P/Churyumov-Gerasimenko come from a dusty crust that quenches the material outflow activity at the comet surface. The larger grains (exceeding 50 micrometres across) are fluffy (with porosity over 50 per cent), and many shattered when collected on the target plate, suggesting that they are agglomerates of entities in the size range of interplanetary dust particles. Their surfaces are generally rich in sodium, which explains the high sodium abundance in cometary meteoroids. The particles collected to date therefore probably represent parent material of interplanetary dust particles. This argues against comet dust being composed of a silicate core mantled by organic refractory material and then by a mixture of water-dominated ices. At its previous recurrence (orbital period 6.5 years), the comet's dust production doubled when it was between 2.7 and 2.5 astronomical units from the Sun, indicating that this was when the nucleus shed its mantle. Once the mantle is shed, unprocessed material starts to supply the developing coma, radically changing its dust component, which then also contains icy grains, as detected during encounters with other comets closer to the Sun.

The presence and distribution of preserved organic matter on the surface of Mars can provide key information about the Martian carbon cycle and the potential of the planet to host life throughout its history. Several types of organic molecules have been previously detected in Martian meteorites1 and at Gale crater, Mars2–4. Evaluating the diversity and detectability of organic matter elsewhere on Mars is important for understanding the extent and diversity of Martian surface processes and the potential availability of carbon sources1,5,6. Here we report the detection of Raman and fluorescence spectra consistent with several species of aromatic organic molecules in the Máaz and Séítah formations within the Crater Floor sequences of Jezero crater, Mars. We report specific fluorescence-mineral associations consistent with many classes of organic molecules occurring in different spatial patterns within these compositionally distinct formations, potentially indicating different fates of carbon across environments. Our findings suggest there may be a diversity of aromatic molecules prevalent on the Martian surface, and these materials persist despite exposure to surface conditions. These potential organic molecules are largely found within minerals linked to aqueous processes, indicating that these processes may have had a key role in organic synthesis, transport or preservation. © 2023, The Author(s).

The characterization of any organic molecules on Mars is a top-priority objective for the ExoMars European Space Agency-Russian Federal Space Agency joint mission. The main instrument for organic analysis on the ExoMars rover is the Mars Organic Molecule Analyzer (MOMA). In preparation for the upcoming mission in 2018, different Mars analog samples are studied with MOMA and include samples collected during the Arctic Mars Analog Svalbard Expedition (AMASE) to Svalbard, Norway. In this paper, we present results obtained from two different Mars analog sites visited during AMASE11, Colletthøgda and Botniahalvøya. Measurements were performed on the samples during AMASE11 with a MOMA gas chromatograph (GC) prototype connected to a commercial mass spectrometer (MS) and later in home institutions with commercial pyrolysis-GCMS instruments. In addition, derivatization experiments were performed on the samples during AMASE11 and in the laboratory. Three different samples were studied from the Colletthøgda that included one evaporite and two carbonate-bearing samples. Only a single sample was studied from the Botniahalvøya site, a weathered basalt covered by a shiny surface consisting of manganese and iron oxides. Organic molecules were detected in all four samples and included aromatics, long-chained hydrocarbons, amino acids, nucleobases, sugars, and carboxylic acids. Both pyrolysis and derivatization indicated the presence of extinct biota by the detection of carboxylic acids in the samples from Colletthøgda, while the presence of amino acids, nucleobases, carboxylic acids, and sugars indicated an active biota in the sample from Botniahalvøya. The results obtained with the prototype flight model in the field coupled with repeat measurements with commercial instruments within the laboratory were reassuringly similar. This demonstrates the performance of the MOMA instrument and validates that the instrument will aid researchers in their efforts to answer fundamental questions regarding the speciation and possible source of organic content on Mars.

Organic phases trapped inside natural mineral samples are of considerable interest in astrobiology, geochemistry and geobiology. Examples of such organic phases are microfossils, kerogen and oil. Information about these phases is usually retrieved through bulk crushing of the rock which means both a risk of contamination and that the composition and spatial distribution of the organics to its host mineral is lost. An attractive of way to retrieve information about the organics in the rock is depth profiling using a focused ion beam. Recently, it was shown that it is possible to obtain detailed mass spectrometric information from oil-bearing fluid inclusions, i.e. small amounts of oil trapped inside a mineral matrix, using ToF-SIMS. Using a 10 keV C-60(+) sputter beam and a 25 keV Bi-3(+) analysis beam, oil-bearing inclusions in different minerals were opened and analysed individually. However, sputtering with a C-60(+) beam also induced other changes to the mineral surface, such as formation of topographic features and carbon deposition. In this paper, the cause of these changes is explored and the consequences of the sputter-induced features on the analysis of organic phases in natural mineral samples (quartz, calcite and fluorite) in general and fluid inclusions in particular are discussed. The dominating topographical features that were observed when a several micrometers deep crater is sputtered with 10 keV C-60(+) ions on a natural mineral surface are conical-shaped and ridge-like structures that may rise several micrometers, pointing in the direction of the incident C-60(+) ion beam, on an otherwise flat crater bottom. The sputter-induced structures were found to appear at places with different chemistry than the host mineral, including other minerals phases and fluid inclusions, while structural defects in the host material, such as polishing marks or scratches, did not necessarily result in sputter-induced structures. The ridge-like structures were often covered by a thick layer of deposited carbon. Despite the appearance of the sputter-induced structures and carbon deposition, most oil-bearing inclusions could successfully be opened and analysed. However, smaller inclusion (

The Mars Organic Molecule Analyzer (MOMA) is a key scientific instrument on the ExoMars Rover mission. MOMA is designed to detect and characterize organic compounds, over a wide range of volatility and molecular weight, in samples obtained from up to 2 m below the martian surface. Thorough analog sample studies are required to best prepare to interpret MOMA data collected on Mars. We present here the MOMA characterization of Mars analog samples, microbial streamer communities composed primarily of oxygenic and anoxygenic phototrophs, collected from an alkaline silica-depositing hot spring in Yellowstone National Park, Wyoming, USA. Samples of partly mineralized microbial streamers and their total lipid extract (TLE) were measured on a MOMA Engineering Test Unit (ETU) instrument by using its laser desorption/ionization mass spectrometry (LDI-MS) mode. MOMA LDI-MS detected a variety of lipids and pigments such as chlorophyll a, monogalactosyldiacylglycerol, digalactosyldiacylglycerol, diacylglycerols, and β-carotene in the TLE sample. Only chlorophyll a was detected in the untreated streamer samples when using mass isolation, which was likely due to the higher background signal of this sample and the relative high ionization potential of the chlorophyll a compared with other compounds in unextracted samples. The results add to the LDI-MS sample characterization database and demonstrate the benefit of using mass isolation on the MOMA instrument to reveal the presence of complex organics and potential biomarkers preserved in a natural sample. This will also provide guidance to in situ analysis of surface samples during Mars operations.