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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.

Molar-tooth structure (MTS) is an unusual carbonate fabric that is composed of variously shaped cracks and voids filled with calcite microspar. Despite a century of study, MTS remains enigmatic because it juxtaposes void formation within a cohesive yet unlithified substrate with the penecontemporaneous precipitation and lithification of void-filling carbonate microspar. MTS is broadly restricted to shallow marine carbonate strata of the Mesoproterozoic and Neoproterozoic, suggesting a fundamental link between the formation of MTS and the biogeochemical evolution of marine environments. Despite uncertainties in the origin of MTS, molar-tooth (MT) microspar remains a popular target for geochemical analysis and the reconstruction of Precambrian marine chemistry. Here we review models for the formation of MTS and show how detailed petrographic analysis of MT microspar permits identification of a complex process of precipitation and diagenesis that must be considered when the microspar phase is used as a geochemical proxy. ▪ Molar-tooth fabric is an enigmatic structure in Precambrian sedimentary rocks that is composed of variously shaped cracks and voids filled with carbonate microspar. ▪ Time restriction of this fabric suggests a link between this unusual structure and the biogeochemical evolution of marine environments. ▪ Petrographic analysis of molar-tooth fabric provides insight into fundamental processes of crystallization.

At a Mars analog site in Utah, we tested two science operation methods for data acquisition and decision-making protocols: a scenario where the tactical day is preplanned, but major adjustments may still be made before plan delivery; and a scenario in which the sol path must largely be planned before a given tactical planning day and very few adjustments to the plan may be made. The goal was to provide field-tested insight into operations planning for rover missions where science operations must facilitate the efficient choice of sampling locations at a site relevant to searching for habitability and biosignatures. Results of the test indicate that preplanning sol paths did not result in a sol cost savings nor did it improve science return or optimal biologically relevant sample collection. In addition because facies variations in an environment can be subtle and evident only at scales below orbital resolution, acquiring systematic observations is crucial. We also noted that while spectral data provided insight into the chemical components as a whole at this site, they did not provide a guide to targets for which the traverse should be altered. Finally, strategic science planning must include a special effort to account for terrain.

Time-distinctive features within carbonate rocks, specifically the presence, abundance and distribution of stromatolites, molar-tooth fabric and specific morphologies of marine cement, have been identified as potential indicators of global-scale changes in the chemistry of marine environments. Recently, Cantineet al.(2019) introduced a database approach seeking to quantify spatial and temporal patterns in these carbonate features through the Precambrian. Despite the coarse temporal scale, results support earlier inferences of temporal change in carbonate sedimentation. Here, we use original field notes to dissect late Mesoproterozoic (˜1.3 to 1.0 Ga) carbonate strata at a high resolution, analyse time-distinctive carbonate fabrics within a database context and compare sedimentological patterns within this narrow time range to observations of the Proterozoic as a whole. Late Mesoproterozoic strata contain a variety of features (e.g. stromatolites, seafloor precipitates, herringbone carbonate, molar-tooth carbonate), often in close spatial and temporal proximity, that are commonly considered to be temporally restricted during the Precambrian. The spatial distribution of such features within Mesoproterozoic basins demonstrates the importance of recognizing even rare occurrences of time-distinctive facies and permits inference of environmental drivers that may have interacted to affect carbonate precipitation. Such spatial variability reflects a subtle division of Mesoproterozoic carbonate platform environments driven by globally high sea level, elevated carbonate saturation and a low-oxygen water column. The heterogeneous, mosaic nature of environments appears to be a hallmark of Mesoproterozoic carbonate sedimentation and emphasizes the importance of these basins in understanding longer-term trends in carbonate deposition.

We conducted a field test at a potential Mars analog site to provide insight into planning for future robotic missions such as Mars 2020, where science operations must facilitate efficient choice of biologically relevant sampling locations. We compared two data acquisition and decision-making protocols currently used by Mars Science Laboratory: (1) a linear approach, where sites are examined as they are encountered and (2) a walkabout approach, in which the field site is first examined with remote rover instruments to gain an understanding of regional context followed by deployment of time- and power-intensive contact and sampling instruments on a smaller subset of locations. The walkabout method was advantageous in terms of both the time required to execute and a greater confidence in results and interpretations, leading to enhanced ability to tailor follow-on observations to better address key science and sampling goals. This advantage is directly linked to the walkabout method's ability to provide broad geological context earlier in the science analysis process. For Mars 2020, and specifically for small regions to be explored (e.g.

We tested rover science operations strategies to determine best practices for interrogating geologic sections where the bulk composition is igneous but depositional/emplacement processes range from sedimentary to volcanic. This scenario may mirror locations on Mars interrogated by mobile vehicles (e.g., Perseverance rover in Jezero crater). Two field teams studied a 60 m vertical outcrop on Iceland’s Tjörnes peninsula as an analog for a Martian site containing interleaved layers of sedimentary and volcanic units. A Rover team commanded a human rover to execute observations based on common Mars rover sequences; the resulting data were used to characterize the geologic history of the location. Results were compared to that of a Tiger team using traditional terrestrial field methods to interrogate the same site. The goal was to understand which instruments, at what resolution, are required to assess the provenance of volcanic or sedimentary layers of similar chemical composition. Results suggest that, in a succession dominated by rocks having basaltic composition, current rover-driven decision-making protocols are sufficient to support a first-order interpretation of a sequence of sedimentary and volcanic layers. Two crucial data sets in maximizing science return in this scenario are (1) handlens-scale images revealing grain morphology and relationships and (2) data sets that allow comparison between surface and bulk geochemistry. Certain sedimentary features can be difficult to confidently identify if not viewed at a specific angle and resolution, and confident interpretations appear to require lateral scanning of beds at meter scales. This work illuminates the need for strategic planning, particularly of resource-intensive observations.

Otoliths are frequently used to infer environmental conditions or fish life history events based on trace-element concentrations. However, otoliths can be comprised of any one or combination of the three most common polymorphs of calcium carbonate—aragonite, calcite, and vaterite—which can affect the ecological interpretation of otolith trace-element results. Previous studies have reported heterogeneous calcium carbonate compositions between left and right otoliths but did not provide quantitative assessments of polymorph abundances. In this study, neutron diffraction and Raman spectroscopy were used to identify and quantify mineralogical compositions of Chinook salmon Oncorhynchus tshawytscha otolith pairs. We found mineralogical compositions frequently differed between otoliths in a pair and accurate calcium carbonate polymorph identification was rarely possible by visual inspection alone. The prevalence of multiple polymorphs in otoliths is not well-understood, and future research should focus on identifying otolith compositions and investigate how variations in mineralogy affect trace-element incorporation and potentially bias environmental interpretations.

Reconstructing Earth's oxygenation history is key to deciphering environmental controls on early biospheric evolution. During the mid-Proterozoic Eon, low (but potentially variable) atmospheric pO2 led to highly heterogeneous marine redox conditions, with most studies indicating a relatively shallow depth of oxygen penetration. The relative proportion of oxic, anoxic and iron-rich (ferruginous), and anoxic and sulfide-rich (euxinic) conditions on the global seafloor is difficult to quantify, however, due to a general reliance on local redox proxies applied to the temporally discontinuous black shale record. It is particularly important to constrain the global prevalence of euxinic bottom waters because sulfide toxicity has been implicated as a primary constraint on evolution in mid-Proterozoic oceans and limits the solubility of bioessential trace metals such as copper, zinc, and molybdenum. Here, we present a suite of new uranium (U) isotope data from marine carbonate rocks that span the entire mid-Proterozoic interval (∼1.8 to 0.8 Ga). U-isotopes in well-preserved carbonate rocks represent a powerful new proxy that can be used to quantitatively constrain the global extent of marine euxinia. The median δ 238 U value for mid-Proterozoic carbonate samples is −0.43‰, which is lower than the median value for modern post-depositional carbonate sediments from the Bahamas, yet significantly higher than carbonate δ 238 U values recorded during other times of expanded anoxia in Earth history, such as during the end-Permian mass extinction. When paired with a three-sink isotope mass balance model, our data indicate that no more than 7% of the global seafloor was euxinic during the mid-Proterozoic Eon, although transient pulses of expanded euxinia are recorded. Although these results challenge early expectations of a sulfide-rich mid-Proterozoic ocean, they are consistent with more recent inferences from the black shale trace metal record. Evidence therefore indicates that euxinic bottom waters were relatively limited in their spatial extent in the mid-Proterozoic oceans.

The Mars Science Laboratory Curiosity rover conducted a reconnaissance traverse across the Pahrump Hills outcrop within Gale crater from Sols 780–797. During the traverse, the Mars Descent Imager (MARDI) acquired a continuous imaging record of primary and secondary sedimentary features throughout the outcrop. The characteristics of the features (laminae, resistant features, fractures, gray clasts) and their spatial distribution provide insight into the processes that contributed to the formation of Pahrump Hills. Thin, regular laminae (mm-scale) are ubiquitous in the bedrock, implying that depositional processes at that scale did not change appreciably during deposition of the mudstone succession at Pahrump Hills. Higher bedrock slopes correlate with undulatory bedrock surfaces, bedrock with elevated Mg contents, and fractures exhibiting wide, raised edges. These collective features are consistent with increased erosional resistance caused by greater quantities of erosionally-resistant, Mg-bearing cement within the bedrock permitted by coarser grain sizes. Resistant features exhibit a range of morphologies, elevated Mg contents, and do not deflect laminae within the bedrock. Their characteristics implicate the involvement of Mg-enriched fluids in a late diagenetic overprint affecting the bedrock. The variations of fracture fill and edge morphologies and chemistries further suggest repeated fracturing and fluid interaction events within the strata exposed at Pahrump Hills. Gray clasts strongly resemble fragments eroded from sandstone horizons interspersed throughout the Pahrump Hills outcrop.

Recent robotic missions to Mars have offered new insights into the extent, diversity and habitability of the Martian sedimentary rock record. Since the Curiosity rover landed in Gale crater in August 2012, the Mars Science Laboratory Science Team has explored the origins and habitability of ancient fluvial, deltaic, lacustrine and aeolian deposits preserved within the crater. This study describes the sedimentology of a ca 13 m thick succession named the Pahrump Hills member of the Murray formation, the first thick fine‐grained deposit discovered in situ on Mars. This work evaluates the depositional processes responsible for its formation and reconstructs its palaeoenvironmental setting. The Pahrump Hills succession can be sub‐divided into four distinct sedimentary facies: (i) thinly laminated mudstone; (ii) low‐angle cross‐stratified mudstone; (iii) cross‐stratified sandstone; and (iv) thickly laminated mudstone–sandstone. The very fine grain size of the mudstone facies and abundant millimetre‐scale and sub‐millimetre‐scale laminations exhibiting quasi‐uniform thickness throughout the Pahrump Hills succession are most consistent with lacustrine deposition. Low‐angle geometric discordances in the mudstone facies are interpreted as ‘scour and drape’ structures and suggest the action of currents, such as those associated with hyperpycnal river‐generated plumes plunging into a lake. Observation of an overall upward coarsening in grain size and thickening of laminae throughout the Pahrump Hills succession is consistent with deposition from basinward progradation of a fluvial‐deltaic system derived from the northern crater rim into the Gale crater lake. Palaeohydraulic modelling constrains the salinity of the ancient lake in Gale crater: assuming river sediment concentrations typical of floods on Earth, plunging river plumes and sedimentary structures like those observed at Pahrump Hills would have required lake densities near freshwater to form. The depositional model for the Pahrump Hills member presented here implies the presence of an ancient sustained, habitable freshwater lake in Gale crater for at least ca 10^3 to 10^7 Earth years.

The Scanning Habitable Environments with Raman and Luminescence for Organics and Chemicals (SHERLOC) is a robotic arm-mounted instrument on NASA’s Perseverance rover. SHERLOC has two primary boresights. The Spectroscopy boresight generates spatially resolved chemical maps using fluorescence and Raman spectroscopy coupled to microscopic images (10.1 μm/pixel). The second boresight is a Wide Angle Topographic Sensor for Operations and eNgineering (WATSON); a copy of the Mars Science Laboratory (MSL) Mars Hand Lens Imager (MAHLI) that obtains color images from microscopic scales (∼13 μm/pixel) to infinity. SHERLOC Spectroscopy focuses a 40 μs pulsed deep UV neon-copper laser (248.6 nm), to a ∼100 μm spot on a target at a working distance of ∼48 mm. Fluorescence emissions from organics, and Raman scattered photons from organics and minerals, are spectrally resolved with a single diffractive grating spectrograph with a spectral range of 250 to ∼370 nm. Because the fluorescence and Raman regions are naturally separated with deep UV excitation (−1 (250 to 273 nm) and the fluorescence region (274 to ∼370 nm) are acquired simultaneously without time gating or additional mechanisms. SHERLOC science begins by using an Autofocus Context Imager (ACI) to obtain target focus and acquire 10.1 μm/pixel greyscale images. Chemical maps of organic and mineral signatures are acquired by the orchestration of an internal scanning mirror that moves the focused laser spot across discrete points on the target surface where spectra are captured on the spectrometer detector. ACI images and chemical maps (< 100 μm/mapping pixel) will enable the first Mars in situ view of the spatial distribution and interaction between organics, minerals, and chemicals important to the assessment of potential biogenicity (containing CHNOPS). Single robotic arm placement chemical maps can cover areas up to 7x7 mm in area and, with the < 10 min acquisition time per map, larger mosaics are possible with arm movements. This microscopic view of the organic geochemistry of a target at the Perseverance field site, when combined with the other instruments, such as Mastcam-Z, PIXL, and SuperCam, will enable unprecedented analysis of geological materials for both scientific research and determination of which samples to collect and cache for Mars sample return.

International audience; Fine scale (submillimeter to centimeter) depositional and diagenetic features encountered during the Curiosity rover's traverse in Gale crater provide a means to understand the geologic history of Vera Rubin ridge (VRR). VRR is a topographically high feature on the lower north slope of Aeolis Mons, a 5 km high stratified mound within Gale crater. We use high spatial resolution images from the Mars Hand Lens Imager (MAHLI) as well as grain sizes estimated with the Gini index mean score technique that uses ChemCam Laser Induced Breakdown Spectroscopy (LIBS) chemical data to constrain the postdepositional history of the strata exposed on this ridge. MAHLI images were used to examine the color, grain size, and style of lamination of the host rocks, as well as to explore the occurrence of nodules, diagenetic crystals, pits, and a variety of dark gray iron rich features. This survey revealed abundant and widespread diagenetic features within the rocks exposed on VRR and demonstrated that rock targets estimated to be coarser generally contain more diagenetic features than those estimated to have finer grains, which indicate that grain size may have influenced the degree and type of diagenesis. A subset of rocks within VRR are gray in color and exhibit the highest proportion of diagenetic features. We suggest that these targets experienced a different diagenetic history than the other rocks on VRR and hypothesize that redistribution and recrystallization of iron within specific intervals may have resulted in both the gray color and the abundance of dark gray iron rich diagenetic features.

Rock fractures and veins have been well documented by the Curiosity rover in the lithologies within Gale crater, Mars, and an understanding of the rock mechanical properties of Mars analog samples will improve our capabilities to predict fracture formation conditions (e.g., burial depth and influence of fluids). Data collected by Curiosity's drill allow estimation of unconfined compressive strength (UCS) for rocks that have been sampled by the drill. These estimates reveal that the drilled rock types are considerably weak. Qualitative assessments of rock types that were not drilled, however, suggest that stronger lithologies also exist within Gale crater. Here we integrate experimental testing, computational simulation, and uncertainty quantification to evaluate a predictive approach using the UCS obtained from the rover to determine a suite of mechanical properties for Gale lithologies. This method is demonstrated using analog rocks, specifically iron‐cemented sandstone and poorly lithified mudstone. The range of properties determined from sandstone testing is consistent with very strong terrestrial lithologies, and mudstone testing is consistent with extremely weak lithologies, both representative of rock types identified in Gale crater. We evaluate the use of established correlations between measured properties and quantify the uncertainty in using predicted properties to simulate fracture through analog lithologies. Sensitivity analysis indicates the properties of tensile strength and fracture energy derived from the UCS are highly influential properties in predicting fracture. The predictive approach was successful for a well‐sorted and well‐cemented fine sandstone with no visible porosity and exhibited substantially large errors for analog eolian siltstone lithologies.

The GHOST field tests are designed to isolate and test science-driven rover operations protocols, to determine best practices. During a recent field test at a potential Mars 2020 landing site analog, we tested two Mars Science Laboratory data-acquisition and decision-making methods to assess resulting science return and sample quality: a linear method, where sites of interest are studied in the order encountered, and a “walkabout-first” method, where sites of interest are examined remotely before down-selecting to a subset of sites that are interrogated with more resource-intensive instruments. The walkabout method cost less time and fewer resources, while increasing confidence in interpretations. Contextual data critical to evaluating site geology was acquired earlier than for the linear method, and given a higher priority, which resulted in development of more mature hypotheses earlier in the analysis process. Combined, this saved time and energy in the collection of data with more limited spatial coverage. Based on these results, we suggest that the walkabout method be used where doing so would provide early context and time for the science team to develop hypotheses-critical tests; and that in gathering context, coverage may be more important than higher resolution.

The Vindhyan Basin of north-central India contains a thick, areally extensive, largely unmetamorphosed succession of sedimentary rocks deposited during the Proterozoic Eon. Despite a wealth of studies aimed at using Vindhyan Basin strata as an archive for Proterozoic global events, fundamental questions persist about basic aspects of Vindhyan Basin stratigraphy. Specifically, we lack detailed age constraints for units within the Upper Vindhyan succession, discrete correlation of units across the basin, and critical understanding of the extent to which diagenetic processes have compromised primary geochemical signals. Here, we focus on Vindhyan Basin carbonates—their chemostratigraphy and diagenesis. We present a new petrographic and geochemical dataset—including carbon isotopes, oxygen isotopes, and trace element signatures—for a variety of carbonate units exposed within the Vindhyan Basin, both in the Son Valley and Rajasthan sectors. Results of our diagenetic assessment indicate a range of preservation states in strata of the Lower Vindhyan sequence. The Bhagwanpura Limestone is pervasively dolomitized (largely fabric-destructive), and has been subjected to multiple generations of burial diagenesis in the presence of iron-rich, reducing fluids that altered oxygen isotope and trace element trends. By contrast, the Nimbahera Limestone is dominantly composed of micritic to microsparitic calcite that preserves largely marine isotopic and trace element signatures. The Tirohan Limestone is also pervasively dolomitized, but unlike the Bhagwanpura Limestone, dolomitization potentially occurred during early marine diagenesis, preserving seawater-like isotopic and trace element trends, with the exception of Sr depletion. Upper Vindhyan sequence carbonate units (the Lakheri and Bhander limestones) are largely characterized by micritic to microsparitic fabric-retentive microstructure, as well as isotopic and trace element trends that suggest diagenetic stabilization in the presence of marine fluids. Carbon isotope chemostratigraphy builds on previous work, and when interpreted in the context of recent geochronology, provides new information on the age of the Upper Vindhyan sequence. In the Lakheri Limestone, a stratigraphically coherent pattern of δ13C values between +2 and +3‰ with a minor negative excursion down to +1‰ is observed. This isotopic profile is consistent with global patterns of muted isotopic variability during the late Mesoproterozoic to earliest Neoproterozoic eras, thus supporting recent geochronology that suggests a much older age for the Upper Vindhyan sequence than traditionally thought, at least in the Rajasthan sector. Similar age revisions have recently been proposed for other ‘Purana’ basins in India. In Son Valley, however, strongly positive δ13C values (between +4 and +6‰) are recorded in the Bhander Limestone, suggesting that the Lakheri and Bhander limestones are not stratigraphic equivalents and that the Bhander Limestone may be fully Neoproterozoic in age. Ultimately, our data provide new diagenetic and chemostratigraphic information that will inform future studies of Vindhyan Basin strata.

We investigate the expression of the Middle Darriwilian isotope carbon excursion (MDICE) across marine shelf environments in the Argentine Precordillera. Previous work identified the MDICE in the Las Chacritas Formation in Argentina, but did not recognize the expression of the MDICE in time-equivalent strata of the deeper-water Las Aguaditas Formation (Albanesi et al., 2013; Palaeogeography, Palaeoclimatology, Palaeoecology, v. 398, p. 48?66). Recent biostratigraphic investigations of these units have, for the first time, provided the opportunity for high-resolution correlation, which suggest that the MDICE, or at least the initiation of the MDICE, should be observed in both the Las Chacritas and Las Aguaditas formations. Here we present new paired carbon isotope data of carbonate and organic carbon from the Las Chacritas and Las Aguaditas formations. We identify a 2 ? positive shift in the isotopic composition of marine carbonate in the Las Chacritas Formation, whereas values abruptly fall to < −1 ? in equivalent strata of the Las Aguaditas Formation. This is the first record of divergence from the globally recognized MDICE event. There are also small, yet distinct differences in the isotopic composition of marine organic matter between these two sections. We suggest that the divergent C-isotope trends of carbonate in the Las Chacritas and Las Aguaditas formations represent deposition in fundamentally different parts of the water column above and below the marine chemocline, respectively during the MDICE interval. This interpretation is consistent with data from the Las Aguaditas Formation that shows elevated Mn and Fe concentrations in carbonate phases with little evidence for recrystallization, and with a growing consensus for regionally anoxic conditions for the Middle Ordovician. Our data indicate that redox gradients can play a critical role in the behavior of marine carbon isotope excursions. Fil: Henderson, Miles A.. University of Tennessee; Estados Unidos Fil: Serra, Fernanda. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina Fil: Feltes, Nicolás Alexis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales. Museo de Paleontología; Argentina Fil: Albanesi, Guillermo Luis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Centro de Investigaciones en Ciencias de la Tierra. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas Físicas y Naturales. Centro de Investigaciones en Ciencias de la Tierra; Argentina. Universidad Nacional de Córdoba. Facultad de Ciencias Exactas, Físicas y Naturales. Museo de Paleontología; Argentina Fil: Kah, Linda C.. University of Tennessee; Estados Unidos

The Proterozoic Eon hosted the emergence and initial recorded diversification of eukaryotes. Oxygen levels in the shallow marine settings critical to these events were lower than today's, although how much lower is debated. Here, we use concentrations of iodate (the oxidized iodine species) in shallow-marine limestones and dolostones to generate the first comprehensive record of Proterozoic near-surface marine redox conditions. The iodine proxy is sensitive to both local oxygen availability and the relative proximity to anoxic waters. To assess the validity of our approach, Neogene–Quaternary carbonates are used to demonstrate that diagenesis most often decreases and is unlikely to increase carbonate-iodine contents. Despite the potential for diagenetic loss, maximum Proterozoic carbonate iodine levels are elevated relative to those of the Archean, particularly during the Lomagundi and Shuram carbon isotope excursions of the Paleo- and Neoproterozoic, respectively. For the Shuram anomaly, comparisons to Neogene–Quaternary carbonates suggest that diagenesis is not responsible for the observed iodine trends. The baseline low iodine levels in Proterozoic carbonates, relative to the Phanerozoic, are linked to a shallow oxic–anoxic interface. Oxygen concentrations in surface waters would have at least intermittently been above the threshold required to support eukaryotes. However, the diagnostically low iodine data from mid-Proterozoic shallow-water carbonates, relative to those of the bracketing time intervals, are consistent with a dynamic chemocline and anoxic waters that would have episodically mixed upward and laterally into the shallow oceans. This redox instability may have challenged early eukaryotic diversification and expansion, creating an evolutionary landscape unfavorable for the emergence of animals.

Patterns of change in the isotope composition of sulfur-bearing minerals play a key role in reconstructing the marine sulfur cycle. Determining marine sulfate concentration, in particular, is critical to understanding the linkages between oxygenation of the Earth's atmosphere and oceans, and the history of life. Much of our current understanding of marine oxygenation relies on a traditional single reservoir model, wherein the isotopic composition of marine sulfate is controlled primarily by burial of sedimentary pyrite. Utility of this model is limited, however, during times of persistent marine euxinia, which marks a fundamental decoupling between oxic and anoxic marine sulfur reservoirs. At these times, short-term fluxes that act between the two reservoirs (e.g., sulfate reduction and sulfide oxidation processes) often dominate over the long term fluxes (e.g., weathering and pyrite burial) that control the single reservoir ocean model. Ordovician strata from Argentina, western Newfoundland, and South China illustrate how the marine sulfur cycle is affected by the presence of a persistent euxinic reservoir. Regional euxinic reservoirs remain generally stable from the Floian through the Dapingian, despite evidence for periodic short-term oxygenation events. Dramatic reorganization of the marine sulfur cycle in the early Darriwilian, however, reflects dynamic disequilibrium between oxic and anoxic (euxinic) marine reservoirs, driven by ocean ventilation. Ventilation resulted in a rapid change in the isotopic composition of marine sulfate in surface oceans, and ultimately led to the near depletion of hydrogen sulfide within the anoxic reservoir, as marked by formation of superheavy pyrite. Ventilation occurred coincident with a decline in sea surface temperatures and may represent the onset of climatic change that ultimately led to late Ordovician glaciation.

Through Earth history, atmospheric oxygen has increased from initial values near zero to its present day level of about 21 % by volume; concomitantly, changes in ocean redox conditions have fundamentally altered global biogeochemical cycles. While there is a reasonable understanding of where oxygen history begins and ends, the quantitative timetable of oxygenation that links the endpoints has proven contentious. Equilibrium between marine surface environments and the overlying atmosphere suggests that carbonate-based redox proxies could refine palaeoredox records in time and space. Here we explore the use of Zn/Fe ratios to infer the evolution of atmospheric O2 through time, based on marine carbonate rocks that are well characterised in terms of depositional age, environmental setting, and diagenetic history. While Fe and Zn in the shallow ocean are mainly sourced from hydrothermal inputs, their redox sensitivities differ significantly, so that geological intervals with higher O2 would be characterised by stepped increases in Zn/Fe as preserved in shallow marine carbonates. Therefore, Zn/Fe analyses of ancient carbonates allow us to constrain past atmospheric pO2 levels, providing a secular record of atmospheric O2 over the past 3.5 billion years. In particular, we corroborate an earlier proposal that for much of the Proterozoic Eon, O2 levels were as low as 0.1-1 % of present atmospheric level. We conclude that Zn/Fe in shallow marine carbonate rocks has potential to provide a quantitative tracer for the long-term redox evolution of the oceans and the rise of atmospheric O2.

We assessed dust coverage on the Mars Science Laboratory Mars Hand Lens Imager (MAHLI) and Alpha Particle X-Ray Spectrometer (APXS) calibration targets from 14 MAHLI images acquired at

Marine sulfate ( SO 4 2 − ) is intimately connected to the global carbon and oxygen cycles through its important role as an electron acceptor for the microbial respiration of organic carbon. The biogeochemical feedbacks within the sulfur, carbon, and oxygen cycles may have changed through time, reflecting changes in the concentration of sulfate in the oceans. Unfortunately, there is much uncertainty about the size of the marine sulfate reservoir throughout Earth history. In particular, conflicting estimates for marine sulfate exist during the latest Neoproterozoic, an interval of time associated with striking changes in Earth system evolution and oxidation: published interpretations of fluid inclusion chemistry place sulfate greater than 16 mmol/kg, whereas other interpretations of carbonate-associated sulfate data suggest concentrations less than 2 mmol/kg. Calcium isotope ratios in evaporite successions provide an independent method for deriving semi-quantitative constraints on sulfate concentrations, as well as other properties of seawater chemistry. Here, the calcium isotope behavior of bedded sulfate evaporites from ∼1050 Ma (Baffin and Bylot Islands, Nunavut, Canada), ∼830 Ma (Officer Basin, Western Australia), and ∼545 Ma (South Oman Salt Basin, Sultanate of Oman) are examined. In combination with other geological observations, the results suggest relatively low, millimolal-level sulfate in the latest Mesoproterozoic and a more specific range of 6–10 mmol/kg sulfate during the latest Neoproterozoic. These new constraints suggest that previous interpretations of sulfate concentrations and seawater chemistry need to be revised, opening up new possible solution spaces for the major ion composition of seawater.

Photic zone euxinia (PZE) is a condition where anoxic, H(2)S-rich waters occur in the photic zone (PZ). PZE has been invoked as an impediment to the evolution of complex life on early Earth and as a kill mechanism for Phanerozoic mass extinctions. Here, we investigate the potential application of mercury (Hg) stable isotopes in marine sedimentary rocks as a proxy for PZE by measuring Hg isotope compositions in late Mesoproterozoic (∼1.1 Ga) shales that have independent evidence of PZE during discrete intervals. Strikingly, a significantly negative shift of Hg mass-independent isotope fractionation (MIF) was observed during euxinic intervals, suggesting changes in Hg sources or transformations in oceans coincident with the development of PZE. We propose that the negative shift of Hg MIF was most likely caused by (i) photoreduction of Hg(II) complexed by reduced sulfur ligands in a sulfide-rich PZ, and (ii) enhanced sequestration of atmospheric Hg(0) to the sediments by thiols and sulfide that were enriched in the surface ocean as a result of PZE. This study thus demonstrates that Hg isotope compositions in ancient marine sedimentary rocks can be a promising proxy for PZE and therefore may provide valuable insights into changes in ocean chemistry and its impact on the evolution of life.

Environmental fluctuations are recorded in a variety of sedimentary archives of lacustrine depositional systems. Geochemical signals recovered from bottom sediments in closed-basin lakes are among the most sensitive paleoenvironmental indicators and are commonly used in reconstructing lake evolution. Microbialites (i.e., organosedimentary deposits accreted through microbial trapping and binding of detrital sediment or in situ mineral precipitation on organics [Palaios, 2, 1987, 241]), however, have been largely overlooked as paleoenvironmental repositories. Here, we investigate concentrically laminated mineralized microbialites from Laguna Negra, a high-altitude (4,100 m above sea level) hypersaline, closed-basin lake in northwestern Argentina, and explore the potential for recovery of environmental signals from these unique sedimentary archives. Spatial heterogeneity in hydrological regime helps define zones inside Laguna Negra, each with their own morphologically distinct microbialite type. Most notably, platey microbialites (in Zone 3A) are precipitated by evaporative concentration processes, while discoidal oncolites (in Zone 3C) are interpreted result from fluid mixing and biologically mediated nucleation. This spatial heterogeneity is reflected in petrographically distinct carbonate fabrics: micritic, botryoidal, and isopachous. Fabric type is interpreted to reflect a combination of physical and biological influences during mineralization, and paired C-isotope measurement of carbonate and organic matter supports ecological differences as a dominant control on C-isotopic evolution between zones. Laminae of Laguna Negra microbialites preserve a range of δ13 Ccarb from +5.75‰ to +18.25‰ and δ18 Ocarb from -2.04‰ to +9.28‰. Temporal trends of lower carbon and oxygen isotopic compositions suggest that the influence of CO2 degassing associated with evaporation has decreased over time. Combined, these results indicate that microbialite archives can provide data that aid in interpretation of both lake paleohydrology and paleoenvironmental change.

Craters within Arabia Terra, Mars, contain hundreds of meters of layered strata showing systematic alternation between slope- and cliff-forming units, suggesting either rhythmic deposition of distinct lithologies or similar lithologies that experienced differential cementation. On Earth, rhythmically deposited strata can be examined in terms of stratal packaging, wherein the interplay of tectonics, sediment deposition, and base level (i.e., the position above which sediment accumulation is expected to be temporary) result in changes in the amount of space available for sediment accumulation. These predictable patterns of sediment deposition can be used to infer changes in basin accommodation regardless of the mechanism of deposition (e.g. fluvial, lacustrine, or aeolian). Here, we analyze sedimentary deposits from three craters (Becquerel Crater, Danielson Crater, Crater A) in Arabia Terra. Each crater contains layered deposits that are clearly observed in orbital images. Although orbital images are insufficient to specifically determine the origin of sedimentary deposits, depositional couplets can be interpreted in terms of potential accommodation space available for deposition, and changes in the distribution of couplet thickness through stratigraphy can be interpreted in terms of changing base level and the production of new accommodation space. Differences in stratal packaging in these three craters suggest varying relationships between sedimentary influx, sedimentary base level, and concomitant changes in accommodation space. Previous groundwater upwelling models hypothesize that layered sedimentary deposits were deposited under warm climate conditions of early Mars. Here, we use observed stacking patterns to propose a model for deposition under cold climate conditions, wherein episodic melting of ground ice could raise local base level, stabilize sediment deposition, and result in differential cementation of accumulated strata. Such analysis demonstrates that a first-order understanding of sedimentary deposition and accumulation—despite a lack of textural information that inhibits interpretation of depositional mechanism—can provide insight into potentially changeable depositional conditions of early Mars.

International audience; The Yellowknife Bay formation represents a similar to 5m thick stratigraphic section of lithified fluvial and lacustrine sediments analyzed by the Curiosity rover in Gale crater, Mars. Previous works have mainly focused on the mudstones that were drilled by the rover at two locations. The present study focuses on the sedimentary rocks stratigraphically above the mudstones by studying their chemical variations in parallel with rock textures. Results show that differences in composition correlate with textures and both manifest subtle but significant variations through the stratigraphic column. Though the chemistry of the sediments does not vary much in the lower part of the stratigraphy, the variations in alkali elements indicate variations in the source material and/or physical sorting, as shown by the identification of alkali feldspars. The sandstones contain similar relative proportions of hydrogen to the mudstones below, suggesting the presence of hydrous minerals that may have contributed to their cementation. Slight variations in magnesium correlate with changes in textures suggesting that diagenesis through cementation and dissolution modified the initial rock composition and texture simultaneously. The upper part of the stratigraphy (similar to 1m thick) displays rocks with different compositions suggesting a strong change in the depositional system. The presence of float rocks with similar compositions found along the rover traverse suggests that some of these outcrops extend further away in the nearby hummocky plains.

Oxygenation of Earth's oceans in the Proterozoic was a protracted process that began prior to the Great Oxidation Event (GOE) and culminated in deep ocean ventilation following Neoproterozoic glacial episodes, with both of these major thresholds accompanied by profound changes in the evolution of Earth's biosphere. Our understanding of the redox structure of Mesoproterozoic oceans, however, is considerably less certain. Limited proxy investigations of oceanic redox in the Mesoproterozoic have focused largely on early Mesoproterozoic shelf to basinal settings, with comparatively little attention paid to epeiric sea environments that dominate the late Mesoproterozoic sedimentary record. Here we report multi-proxy shale redox data from epicratonic and pericratonic environments of the 1.1 Ga Atar and El Mreiti Groups, Taoudeni Basin, Mauritania. These strata were deposited across the West African craton during global sea level highstand, and provide insight into the redox structure of Mesoproterozoic epeiric seas. Iron speciation, pyrite sulfur isotope, and trace metal concentration data suggest a shallow chemocline and highly heterogeneous redox conditions, with fundamental heterogeneities in sulfate concentration and the extent and persistence of euxinia between onshore and offshore environments. We suggest that a protracted increase in biospheric oxygenation in the late Mesoproterozoic was accompanied by unstable and heterogeneous redox conditions in shallow, nearshore areas, contributing to the fragmentary pattern of early eukaryotic evolution and diversification.