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Geochemistry of Diagenetic Fluids and Sedimentary Protolith of Gale Crater

The geochemical composition of the sediments of Gale crater can be modeled using two component mixing between a weathered basalt and a sulfate rich endmember. This suggests that the amount of in-situ weathering occurring after deposition was minimal, and most of the variation in weathering indi-ces can be explained simply through addition of Ca-sulfate minerals during diagenesis. Evidence for burial of Gale sediments can be explained through the pres-ence of large ice/dust deposits.

Niles, P. B.↗

Untangling Source-To-Sink Geochemical Signals in a ~3.5 Ga Martian Lake: Sedimentology and Geochemistry of the Murray Formation

Sedimentary rocks are historical archives of planetary surface processes; their grains, textures, and chemistry integrate the effects of source terrains, paleoclimatic conditions, weathering and transport processes, authigenic mineral precipitation, and diagenesis, which records groundwater chemistry through time. “Source to Sink” basin analysis seeks to constrain the influence of each of these different signals through sedimentary and geochemical analyses. Here, we use Mars Science Laboratory (MSL) Curiosity rover images and geochemical and mineralogical data from a traverse across a portion of the Murray formation—the lowermost unit exposed in the Gale crater central mound—to begin to constrain the aspects of the source to sink system that formed this Martian mudstone between 3.7 and 3.2 Ga.

Siebach, K. L.↗

Glen Torridon Mineralogy and the Sedimentary History of the Clay Mineral Bearing Unit

Clay minerals are common in ancient terrains on Mars and their presence at the surface alludes to aqueous processes in the Noachian to Early Hesperian (>3.5 Ga). Gale crater was selected as Curiosity’s landing site largely because of the identification of clay mineral rich strata from orbit. On Earth, the types of clay minerals (i.e., smectites) identified in Gale crater are typically juvenile weathering products that ultimately record the interaction between primary igneous minerals with the hydrosphere, atmosphere, and biosphere. Trioctahedral and dioctahedral smectite were identified by Curiosity in units stratigraphically below the Clay Mineral-Bearing Unit (CBU) identified from orbit. Compositional and sedimentological data suggest the smectite formed via authigenesis in a lake environment and may have been altered during early diagenesis. The CBU is stratigraphically equivalent to a hematite-rich unit to the north and stratigraphically underlies sulfate-rich units to the south, suggesting a dynamic environment and evolving history of water in the ancient Gale crater lake. Targeting these clay mineral rich areas on Mars with rover missions provides an opportunity to explore the aqueous and sedimentary history of the planet.

Thorpe, M. T.↗

Automated Identification and Differentiation of Spectrally Similar Hydrothermal Minerals on Mars

Early telescopic observations corroborated hydration related absorptions on Mars in the infrared. Images from the Viking missions led to speculation of hydrothermal alteration and were followed by two missions which mapped the spatial variability of the ~ 3 μm hydration feature. Since then, the Compact Reconnaissance Imager for Mars (CRISM) has provided high spatial resolution (up to 18m) spectral identification of a suite of hydrothermal and diagenetic minerals which have illuminated a range of formation mechanisms. Presence/absence and spatial segregation or mixing of minerals like prehnite, epidote, chlorite amphiboles, and mixed-layer Fe/Mg smectite-chlorite provide valuable evidence for the geologic setting of deposits on Earth, and these phases are often used as temperature and aqueous chemistry indicators in terrestrial systems. Mapping the distribution of these phases will help to answer whether Mars had widespread conditions favorable for low-grade metamorphism and diagenesis, or only focused hydrothermal systems in areas of high heat flow. Further characterizing the chemistry and structure of these phases will then help to answer how most of the widespread Fe/Mg phyllosilicates formed, further defining early geochemical cycling and climate. A fully automated approach for accurate mapping of important hydrothermal mineral phases on Mars has been a challenge. Due to overlapping features in the M-OH region (~2.2-2.4 μm), the strongest absorption features of chlorite, prehnite, and epidote in the short-wave infrared are difficult to distinguish from one another and from the most commonly occurring hydrated silicates on Mars, Fe/Mg smectites. Weaker absorptions are present in both prehnite and epidote which help to distinguish them from chlorite and smectites, but their relative strength in the presence of noise and spatial mixing is often too low to confidently identify them without the noise suppression and feature enhancement methods described here. The spectral signatures of mixed-layer Fe/Mg smectite-chlorite and partially chloritized Fe/Mg smectites have not yet been adequately assessed. Here we evaluate the effectiveness of two empirical and statistical methods for identifying and differentiating these phases using CRISM data.

Rasmussen, B. P.↗

Sediment Sorting and Rounding in a Basaltic Glacio-Fluvio-Aeolian Environment: Ϸhórisjökull Glacier, Iceland

Sediments and sedimentary rocks preserve a rich history of environment and climate. Identifying these signals requires an understanding of the physical and chemical processes that have affected sedimentary deposits [1]. Such processes include sorting and rounding during transport and chemical alteration through weathering and diagenesis. Although these processes have long been studied in quartz-dominated sedimentary systems [2], a lack of studies of basaltic sedimentary systems limits our interpretations of the environment and climate where mafic source rocks dominate, such as on Mars [3,4]. As part of the SAND-E: Semi-Autonomous Navigation for Detrital Environments project [5], which uses robotic operations to examine physical and chemical changes to sediments in basaltic glacio-fluvialaeolian environments, this research studies changes in sorting and rounding of fluvial-aeolian sediments along a glacier-proximal-to-glacier-distal transect in the outwash-plain of the Ϸόrisjökull glacier in SW Iceland (Fig. 1)

Mason, K. G.↗

Mineralogy of Vera Rubin Ridge from the Mars Science Laboratory CheMin Instrument

Vera Rubin ridge (VRR) is an erosion-resistant feature on the northwestern slope of Mount Sharp in Gale crater, Mars, and orbital visible/short-wave infrared measurements indicate it contains red-colored hematite. The Mars Science Laboratory Curiosity rover performed an extensive campaign on VRR to study its mineralogy, geochemistry, and sedimentology to determine the depositional and diagenetic history of the ridge and constrain the processes by which the hematite could have formed. X-ray diffraction (XRD) data from the CheMin instrument of four samples drilled on and below VRR demonstrate differences in iron, phyllosilicate, and sulfate mineralogy and hematite grain size. Hematite is common across the ridge, and its detection in a gray-colored outcrop suggested localized regions with coarse-grained hematite, which commonly forms from warm fluids. Broad XRD peaks for hematite in one sample below VRR and the abundance of FeOT in the amorphous component suggest the presence of nano-crystalline hematite and amorphous Fe oxides/oxyhydroxides. Well-crystalline akaganeite and jarosite are present in two samples drilled from VRR, indicating at least limited alteration by acid-saline fluids. Collapsed nontronite is present below VRR, but samples from VRR contain phyllosilicate with d(001) = 9.6 Å, possibly from ferripyrophyllite or an acid-altered smectite. The most likely cementing agents creating the ridge are hematite and opaline silica. We hypothesize late diagenesis can explain much of the mineralogical variation on the ridge, where multiple fluid episodes with variable pH, salinity, and temperature altered the rocks, causing the precipitation and crystallization of phases that are not otherwise in equilibrium.

E. B. Rampe↗

Recent Mineralogical Discoveries in Gale Crater, Mars from the CheMin XRD Instrument, Demonstrating a Watery Past

Curiosity landed in Gale crater August 2012 and has traversed (~27 km) sedimentary rocks that comprise a ~5 km-high mound, informally known as Mount Sharp, to investigate depositional/diagenetic environments and potential habitability. VSWIR spectra revealed the lowermost slopes of Mount Sharp contain mineral assemblages that are indicative of water-rock interactions (1-3), with sulfate-bearing units overlying phyllosilicate-bearing units. This mineralogical succession may mark the beginning of the transition from a relatively wet/warm to a very dry/cold Mars (e.g., 1, 4). Thirty-four powdered rock samples have been analyzed by the CheMin XRD instrument and mineralogical results from the first 6 years of the mission are reviewed in [5]. Here we describe the mineralogical diversity observed over the most recent 4 years. Sediments in the Vera Rubin Ridge (VRR) and Glen Torridon (GT) region were deposited in a lacustrine-fluvial environment and are syndepositional. The mineralogy suggests post-depositional fluid-rock interaction. Differences in mineralogy could have been the result of silica-poor, briny groundwater that destabilized smectite and precipitated hematite in VRR [6]. Other hypotheses include lake water-groundwater mixing or diagenesis driven by deeply sourced fluids altering smectite to precipitate hematite and amorphous silica. Preserved bedforms in the clay-sulfate transition region indicate a change from lacustrine-fluvial to aeolian depositional environments. Mineralogical changes include the identification of goethite along with the disappearance of phyllosilicate. The absence of crystalline Mg-sulfate in drilled samples from this transition region may mean that: 1) Sulfates are concentrated in secondary concretions not sampled by Curiosity’s drill, or 2) Sulfate components are either X-ray amorphous or if crystalline, became amorphous in the relatively low-humidity environment of the rover. Continued exploration of sulfate-rich rocks will elucidate this environmental transition above the phyllosilicate-rich sediments.

V M Tu↗

The Role of Olivine in Fe-Carbonate Formation in Gale Crater, Mars

Carbonates have been identified in remote sensing datasets, martian meteorites, and in-situ with rovers at Gale and Jezero craters. In Gale crater, traces of carbonate have been found by the SAM instrument throughout the Mars Science Laboratory mission, e.g., at Rocknest and Pahrump Hills, with models for carbonate formation at Pahrump Hills explored by [9]. Further up-section, CheMin data of clay-rich Glen Torridon (GT) samples show that five out of seven drill samples from GT contain Fe-carbonate alongside phyllosilicates. The GT sediments were deposited in a lacustrine environment and subsequently underwent multiple episodes of diagenesis. In this work, we explore the role of olivine in the formation of carbonates by modelling the interaction of different martian olivines with a previously modeled Gale groundwater. We then explore the incongruent dissolution of host rocks within the GT sediments by mixing olivine with quantities of the Kilmarie drill sample chemical composition as the reactant rock.

S M R Turner↗

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

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

Kristen A Bennett↗

Diverse organic molecules on Mars revealed by the first SAM TMAH experiment

The search for organic matter on Mars has rapidly evolved in the past decade with simple aromatic, S-heterocycles, and aliphatic organic molecules detected in Gale crater. We report the in situ detection of >20 organic molecules from clay-bearing sandstones in the ~3.5-billion-year-old Knockfarrill Hill member of Glen Torridon, Gale crater, by the Sample Analysis at Mars instrument suite onboard the Curiosity rover. These molecules were liberated by the onboard tetramethylammonium hydroxide wet chemistry experiment. Diverse thermochemolysis products, including benzothiophene, methyl benzoate, and single and dicyclic aromatic molecules were released and detected by evolved gas analysis and gas chromatography-mass spectrometry. Results indicate the experiment successfully released molecules preserved in ancient macromolecular or free organic matter within Martian bedrock despite ~3.5 billion years of diagenesis and radiation exposure.

Amy J Williams↗

Intact archeological human bones and age at death studied with transmission x–ray diffraction and small angle x–ray scattering

In this work, high-energy, wide-angle x-ray scattering (WAXS, x-ray diffraction) and small-angle x-ray scattering (SAXS) were used to study intact human second metacarpal bones (mc2) from two UK archeological sites. A novel method correcting for irregular mass distribution was applied in these transmission geometry experiments done at beamline 1-ID of the Advanced Photon Source. The authors asked whether there were age-at-death-related changes in carbonated apatite (cAp) lattice parameters and whether SAXS could detect collagen D-period peaks in the archeological mc2. For each of the two sites, Ancaster and Wharram Percy in England, six female mc2s were studied; for each site, two were from each of three age-at-death cohorts (young, 18-29 years; middle, 30-49 years; old >= 50 years) along with a modern control mc2. The Rietveld method was applied to the WAXS patterns to provide precise lattice parameter values. The cAp lattice parameters did not correlate with age-at-death estimated from dental wear. From WAXS and the 00.2 diffraction peak widths, four archeological mc2s possessed coherently scattering domain lengths (crystallite c-axis sizes) that matched that of the modern mc2; SAXS revealed the same four archeological mc2 had D-period peak intensities equivalent to that of the modern mc2. The other eight archeological mc2s had significantly larger crystallite sizes (than the modern mc2) and weak or absent D-period peaks, differences attributed to diagenetic changes. Based on these data, the authors suggest that WAXS 00.2 peak width and SAXS D-period peak intensity can be used with intact bones to select those likely to retain largely unaltered tissue nanostructure, which might be required for other analyses. Taken as a whole, the results suggest detecting age-related deterioration in nanostructural features may be difficult in bone showing significant bioerosion.

59 BASIC BIOLOGICAL SCIENCES↗

Potential for constraining sequence stratigraphy and cycle stratigraphy with U-Pb dating of carbonates

Studies of sequence stratigraphy and cycle stratigraphy in carbonate formations increasingly improve our understanding of depositional systems and basinal to global correlations. However, there is still a scarcity of dated sequences to determine the time length of sequences and cycles. Furthermore, the durations of sequences and cycles provide tests of the processes that produce them. Poor age resolution mostly stems from the lack of recognizable volcanic ash deposits in many sections. Through continuing advances in analytical techniques and approaches to sampling, the current state of Usingle bondPb dating of carbonate sedimentary rocks provides opportunities to fill in age gaps. The approach should build on well-constrained 3-dimensional stratigraphic architectures and diagenetic stratigraphies.

58 GEOSCIENCES↗

Early diagenetic processes in an iron-dominated marine depositional system

The early diagenetic interplay between reactive iron, sulfur, and organic matter in the bathymetrically isolated Santa Monica Basin (SMB) sediments are investigated in this study. Here, we explore solid-phase and porewater profiles from the basin, supplemented with a transect from 71 to 907 m water depth that includes oxygenated (>60 μM O 2 ) bottom waters near the coast and oxygen-deficient waters (~4 µM O 2 ) in the basin. The geochemical data of the basin sediments are further scrutinized by means of reactive transport modeling. The results show that the basin sediments do not follow the traditional geochemical signatures of oxygen-deficient settings. A lack of dissolved sulfide accumulation and sulfurized iron persists despite the sediments being deposited under reducing conditions (without bioturbation/bioirrigation), strong organic carbon input (TOC up to 5.0 wt%), and active dissimilatory sulfate reduction. Not only did we find an exceptional enrichment in highly reactive Fe in the surface sediments (~45 % of total Fe), but the enrichment of reactive Fe, including ferrihydrite, persists downcore and coexists with high levels of dissolved Fe. The enhanced preservation of Fe oxides and lack of iron-sulfide precipitation is in part explained by detection via Mössbauer spectra of iron oxides bounded to organic matter (Fe[III]-OM coprecipitates). The modeled Fe budget shows that most of the Fe oxides in the surface sediments are internally recycled by upward diffusion and subsequent oxidation of Fe 2+ . Sulfide oxidation coupled to Fe reduction effectively precludes sulfide accumulation while enhancing build-up of dissolved Fe, fueling the Fe cycle within the first 5 cm depth. Continuous reoxidation of Fe 2+ enhances the formation of Fe(III)-OM coprecipitates, limiting the amount of reactive organic matter. In the unavailability of labile organic matter, other than within the uppermost layers, the organic-rich sediment profiles are dominated by Fe cycling that limits the production and preservation of sulfides and enhances the preservation of Fe oxides and organic carbon. Finally, this study highlights key local controls on Fe availability in marginal basins and describes an intricate biogeochemical C-Fe-S cycling in modern and possibly ancient marine systems with important implications for Fe availability in the marine realm.

58 GEOSCIENCES↗

Boron adsorption in clay minerals: Implications for martian groundwater chemistry and boron on Mars

Boron has been detected on Mars in calcium-sulfate veins found within clay mineral rich rocks on Mars by the Mars Science Laboratory (MSL) Curiosity rover using Laser Induced Breakdown Spectroscopy (LIBS) analysis. Borates play a vital role in stabilizing ribose on Earth and has been suggested as a key requirement for life. Borate ions readily adsorb to phyllosilicate clay minerals. The discovery of boron on Mars in proximity to phyllosilicate-bearing bedrock may have strong implications for potential past prebiotic conditions on Mars. In this study we generated a suite of clay minerals with adsorbed borate, including both typical terrestrial clay minerals (montmorillonite) and Mars-analog clay minerals (nontronite, saponite, griffithite), to understand controls on borate adsorption and to analyze with LIBS to compare with MSL data. Clay minerals were subjected to mineralogical and chemical analysis before and after adsorption. Adsorption analysis revealed that the Mars analog clay minerals adsorbed less boron than terrestrial counterparts, but within comparable amounts to those detected on Mars and in meteorites. Post-adsorption analysis by X-ray diffraction (XRD) revealed slight changes in the interlayer spacing of many of the clay minerals. Based on the adsorption analysis of the Mars-analog clay minerals, phyllosilicate-bearing bedrock in Gale crater may contain up to 90-110 ppm B. A series of borate-enriched samples were created for analysis of LIBS spectra from ChemCam on the Curiosity rover and SuperCam on the Perseverance Rover. Finally, the results of this study may provide insight into martian groundwater geochemistry processes and the mobility of a key molecule connected with life.

58 GEOSCIENCES↗

Vertical effective stress and temperature as controls of quartz cementation in sandstones: Evidence from North Sea Fulmar and Gulf of Mexico Wilcox sandstones

Here we present quantitative petrographic data, high spatial resolution oxygen isotope analyses of quartz cement, basin modelling and a kinetic model for quartz precipitation for two Paleocene-Eocene Wilcox Group sandstones from Texas and two Jurassic Fulmar Formation sandstones from the Central North Sea. At each location, one sandstone has been buried to ca. 145 °C and one to ca. 185 °C. A key difference between the Wilcox and Fulmar burial histories is that the Wilcox sandstones are currently at higher vertical effective stresses and, from basin modelling studies, have been subjected to generally higher vertical effective stresses through their burial history. The amounts of quartz cement in the Wilcox sandstones are between 12 and 18%, and between 2 and 6% in the Fulmar sandstones. High-spatial-resolution oxygen isotope data obtained from the quartz cements suggest temperature ranges for quartz precipitation from 60 to 80 °C to values approaching maximum burial temperature. Factors such as grain coatings or the timing of petroleum emplacement cannot explain the differences in the amounts of quartz cement. Petrographic data show that most of the silica for quartz cement can be derived from intergranular pressure dissolution. Although the sample set is small, we interpret the results to suggest that the differences in quartz cementation in Fulmar and Wilcox sandstones can be explained better by differences in their vertical effective stress history than their temperature history; in this case, the supply of silica rather than the precipitation of quartz becomes an important control on the rate and extent of cementation.

58 GEOSCIENCES↗

Illitization in the Mt. Simon Sandstone, Illinois Basin, USA: Implications for carbon dioxide storage

Clay mineral cementation is one of the most important controls on sandstone reservoir properties. Here, in this paper, the diagenetic history of the Mt. Simon reservoir complex is studied to reveal the origin, timing, and controls of illitization. Samples of sandstone and shale from Mt. Simon reservoir complex were acquired from the Illinois Basin–Decatur Project (IBDP), a CO 2 storage demonstration project in the central Illinois Basin. Petrographic, SEM, TEM, XRD analyses and K/Ar age dating were completed to identify the major detrital and diagenetic components of the samples and reveal illite to be the major clay component in all samples. Illitic clay coatings in the lower Mt. Simon reservoir are identified as a major control on reservoir properties by inhibiting major precipitation of authigenic quartz during illitization, resulting in highly permeable sandstone, essential for CO 2 storage. The coating box-work morphology and mineralogy are indicative of a detrital smectite origin with subsequent illite growth associated with feldspar dissolution and kaolinite alteration. The mineralogy of bulk material and separate grain size fractions (2–0.6 μm; 0.6–0.2 μm; < 0.2 μm) with illite polytypes 2M 1 , 1M, and 1M d were quantified and age dated via 40 K- 40 Ar methods. The shales or reservoir seals contain the highest proportions of detrital illite with illite in the lower Mt. Simon Sandstone reservoir identified as solely diagenetic. Two major events of illitization are identified throughout the Mt. Simon with more porous reservoir rock exhibiting the older event from approximately 360 to 315 Ma and tighter sandstone units with reservoir properties too low to be considered reservoir exhibiting illite dates from 250 to 220 Ma. This partitioning of illitization is attributed to varied mineralogy controlled by depositional changes and evolution of the greater basin.

58 GEOSCIENCES↗

Overview of the Morphology and Chemistry of Diagenetic Features in the Clay-Rich Glen Torridon Unit of Gale Crater, Mars

The clay-rich Glen Torridon region of Gale crater, Mars, was explored between sols 2300 and 3007. Here, we analyzed the diagenetic features observed by Curiosity, including veins, cements, nodules, and nodular bedrock, using the ChemCam, Mastcam, and Mars Hand Lens Imager instruments. We discovered many diagenetic features in Glen Torridon, including dark-toned iron- and manganese-rich veins, magnesium- and fluorine-rich linear features, Ca-sulfate cemented bedrock, manganese-rich nodules, and iron-rich strata. We have characterized the chemistry and morphology of these features, which are most widespread in the higher stratigraphic members in Glen Torridon, and exhibit a wide range of chemistries. These discoveries are strong evidence for multiple generations of fluids from multiple chemical endmembers that likely underwent redox reactions to form some of these features. In a few cases, we may be able to use mineralogy and chemistry to constrain formation conditions of the diagenetic features. For example, the dark-toned veins likely formed in warmer, highly alkaline, and highly reducing conditions, while manganese-rich nodules likely formed in oxidizing and circumneutral conditions. We also hypothesize that an initial enrichment of soluble elements, including fluorine, occurred during hydrothermal alteration early in Gale crater history to account for elemental enrichment in nodules and veins. The presence of redox-active elements, including Fe and Mn, and elements required for life, including P and S, in these fluids is strong evidence for habitability of Gale crater groundwater. Hydrothermal alteration also has interesting implications for prebiotic chemistry during the earliest stages of the crater’s evolution and early Mars.

58 GEOSCIENCES↗