The microbially mediated replacement of sulfate-bearing evaporites by authigenic carbonate and native sulfur under anoxic conditions is poorly understood. Sulfur-bearing carbonates from the Monte Palco ridge (Sicily) replacing Messinian gypsum were therefore studied to better characterize the involved microorganisms. The lack of (1) sedimentary bedding, (2) lamination, and (3) significant water-column-derived lipid biomarkers in the secondary carbonates implies replacement after gypsum deposition (epigenesis). Allochthonous clasts from the older Calcare di Base and the younger Trubi Formation within these carbonates further evidence epigenetic formation. The sulfur-bearing carbonates are significantly 13C-depleted (δ13C as low as -51‰), identifying methane as a major carbon source. The 18O-enrichment of the carbonates (δ18O as high as 5.4‰) probably reflects precipitation from 18O-enriched fluids transported along adjacent faults or precipitation in a closed system with very little water. Native sulfur with variable 34S-enrichment (δ34S as high as 18.9‰), a relatively small maximum offset (12.3‰) between the sulfate source (gypsum) and native sulfur, and high δ34S values of carbonate-associated sulfate (as high as 61.1‰) suggest a high conversion to native sulfur in a (semi-)closed system, with insignificant sulfate removal. Anaerobic methanotrophic archaea (ANME) apparently affiliated with the ANME-1 clade mediated secondary mineral formation as evidenced by the biomarker inventory, which contains abundant 13C-depleted isoprenoids including sn3-hydroxyarchaeol as the sole hydroxyarchaeol isomer and glycerol dibiphytanyl glycerol tetraethers (GDGTs). A series of various, tentatively identified 13C-depleted non-isoprenoidal dialkyl glycerol diethers (DAGEs), 10me-C16 fatty acid, hydroxy C16 fatty acids, and cyclopropyl-C17:0ω7,8 fatty acid agree with sulfate-reducing bacteria participating in the anaerobic oxidation of methane. Specific conditions during gypsum replacement, unlike those at marine methane seeps, are reflected by the occurrence of 13C-depleted lipids such as lycopane, 9me-C17 fatty acid, and novel DAGEs. As a response to a confined environment probably characterized by high sulfate concentrations, sulfidic conditions, and elevated salinity, ANMEs and sulfate-reducing bacteria apparently adapted their membrane compositions to cope with such stressors.

Lehman Caves is an extensively decorated high desert cave that represents one of the main tourist attractions in Great Basin National Park, Nevada. Although traditionally considered a water table cave, recent studies identified abundant speleogenetic features consistent with a hypogenic and, potentially, sulfuric acid origin. Here, we characterized white mineral deposits in the Gypsum Annex (GA) passage to determine whether these secondary deposits represent biogenic minerals formed during sulfuric acid corrosion and explored microbial communities associated with these and other mineral deposits throughout the cave. Powder X-ray diffraction (pXRD), scanning electron microscopy with electron dispersive spectroscopy (SEM-EDS), and electron microprobe analyses (EPMA) showed that, while most white mineral deposits from the GA contain gypsum, they also contain abundant calcite, silica, and other phases. Gypsum and carbonate-associated sulfate isotopic values of these deposits are variable, with δ34SV-CDT between +9.7‰ and +26.1‰, and do not reflect depleted values typically associated with replacement gypsum formed during sulfuric acid speleogenesis. Petrographic observations show that the sulfates likely co-precipitated with carbonate and SiO2 phases. Taken together, these data suggest that the deposits resulted from later-stage meteoric events and not during an initial episode of sulfuric acid speleogenesis. Most sedimentary and mineral deposits in Lehman Caves have very low microbial biomass, with the exception of select areas along the main tour route that have been impacted by tourist traffic. High-throughput 16S rRNA gene amplicon sequencing showed that microbial communities in GA sediments are distinct from those in other parts of the cave. The microbial communities that inhabit these oligotrophic secondary mineral deposits include OTUs related to known ammonia-oxidizing Nitrosococcales and Thaumarchaeota, as well as common soil taxa such as Acidobacteriota and Proteobacteria. This study reveals microbial and mineralogical diversity in a previously understudied cave and expands our understanding of the geomicrobiology of desert hypogene cave systems.

Abstract The energy transition is an inevitable global development driven by geopolitical, environmental, economic and societal factors. It will fundamentally change how we access energy resources and how we will rebalance the growing demand in critical commodities. The global mobility sector consumes about 2/3 of the world crude oil production, which stands currently at or above 105 million barrels of oil per day (mmbopd). Even a minor reduction, for instance by increasing the electric vehicle fleet, would reduce greenhouse gas emissions but further stress our power grids along with an increasing demand in critical minerals, required by clean tech manufacturing. Industry strategies and technology developments have to address this conundrum. Renewable energy sources already significantly contributing to the domestic electricity grid (13% in US in 2021) but are dominated by intermittent resources like wind and solar energy, whereas dispatchable, clean energy resources are neglected. The potential of dispatchable geothermal energy is undisputed, though challenges in subsurface risk assessment, completion technologies, upfront investments and lengthy permitting processes impact the economic potential of this technology. Lithium is the key critical mineral in clean tech, particularly for batteries in the mobility sector due to its excellent energy density to weight ratio. Environmental impact of invasive lithium mineral mining or large evaporation ponds can be avoided by Direct Lithium Extraction from brines. It is a valuable solution particularly when deployed in proximity to mature hydrocarbon basins, attributed to a wealth in subsurface data, existing infrastructure, and qualified human resources. DLE technologies are facing some challenges in terms of freshwater usage, the application of chemical agents, excessive land usage and reliance on external energy supply. Finally, not every brine chemistry is suitable for the envisaged DLE technology. Direct lithium extraction based on electrodialysis employs ion-selective membranes in a clean, emission free process. The technology is robust and takes advantage of successful membrane applications at multiple desalination plants around the world. Along with battery-grade lithium the electrodialysis produces green hydrogen, outputs freshwater and sequesters CO2 as by-products. When combined with a geothermal power generation the technology uses onsite energy and the produced brine in a clean and environmentally friendly process. Lithium-rich reservoirs with a favorable geothermal signature have been reported from mature hydrocarbon basins across the United States and their direct lithium extraction offers attractive economics, given the growing lithium demand forecasted for the next decades. The operations are 100% green and self-sustainable when combined with novel low enthalpy geothermal power production technology. It opens a new running room to rejuvenate mature hydrocarbon basins into energy super basins.

Organoclastic sulfate reduction and bacterial sulfide oxidation have been suggested to explain the formation of authigenic carbonate and native sulfur replacing gypsum in the Lorca Basin, Spain. To gain more insight into the nature of this replacement, two types of sulfur-bearing carbonate (laminated and brecciated) from the late Miocene Lorca Basin were studied. Petrographic observations revealed that a sulfur-bearing laminated carbonate consists of clay-rich and dolomite-rich laminae with carbonate and native sulfur pseudomorphs after gypsum. Positive δ18Ocarbonate values in the laminae (δ18O = 2.6‰) and lipid biomarkers of halophilic archaea (e.g., extended archaeol) suggest formation under hypersaline conditions. Bacterial sulfate reduction, evidenced by biomarkers such as iso-C15, iso-C16, and iso-C17 fatty acids, produced hydrogen sulfide inducing the abiotic formation of organic sulfur compounds. Gypsum in the laminated carbonate likely dissolved due to undersaturation as evidenced by a low content of carbonate-associated sulfate (3,668 ppm) and 34S-enriched native sulfur (δ34S = 22.4‰), reflecting sulfate limitation. Such 34S-enrichment implies limited fluid flow, which probably restricted the supply of molecular oxygen required for native sulfur formation through oxidation of hydrogen sulfide. Alternatively, sulfate-reducing bacteria may have mediated native sulfur formation directly as a stress response to environmental conditions. The formation of sulfur-bearing calcite in brecciated carbonates is due to post-depositional alteration. Negative δ18O values of the calcite (δ18O = −1.5‰) and a tenfold decrease in carbonate-associated sulfate content (752 ppm) suggest gypsum dissolution and subsequent calcite precipitation from meteoric water. Relatively 34S-depleted native sulfur (δ34S = 13.1‰) leaves it ambiguous whether meteoric water influx could have supplied sufficient molecular oxygen for oxidation of hydrogen sulfide. In case of the brecciated carbonate, methanogenesis, anaerobic oxidation of methane, and bacterial sulfate reduction apparently mediated the formation of secondary minerals as indicated by 13C-depleted lipid biomarkers representative for the respective metabolisms. This study reveals that the conditions and timing of gypsum replacement are variable–taking place 1) during or shortly after gypsum deposition or 2) significantly after sedimentation–and suggests that methanogens in addition to anaerobic methanotrophic archaea and sulfate-reducing bacteria may be involved in the mineral-forming processes in the sedimentary subsurface.

The mid-Cretaceous greenhouse climate was induced by volcanic outgassing and the release of biogenic or thermogenic methane into the ocean-atmosphere system. During this period, major episodes of oceanic anoxic conditions enabled the large scale deposition of marine black shales rich in organic carbon, serving as a source for methane production. Studies on the anaerobic oxidation of methane, the key biogeochemical process at sites where methane is transported toward the seafloor, and its associated authigenic carbonates from mid-Cretaceous strata can contribute to elucidate such extreme climatic conditions. A total of nine layers of authigenic carbonates were recognized in the sequence of mid-Cretaceous inner shelf sedimentary rocks of the Qiangdong section, Gamba area, southern Tibet. In this study, we decipher the mode and causes of carbonate authigenesis by combining field observation, thin section petrography, mineralogy, and carbon and oxygen stable isotope geochemistry. The lowest obtained δ13Ccarb value of −30.5‰ is not low enough to exclude oil compounds as a carbon source, but since other evidence of oil seepage is lacking, methane is the most likely carbon source that was admixed to dissolved inorganic carbon to form authigenic carbonate. Typical seep carbonate phases including 13C depleted matrix micrite, clotted micrite, and banded and botryoidal cement as well as three types of authigenic pyrite comprising framboids, zoned aggregates with radial overgrowths surrounding a framboidal core, and euhedral pyrite crystals indicate the occurrence of methane seepage in the mid-Cretaceous depositional environments. In situ brecciation and subvertical tubular carbonates – the former reflecting rupture caused by local fluid overpressure and the latter interpreted as part of a plumping system – agree with widespread and vigorous seepage. Expanded shallow and deep-water anoxia in combination with low seawater sulfate concentration prior to the oceanic anoxic event 2 (OAE 2) event apparently caused an increased flux of organic matter to the methanogenic zone, stimulating methanogenesis and enabling a higher flux of methane toward the seafloor. In the water column, aerobic oxidation of methane would have enhanced oxygen depletion, thereby contributing to black shale deposition and providing a positive feedback to organic matter preservation and burial. Based on correlation with coeval authigenic carbonate deposits from the Tethyan continental margin, we conclude that organic matter accumulation and sea-level change were the main factors controlling carbonate authigenesis in the mid-Cretaceous.

Magnetic studies of methanic sediments focus mainly on magnetic iron sulfide (greigite, 3C pyrrhotite) formation and magnetic iron oxide (magnetite, titanomagnetite) dissolution, which mainly result from the release of hydrogen sulfide during sulfate-driven anaerobic oxidation of methane. In some instances, authigenic fine-grained magnetite within methanic environments is recognized from magnetic parameters, but the mechanisms for explaining its occurrence remain unclear. We report a novel authigenic nanoscale magnetite source in methanic marine sediments. The magnetite occurs in large concentrations in multiple horizons in a 230-m long sediment core with gas hydrate-bearing intervals. In contrast to typical biogenic magnetite produced by magnetotactic bacteria and dissimilatory iron-reducing bacteria, most particles have sizes of 200-800 nm and many are aligned in distinctive structures that resemble microbial precipitates. This new type of magnetite is interpreted to be a by-product of microbial iron reduction within methanic sediments. It will record younger paleomagnetic signals than surrounding sediments, which is important for paleomagnetic interpretations in methanic sediments.

(MTB) and the other by dissimilatory iron-reducing bacteria (DIRB) (Moskowitz, 1995; Roberts, 2015). Intracellular magnetite produced by MTB has well defined sizes, morphologies, chain arrangements, and stoichiometries (Devouard et al., 1998; Kopp and Kirschvink, 2008). The magnetic nanoparticulate remains of MTB are preserved post-mortem as magnetofossils and are found in diverse sedimentary environments We report a novel authigenic nanoscale magnetite source in marine methane seep sediments. The magnetite occurs in large concentrations in multiple horizons in a 230 m sediment core with gas hydrate?bearing intervals. In contrast to typical biogenic magnetite produced by magnetotactic bacteria and dissimilatory iron-reducing bacteria, most particles have sizes of 200?800 nm and many are aligned in distinctive structures that resemble microbial precipitates. The magnetite is interpreted to be a byproduct of microbial iron reduction within methanic sediments with rapidly changing redox conditions. Iron sulfides that accumulated at a shallow sulfate-methane transition zone were oxidized after methane seepage intensity decreased. The alteration process produced secondary iron (oxyhydr)oxides that then became a reactive iron source for magnetite authigenesis when methane seepage increased again. This interpretation is consistent with 13C depletion in coexisting carbonate nodules. The authigenic magnetite will record younger paleomagnetic signals than surrounding sediments, which is important for paleomagnetic interpretations in seep systems. The microbial and possibly abiotic processes that caused these magnetic minerals to form at moderate burial depths remain to be determined.

ABSTRACT The thickness of microbialite crusts in Holocene barrier and fringing reefs of Bora Bora was quantified in drill cores from windward and leeward settings to decipher possible spatial and temporal patterns as well as controlling environmental factors. Based on the analysis of 145 occurrences in nine rotary cores, microbialite thickness ranges from 0.1–11.0 cm with an average value of 1.97 cm (SD = 2.47). Microbialites occur only from 9.5–5.6 ka corresponding to a period of rapid sea-level rise and reef accretion in the early Holocene. However, there is no statistically significant correlation between microbialite thickness and reef accretion rate. Also, there is no correlation between microbialite abundance and age. The upcore increase in microbialite abundance, however, suggests that time available for carbonate accretion in shallow water plays a role in microbialite formation. Crust thickness is greater on windward as compared to leeward fringing reef settings indicating that flushing of pore space is a likely factor controlling microbialite accretion. Other environmental factors potentially being responsible for the Holocene decrease in microbialite abundance include climate, i.e., decreasing temperatures and precipitation (supporting nutrient input by runoff) as well as decreasing seawater alkalinity. At the mesoscale, structureless and laminated microbialites are by far the most common types. Coated debris, boring infill, and digitate types are less common. Textures at the microscale, including laminated, clotted, and peloidal, do not necessarily match mesoscale textures. The Bora Bora microbialites consist in more or less equal parts of high-magnesium calcite and aragonite. The δ13C values range from +3.0 to +4.1‰ and the δ18O from -0.8 to +0.1‰. The contents of easy soluble sulfate (ESS) and carbonate associated sulfate (CAS) are relatively high. The δ18OCAS (+11.0 to +12.7‰) and δ34SCAS values (+21.9 to +23.6‰) exceed the seawater sulfate standard NBS-127 value and are in the same range as observed in other cryptic, Holocene reefal microbialites. The Bora Bora microbialites contain lipid biomarkers derived from sulfate-reducing bacteria (2–8 wt%), marine plankton, land plants, and unspecified bacteria. The former include branched, short-chain fatty acids and terminally branched fatty acids, whereby iso-fatty acids are more abundant than anteiso-fatty acids. Other compounds with terminally branched alkyl chains include iso- and anteiso-C15 and -C17 alcohols, which are interpreted as degradation products of monoalkyl glycerol ethers (MAGE). Collectively, the organic and inorganic geochemical data together with the sedimentological and mineralogical data suggest that sulfate-reducing bacteria were involved in microbialite development. The temporal and spatial distribution patterns suggest that factors such as exposure to waves and currents, time, nutrient availability, alkalinity, and climate play important roles, however, more quantitative data from other occurrences are needed to be able to better discriminate among them.

Trace metals have been successfully used to reconstruct geochemical seawater conditions of both modern and ancient environments. The majority of these efforts have been limited to marine shales, with little work on carbonate systems. Applying similar methods of trace metal analysis on carbonate-dominated rocks may provide valuable insight into the paleoseawater chemistry, such as redox state, and productivity, of ancient carbonate systems. This study evaluates the application of trace metals as paleoproxies in carbonate rocks. Middle-ramp wackestones to grainstones from the "Mississippian Limestone" in the Midcontinent were analyzed using inductively-coupled plasma mass spectrometry (ICP-MS) for both the carbonate-fraction and the bulk-fraction trace metal content. Our data show that productivity proxies, such as Cd and P, are captured within the carbonate-fraction and may reflect seawater chemistry of the system. High Cd, and moderate bionutrient (P, Ni, Zn) enrichments indicate primary productivity in the system, though it is difficult to quantify to what extent. Vanadium, Cr, U, and Mo appear to be primarily associated with the bulk-fraction content and correlate well with Al content, indicating a detrital origin. Furthermore, V, U, and Mo show no significant enrichments, and Mo/Fe ratios correlate with those of shales from a modern oxic shelf. This suggests that anoxic or euxinic conditions in the water column were not present. Trace metal content of carbonate rocks have the potential to be used in paleoenvironmental reconstruction of carbonate systems, though challenges exist such as the lack of comparable carbonate trace metal data, bias of trace metal incorporation pathways into carbonates, and diagenetic alteration.

Large native (i.e., elemental) sulfur deposits can be part of caprock assemblages found on top of or in lateral position to salt diapirs and as stratabound mineralization in gypsum and anhydrite lithologies. Native sulfur is formed when hydrocarbons come in contact with sulfate minerals in presence of liquid water. The prevailing model for native sulfur formation in such settings is that sulfide produced by sulfate-reducing bacteria is oxidized to zero-valent sulfur in presence of molecular oxygen (O-2). Although possible, such a scenario is problematic because: (1) exposure to oxygen would drastically decrease growth of microbial sulfate-reducing organisms, thereby slowing down sulfide production; (2) on geologic timescales, excess supply with oxygen would convert sulfide into sulfate rather than native sulfur; and (3) to produce large native sulfur deposits, enormous amounts of oxygenated water would need to be brought in close proximity to environments in which ample hydrocarbon supply sustains sulfate reduction. However, sulfur stable isotope data from native sulfur deposits emplaced at a stage after the formation of the host rocks indicate that the sulfur was formed in a setting with little solute exchange with the ambient environment and little supply of dissolved oxygen. We deduce that there must be a process for the formation of native sulfur in absence of an external oxidant for sulfide. We hypothesize that in systems with little solute exchange, sulfate-reducing organisms, possibly in cooperation with other anaerobic microbial partners, drive the formation of native sulfur deposits. In order to cope with sulfide stress, microbes may shift from harmful sulfide production to non-hazardous native sulfur production. We propose four possible mechanisms as a means to form native sulfur: (1) a modified sulfate reduction process that produces sulfur compounds with an intermediate oxidation state, (2) coupling of sulfide oxidation to methanogenesis that utilizes methylated compounds, acetate or carbon dioxide, (3) ammonium oxidation coupled to sulfate reduction, and (4) sulfur comproportionation of sulfate and sulfide. We show these reactions are thermodynamically favorable and especially useful in environments with multiple stressors, such as salt and dissolved sulfide, and provide evidence that microbial species functioning in such environments produce native sulfur. Integrating these insights, we argue that microbes may form large native sulfur deposits in absence of light and external oxidants such as O-2 , nitrate, and metal oxides. The existence of such a process would not only explain enigmatic occurrences of native sulfur in the geologic record, but also provide an explanation for cryptic sulfur and carbon cycling beneath the seabed.

Microbial life below the seafloor has changed over geological time, but these changes are often not obvious, as they are not recorded in the sediment. Sulphur (S) isotope values in pyrite extracted from a Plio- to Holocene sequence of the Peru Margin (Ocean Drilling Program, ODP, Site 1229) show a down-core pattern that correlates with the pattern of carbon (C) isotopes in diagenetic dolomite. Early formation of the pyrite is indicated by the mineralogical composition of iron, showing a high degree of pyritization throughout the sedimentary sequence. Hence, the S-record could not have been substantially overprinted by later pyrite formation. The S- and C-isotope profiles show, thus, evidence for two episodes of enhanced microbial methane production with a very shallow sulphate-methane transition zone. The events of high activity are correlated with zones of elevated organic C content in the stratigraphic sequence. Our results demonstrate how isotopic signatures preserved in diagenetic mineral phases provide information on changes of past biogeochemical activity in a dynamic sub-seafloor biosphere.

Since the advent of modern computing, geochemists have increasingly relied on computers to garner efficiencies in calculations, data analysis, and data presentation. Entirely new fields, such as Monte Carlo-based simulation and geochemical modeling, have developed under this paradigm. With continued growth in computing power, machine learning has become an increasingly popular tool in aqueous geochemistry. However, continued reliance on algorithms to perform mathematical calculations can lead to paths of not understanding how to properly prepare information for models or not the reasons behind apparent patterns in the output. Machine learning algorithms can be heavily impacted by what variables are chosen for the model and how data are pre-processed, including handling of missing and censored values (e.g., above or below a detection limit). We propose an approach of parsimonious variable selection, based partially on the signal-to-noise ratio, and suggest and discuss strategies for handling missing and censored data. An example of unsupervised machine learning, using emergent self-organizing map analysis, is applied to water from oil and gas wells in the northern U.S. Gulf Coast Basin, whose composition is controlled by different processes and is derived from various origins. Findings from this investigation suggest five groups of water samples are present, two of which were not identified using conventional data analysis methods. One notable result is that brines derived from seawater evaporation, presumably waters from which the Jurassic Louann salt precipitated, have migrated upward into shallower reservoirs across the study area. This work demonstrates that focus on understanding data quality and exercises to better interpret the output from numerical models continue to be critical skills to further take advantage of applying machine learning to geochemistry.

The Guaymas Basin spreading center, at 2000 m depth in the Gulf of California, is overlain by a thick sedimentary cover. Across the basin, localized temperature anomalies, with active methane venting and seep fauna exist in response to magma emplacement into sediments. These sites evolve over thousands of years as magma freezes into doleritic sills and the system cools. Although several cool sites resembling cold seeps have been characterized, the hydrothermally active stage of an off-axis site was lacking good examples. Here, we present a multidisciplinary characterization of Ringvent, an ~1 km wide circular mound where hydrothermal activity persists ~28 km northwest of the spreading center. Ringvent provides a new type of intermediate-stage hydrothermal system where off-axis hydrothermal activity has attenuated since its formation, but remains evident in thermal anomalies, hydrothermal biota coexisting with seep fauna, and porewater biogeochemical signatures indicative of hydrothermal circulation. Due to their broad potential distribution, small size and limited life span, such sites are hard to find and characterize, but they provide critical missing links to understand the complex evolution of hydrothermal systems.