Sulfate Burial Constraints on the Phanerozoic Sulfur Cycle

The sulfur cycle influences the respiration of sedimentary organic matter, the oxidation state of the atmosphere and oceans, and the composition of seawater. However, the factors governing the major sulfur fluxes between seawater and sedimentary reservoirs remain incompletely understood. Using macrostratigraphic data, we quantified sulfate evaporite burial fluxes through Phanerozoic time. Approximately half of the modern riverine sulfate flux comes from weathering of recently deposited evaporites. Rates of sulfate burial are unsteady and linked to changes in the area of marine environments suitable for evaporite formation and preservation. By contrast, rates of pyrite burial and weathering are higher, less variable, and largely balanced, highlighting a greater role of the sulfur cycle in regulating atmospheric oxygen

Biologically Induced Initiation of Neoproterozoic Snowball-Earth Events

The glaciations of the Neoproterozoic Era (1,000 to 542 MyBP) were preceded by dramatically light C isotopic excursions preserved in preglacial deposits. Standard explanations of these excursions involve remineralization of isotopically light organic matter and imply strong enhancement of atmospheric $CO_2$ greenhouse gas concentration, apparently inconsistent with the glaciations that followed. We examine a scenario in which the isotopic signal, as well as the global glaciation, result from enhanced export of organic matter from the upper ocean into anoxic subsurface waters and sediments. The organic matter undergoes anoxic remineralization at depth via either sulfate- or iron-reducing bacteria. In both cases, this can lead to changes in carbonate alkalinity and dissolved inorganic pool that efficiently lower the atmospheric $CO_2$ concentration, possibly plunging Earth into an ice age. This scenario predicts enhanced deposition of calcium carbonate, the formation of siderite, and an increase in ocean pH, all of which are consistent with recent observations. Late Neoproterozoic diversification of marine eukaryotes may have facilitated the episodic enhancement of export of organic matter from the upper ocean, by causing a greater proportion of organic matter to be partitioned as particulate aggregates that can sink more efficiently, via increased cell size, biomineralization or increased C∶N of eukaryotic phytoplankton. The scenario explains isotopic excursions that are correlated or uncorrelated with snowball initiation, and suggests that increasing atmospheric oxygen concentrations and a progressive oxygenation of the subsurface ocean helped to prevent snowball glaciation on the Phanerozoic Earth.Earth and Planetary Science

A terrestrial brine-seepage analog for Martian slope streaks near Salar de Pedernales in the Atacama Desert, Chile

Martian slope streaks are elongated down-slope, low-albedo surface features that currently form within sub-annual time scales in the high-albedo (“dusty”) regions of equatorial Mars. These km-scale streaks, which can persist up to several decades on the Martian surface, present one of the most enigmatic and dynamic suites of active surface features on present-day Mars. Two categories of explanations remain in debate regarding their nature: 1) “Dry” formation models, in which surface darkening is associated with mass wasting processes, such as dust avalanches; and 2) “Wet” formation models, in which surface darkening is associated with transient wetting of the surface by either seepage of sub-surface brines or deliquescence of atmospheric moisture. Here, we report recently discovered dark slope streaks that occur in the high Atacama Desert in Chile and display a close geomorphic resemblance to the Martian streaks. Field examination of the Atacama slope streaks revealed that they formed through down-slope seepage of groundwater brines sourced from the Salar de Pedernales located 500 m away. Chemical and mineralogical analyses demonstrate that salts deposited from the Pedernales brines combined with detrital input from soils/dust are responsible for surface darkening in the Atacama case. Field-based spectral measurements in the 0.4-2.5 micron wavelength range compare to those obtained from orbit for the Martian slope streaks. In addition, high-resolution topography derived from drone imagery revealed that the Atacama streaks are rougher than their surroundings at the decimeter-scale roughness of the entire hillslope they occur on. A similar distinction was previously established between Martian slope streaks and their surrounding slopes, although on Mars these roughness variations appear to occur at lower-range sub-centimeter scales. Our study of the unique Atacama slope streaks may support “wet” formation as a viable hypothesis for some of the Martian slope streaks.Fil: Mushkin, Amit. Geological Survey of Israel; IsraelFil: Sletten, Ronal. University of Washington; Estados UnidosFil: Trombotto, Dario Tomas. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Provincia de Mendoza. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales. Universidad Nacional de Cuyo. Instituto Argentino de Nivología, Glaciología y Ciencias Ambientales; ArgentinaFil: Jigjidsurengiin, Batbaatar. University of Washington; Estados UnidosFil: Amit, Rivka. Geological Survey of Israel; IsraelFil: Halevy, Itay. Weizmann Institute Of Science.; IsraelFil: Morag, Navot. Geological Survey of Israel; IsraelFil: Gillespie, Alan R.. University of Washington; Estados UnidosThe Geological Society of America: Connects 2021OregonEstados UnidosThe Geological Society of Americ

Influence of sulfate reduction rates on the Phanerozoic sulfur isotope record

Phanerozoic levels of atmospheric oxygen relate to the burial histories of organic carbon and pyrite sulfur. The sulfur cycle remains poorly constrained, however, leading to concomitant uncertainties in O2 budgets. Here we present experiments linking the magnitude of fractionations of the multiple sulfur isotopes to the rate of microbial sulfate reduction. The data demonstrate that such fractionations are controlled by the availability of electron donor (organic matter), rather than by the concentration of electron acceptor (sulfate), an environmental constraint that varies among sedimentary burial environments. By coupling these results with a sediment biogeochemical model of pyrite burial, we find a strong relationship between observed sulfur isotope fractionations over the last 200 Ma and the areal extent of shallow seafloor environments. We interpret this as a global dependency of the rate of microbial sulfate reduction on the availability of organic-rich sea-floor settings. However, fractionation during the early/mid-Paleozoic fails to correlate with shelf area. We suggest that this decoupling reflects a shallower paleoredox boundary, primarily confined to the water column in the early Phanerozoic. The transition between these two states begins during the Carboniferous and concludes approximately around the Triassic–Jurassic boundary, indicating a prolonged response to a Carboniferous rise in O2. Together, these results lay the foundation for decoupling changes in sulfate reduction rates from the global average record of pyrite burial, highlighting how the local nature of sedimentary processes affects global records. This distinction greatly refines our understanding of the S cycle and its relationship to the history of atmospheric oxygen.Earth and Planetary Science

How local depositional conditions control marine sedimentary pyrite sulfur isotopes: a framework integrating bulk and micro-scale SIMS analyses

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Deconstructing the Dissimilatory Sulfate Reduction Pathway: Isotope Fractionation of a Mutant Unable of Growth on Sulfate

The sulfur isotope record provides key insight into the history of Earth's redox conditions. A detailed understanding of the metabolisms driving this cycle, and specifically microbial sulfate reduction (MSR), is crucial for accurate paleoenvironmental reconstructions. This includes a precise knowledge of the step-specific sulfur isotope effects during MSR. In this study, we aim at resolving the cellular-level fractionation factor during dissimilatory sulfite reduction to sulfide within MSR, and use this measured isotope effect as a calibration to enhance our understanding of the biochemistry of sulfite reduction. For this, we merge measured isotope effects associated with dissimilatory sulfite reduction with a quantitative model that explicitly links net fractionation, reaction reversibility, and intracellular metabolite levels. The highly targeted experimental aspect of this study was possible by virtue of the availability of a deletion mutant strain of the model sulfate reducer Desulfovibrio vulgaris (strain Hildenborough), in which the sulfite reduction step is isolated from the rest of the metabolic pathway owing to the absence of its QmoABC complex (ΔQmo). This deletion disrupts electron flux and prevents the reduction of adenosine phosphosulfate (APS) to sulfite. When grown in open-system steady-state conditions at 10% maximum growth rate in the presence of sulfite and lactate as electron donor, sulfur isotope fractionation factors averaged −15.9‰ (1 σ = 0.4), which appeared to be statistically indistinguishable from a pure enzyme study with dissimilatory sulfite reductase. We coupled these measurements with an understanding of step-specific equilibrium and kinetic isotope effects, and furthered our mechanistic understanding of the biochemistry of sulfite uptake and ensuing reduction. Our metabolically informed isotope model identifies flavodoxin as the most likely electron carrier performing the transfer of electrons to dissimilatory sulfite reductase. This is in line with previous work on metabolic strategies adopted by sulfate reducers under different energy regimes, and has implications for our understanding of the plasticity of this metabolic pathway at the center of our interpretation of modern and palaeo-environmental records

Seasonal melting and the formation of sedimentary rocks on Mars, with predictions for the Gale Crater mound

A model for the formation and distribution of sedimentary rocks on Mars is proposed. The rate-limiting step is supply of liquid water from seasonal melting of snow or ice. The model is run for a O(10^2) mbar pure CO2 atmosphere, dusty snow, and solar luminosity reduced by 23%. For these conditions snow only melts near the equator, and only when obliquity >40 degrees, eccentricity >0.12, and perihelion occurs near equinox. These requirements for melting are satisfied by 0.01-20% of the probability distribution of Mars' past spin-orbit parameters. Total melt production is sufficient to account for aqueous alteration of the sedimentary rocks. The pattern of seasonal snowmelt is integrated over all spin-orbit parameters and compared to the observed distribution of sedimentary rocks. The global distribution of snowmelt has maxima in Valles Marineris, Meridiani Planum and Gale Crater. These correspond to maxima in the sedimentary-rock distribution. Higher pressures and especially higher temperatures lead to melting over a broader range of spin-orbit parameters. The pattern of sedimentary rocks on Mars is most consistent with a Mars paleoclimate that only rarely produced enough meltwater to precipitate aqueous cements and indurate sediment. The results suggest intermittency of snowmelt and long globally-dry intervals, unfavorable for past life on Mars. This model makes testable predictions for the Mars Science Laboratory rover at Gale Crater. Gale Crater is predicted to be a hemispheric maximum for snowmelt on Mars.Comment: Submitted to Icarus. Minor changes from submitted versio

Theoretical Estimates of Equilibrium Carbon and Hydrogen Isotope Effects in Microbial Methane Production and Anaerobic Oxidation of Methane

Microbial production and consumption of methane are widespread in natural and artificial environments, with important economic and climatic implications. Attempts to use the isotopic composition of methane to constrain its sources are complicated by incomplete understanding of the mechanisms of variation in methane\u27s isotopic composition. Knowledge of the equilibrium isotope fractionations among the large organic intracellular intermediates in the microbial pathways of methane production and consumption must form the basis of any exploration of the mechanisms of isotopic variation, but estimates of these equilibrium isotope fractionations are currently unavailable. To address this gap, we calculated the equilibrium isotopic fractionation of carbon (13C/12C) and hydrogen (D/H) isotopes among compounds in anaerobic methane metabolisms, as well as the abundance of multiple isotope substitutions ("clumping," e.g., 13C--D) in these compounds. The Density Functional Theory calculations employed the M06-L/def2-TZVP level of theory and the SMD implicit solvation model, which we have recently optimized for large organic molecules and tested against measured equilibrium isotope fractionations. The computed 13beta and 2beta values decrease with decreasing average oxidation state of the carbon atom in the molecules, resulting in a preference for enrichment of the molecules with more oxidized carbon in 13C and D. Using the computed $\beta$ values, we calculated the equilibrium isotope fractionation factors in the prominent methanogenesis pathways (hydrogenotrophic, methylotrophic and acetoclastic) and in the pathway for anaerobic oxidation of methane (AOM) over a temperature range of 0-700 degrees Celsius. Our calculated equilibrium fractionation factors compare favorably with experimental constrains, where available, and we used them to investigate the relation between the apparent isotope fractionation during methanogenesis and AOM and the thermodynamic drive for these reactions. We show that a detailed map of the equilibrium fractionation factors along these metabolic pathways allows an evaluation of the contribution of equilibrium and kinetic isotope effects to apparent isotope fractionations observed in laboratory, natural and artificial settings. The comprehensive set of equilibrium isotope fractionation factors calculated in this study provides a firm basis for future explorations of isotope effects in methane metabolism

Cathodoluminescence of iron oxides and oxyhydroxides

Iron oxides and oxyhydroxides show promise as superconductor materials and as repositories of paleo-environmental information. However, there are no microscale non-destructive analytical techniques to characterize their combined mineralogy, chemical composition, and crystal properties. We address this by developing cathodoluminescence mounted on a scanning electron microscope (SEM-CL) as an in situ, non-destructive method for the crystallographic and petrographic study of iron oxides and oxyhydroxides. We show that goethite, hematite, and magnetite display different SEM-CL spectra, which may be used for mineral identification. We further show that different formation pH, manganese substitution for iron in goethite and hematite, and titanium substitution for iron in magnetite cause shifts in the SEM-CL spectra of these minerals. These spectral shifts are not always detectable as a change in the emission color but are easily discernable by quantitative analysis of the spectra. Together with subtle but observable variations in the SEM-CL spectra of natural goethite and hematite, we suggest that these dependences of the SEM-CL spectra on pH and chemical composition may be used as a means of identifying multiple episodes of mineralization and recrystallization. We apply the newly developed SEM-CL methods to two polished sections of natural samples and show that quantitative analysis of the spectra obtained allows the identification of differences between varieties of the same mineral that are not observable by other means. Like the application of SEM-CL to geologic samples in this study, we suggest that this approach may be used to explore the in situ chemistry and crystallinity of various natural and manufactured iron oxides and oxyhydroxides.ISSN:0003-004XISSN:1945-302