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1. CO 2 reduction driven by a pH gradient

   https://doi.org/10.1073/pnas.2002659117  

   Hudson, Reuben ; de Graaf, Ruvan ; Strandoo Rodin, Mari ; Ohno, Aya ; Lane, Nick ; McGlynn, Shawn E. ; Yamada, Yoichi M. ; Nakamura, Ryuhei ; Barge, Laura M. ; Braun, Dieter ; et al ( September 2020 , Proceedings of the National Academy of Sciences)

   null (Ed.)

   All life on Earth is built of organic molecules, so the primordial sources of reduced carbon remain a major open question in studies of the origin of life. A variant of the alkaline-hydrothermal-vent theory for life’s emergence suggests that organics could have been produced by the reduction of CO 2 via H 2 oxidation, facilitated by geologically sustained pH gradients. The process would be an abiotic analog—and proposed evolutionary predecessor—of the Wood–Ljungdahl acetyl-CoA pathway of modern archaea and bacteria. The first energetic bottleneck of the pathway involves the endergonic reduction of CO 2 with H 2 to formate (HCOO – ), which has proven elusive in mild abiotic settings. Here we show the reduction of CO 2 with H 2 at room temperature under moderate pressures (1.5 bar), driven by microfluidic pH gradients across inorganic Fe(Ni)S precipitates. Isotopic labeling with 13 C confirmed formate production. Separately, deuterium ( 2 H) labeling indicated that electron transfer to CO 2 does not occur via direct hydrogenation with H 2 but instead, freshly deposited Fe(Ni)S precipitates appear to facilitate electron transfer in an electrochemical-cell mechanism with two distinct half-reactions. Decreasing the pH gradient significantly, removing H 2 , or eliminating the precipitate yielded no detectable product. Our work demonstrates the feasibility of spatially separated yet electrically coupled geochemical reactions as drivers of otherwise endergonic processes. Beyond corroborating the ability of early-Earth alkaline hydrothermal systems to couple carbon reduction to hydrogen oxidation through biologically relevant mechanisms, these results may also be of significance for industrial and environmental applications, where other redox reactions could be facilitated using similarly mild approaches. 

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2. Accessory phases as recorders of subduction redox: Sulfide–oxide– silica equilibria during high-pressure metamorphism

   Walters, JB ; Cruz-Uribe, AM ; Marschall, HR ( December 2018 , 2018 Fall Meeting, AGU)

   Examination of a global suite of eclogite-facies metabasites and metasediments suggests that eclogites tend to exhibit reduced mineral assemblages relative to their protoliths. High-pressure rocks tend to lack sulfides and Fe3+-bearing oxides in the eclogite facies. We suggest that eclogite-facies mineral assemblages are consistent with prograde reactions that balance the oxidation of S2- or S- to S6+ by reducing Fe3+in silicates or oxides: (1)8Fe3+Si O (OH) +S2-=8Fe2+Si O +SO 2-+(H O) abc de42f The oxidation of one mole of S2-or S-is balanced by the reduction of 7 to 8 moles of Fe3+, and typical S concentrations in the oceanic crust are capable of fully reducing the entire Fe3+ budget of metabasites. As most eclogite facies rocks do not preserve peak metamorphic sulfides, petrographic evidence for prograde S oxidation reactions are cryptic; however, textures associated with sulfate reduction in response to influx of external fluids are common (reaction 1 in reverse). These reactions produce Fe3+-rich phases and are observed in both metasedimentary and metabasic rocks across a range of retrograde P-T paths (blueschist to granulite facies). For example, high-P calc- schists exhibit reaction textures that suggest the breakdown of garnet and white mica to produce pyrite + chalcopyrite + epidote + biotite + magnetite. Our thermodynamic models of aS2 and aO2 at subduction zone P-T conditions suggest assemblages of this type are indicative of aO2 0.7 to 4.5 log units above the quartz-fayalite-magnetite buffer. In rehydrated eclogites, pyrite is commonly associated with the breakdown of garnet + omphacite to amphibole + pyrite. Additionally, direct precipitation of sulfide from sulfate is observed in two samples: 1) The retrograde assemblage pyrite + ilmenite + gypsum occurs in one retrogressed metagabbroic eclogite, and 2) Coronas of secondary pyrite + barite + gypsum enclose early retrograde pyrite in a retrogressed garnet blueschist. In many eclogites, S- is reduced to S2- as pyrite is replaced by pyrrhotite, chalcopyrite, and mixed valence Co-Ni sulfides. These reactions are balanced by oxidation of divalent to trivalent Fe-Co-Ni. Reactions of this type are consistent with increasing aS2 during retrograde metamorphism. Thus, ample evidence exists for oxidized S-bearing fluids released from subducting slabs. 

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3. Simulation of REE mobility and evolution of F-NaCl-CO2-bearing fluids in hydrothermal calcite and fluorite ore-forming veins

   https://doi.org/10.7185/gold2021.6309  

   Costa Filho, D. ; Gysi, A.P. ( July 2021 , Goldschmidt)

   Rare earth element (REE) deposits are commonly associated with carbonatites and (per)alkaline rocks where hydrothermal magmatic fluids can play a significant role in REE mobilization and deposition [1]. Thermodynamic modeling permits predicting the evolution of ore-forming fluids and can be used to test different controls on hydrothermal REE mobility including temperature, pressure, the solubility of REE minerals, aqueous REE speciation and pH evolution associated with fluid-rock interaction. Previous modeling studies either focused on REE fluoride/chloride complexation in acidic aqueous fluids [2] or near neutral/alkaline fluids associated with calcite vein formation [3]. Such models were also applied to interpret field observations in REE deposits Bayan Obo in China and Bear Lodge in Wyoming [3,4]. Recent hydrothermal calcite-fluid REE partitioning experiments provide new data to simulate the solubility of REE in calcite, REE carbonates/fluorocarbonates at high temperatures [5, 6]. We studied the competing effects controlling the mobility of REE in hydrothermal fluids between 100 and 400 °C at 500 bar. Speciation calculations were carried out in the Ca-F-CO2-Na-Cl-H2O system using the GEMS code package [7]. The properties of minerals and aqueous species were taken from the MINES thermodynamic database [3,5]. The Gallinas Mountains hydrothermal REE deposit in New Mexico was used as a field analogue to compare our models with the formation of calcite-fluorite veins hosting bastnäsite. Previous fluid inclusion studies hypothesized that the REE were transported as fluoride complexes [8] but more recent modeling studies have shown that fluoride essentially acts as a depositing ligand [2]. Here we show more detailed simulations predicting the stability of fluorite, calcite and REE minerals relevant to ore-forming processes in carbonatites and alkaline systems. [1] Gysi et al. (2016), Econ. Geol. 111, 1241-1276; [2] Migdisov and Williams-Jones (2014), Mineral. Deposita 49, 987-997. [3] Perry and Gysi (2018), Geofluids; [4] Liu et al. (2020), Minerals 10, 495; [5] Perry and Gysi (2020), Geochim. Cosmochim. Acta 286, 177-197; [6] Gysi and Williams-Jones (2015) Chem. Geol. 392, 87-101;[7] Kulik et al. (2013), Computat. Geosci. 17, 1-24; [8] Williams-Jones et al. (2000), Econ. Geol. 95, 327-341 

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4. An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

   https://doi.org/10.2138/am-2022-8250  

   Kim, YoungJae ; Konecke, Brian ; Simon, Adam ; Fiege, Adrian ; Becker, Udo ( November 2022 , American Mineralogist)

   The mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X-ray absorption near-edge structure spectroscopy (S-XANES) where S 6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms.

   One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel.

   The thermodynamics of incorporation of disulfide and bisulfide into apatite is evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S is also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS(aq)(2−n) and HnS(aq)(2−n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite, and decreases for hydroxylapatite, as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures.

    

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5. An ab-initio study on the thermodynamics of disulfide, sulfide, and bisulfide incorporation into apatite and the development of a more comprehensive temperature, pressure, pH, and composition-dependent model for ionic substitution in minerals

   Young Jae Kim, Brian Konecke ( September 2022 , The American mineralogist)

   The mineral apatite, Ca10(PO4)6(F,OH,Cl)2, incorporates sulfur (S) during crystallization from S-bearing hydrothermal fluids and silicate melts. Our previous studies of natural and experimental apatite demonstrate that the oxidation state of S in apatite varies systematically as a function of oxygen fugacity (fO2). The S oxidation states –1 and –2 were quantitatively identified in apatite crystallized from reduced, S-bearing hydrothermal fluids and silicate melts by using sulfur K-edge X‑ray absorption near-edge structure spectroscopy (S-XANES) where S6+/ΣS in apatite increases from ~0 at FMQ-1 to ~1 at FMQ+2, where FMQ refers to the fayalite-magnetite-quartz fO2 buffer. In this study, we employ quantum-mechanical calculations to investigate the atomistic structure and energetics of S(-I) and S(-II) incorporated into apatite and elucidate incorporation mechanisms. One S(-I) species (disulfide, S22−) and two S(-II) species (bisulfide, HS−, and sulfide, S2−) are investigated as possible forms of reduced S species in apatite. In configuration models for the simulation, these reduced S species are positioned along the c-axis channel, originally occupied by the column anions F, Cl, and OH in the end-member apatites. In the lowest-energy configurations of S-incorporated apatite, disulfide prefers to be positioned halfway between the mirror planes at z = 1/4 and 3/4. In contrast, the energy-optimized bisulfide is located slightly away from the mirror planes by ~0.04 fractional units in the c direction. The energetic stability of these reduced S species as a function of position along the c-axis can be explained by the geometric and electrostatic constraints of the Ca and O planes that constitute the c-axis channel. The thermodynamics of incorporation of disulfide and bisulfide into apatite are evaluated by using solid-state reaction equations where the apatite host and a solid S-bearing source phase (pyrite and Na2S2(s) for disulfide; troilite and Na2S(s) for sulfide) are the reactants, and the S-incorporated apatite and an anion sink phase are the products. The Gibbs free energy (ΔG) is lower for incorporation with Na-bearing phases than with Fe-bearing phases, which is attributed to the higher energetic stability of the iron sulfide minerals as a source phase for S than the sodium sulfide phases. The thermodynamics of incorporation of reduced S are also evaluated by using reaction equations involving dissolved disulfide and sulfide species [HnS2(aq)(2–n) and HnS(aq)(2–n); n = 0, 1, and 2] as a source phase. The ΔG of S-incorporation increases for fluorapatite and chlorapatite and decreases for hydroxylapatite as these species are protonated (i.e., as n changes from 0 to 2). These thermodynamic results demonstrate that the presence of reduced S in apatite is primarily controlled by the chemistry of magmatic and hydrothermal systems where apatite forms (e.g., an abundance of Fe; solution pH). Ultimately, our methodology developed for evaluating the thermodynamics of S incorporation in apatite as a function of temperature, pH, and composition is highly applicable to predicting the trace and volatile element incorporation in minerals in a variety of geological systems. In addition to solid-solid and solid-liquid equilibria treated here at different temperatures and pH, the methodology can be easily extended also to different pressure conditions by just performing the quantum-mechanical calculations at elevated pressures. 

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