CO2 H2O System Research Articles

A Combined Experimental and Computational Study on the Effect of the Reactor Configuration and Operational Procedures on the Formation, Growth and Dissociation of Carbon Dioxide Hydrate

Clathrate hydrate-based technologies are considered promising and sustainable alternatives for the effective management of the climate change risks related to emissions of carbon dioxide produced by human activities. This work presents a combined experimental and computational investigation of the effects of the operational procedures and characteristics of the experimental configuration, on the phase diagrams of CO2-H2O systems and CO2 hydrates’ formation, growth and dissociation conditions. The operational modes involved (i) the incremental (step-wise) temperature cycling and (ii) the continuous temperature cycling processes, in the framework of an isochoric pressure search method. Also, two different high-pressure PVT configurations were used, of which one encompassed a stirred tank reactor and the other incorporated an autoclave of constant volume with magnetic agitation. The experimental results implied a dependence of the subcooling degree, (P, T) conditions for hydrate formation and dissociation, and thermal stability of the hydrate phase on the applied temperature cycling mode and the technical features of the utilized PVT configuration. The experimental findings were complemented by a thermodynamic simulation model and other calculation approaches, with the aim to resolve the phase diagrams including the CO2 dissolution over the entire range of the applied (P, T) conditions.

The precipitation mechanisms of scheelite from CO2-rich hydrothermal fluids: Insight from thermodynamic modeling

Scheelite and wolframite are two main tungsten-bearing ore minerals in tungsten deposits. Compared to wolframite formed mostly by NaCl–H2O fluids, scheelite in many but not all tungsten deposits is associated with CO2–bearing hydrothermal fluids, but its precipitation mechanisms from these fluids are poorly understood. The replacement of wolframite by scheelite is common among tungsten deposits where these two tungstates coexist, but how CO2, as the pH-buffering agent, affects their replacement remains unclear. To answer these questions, we first tested the pH-buffering effect of CO2 by comparing available experimental pH values of H2O–CO2±NaCl solutions at 200–280 °C and the corresponding thermodynamic modeling results. The mean absolute errors between the calculated and experimental pH values are 0.14 log units in H2O–CO2 solutions and 0.13 log units in H2O–CO2–NaCl solutions, indicating that the calculated acitivities of H+ in CO2-bearing solutions are reliable. Then, the solubilities of scheelite, scheelite-ferberite, and scheelite-hübnerite in NaCl–H2O–CO2 systems were modeled in this study. Our modeling results suggest that scheelite solubility in CO2-rich fluids is highly dependent on fluid pressure but is insensitive to fluid temperature. A decrease in fluid pressure from lithostatic to hydrostatic levels at a depth of 3–8 km causes CO2 escape and pH rise and precipitates over 70 % of tungsten contents in fluids on average. Therefore, CO2 escape is an efficient mechanism for precipitating scheelite from CO2–rich hydrothermal fluids. The independence of scheelite solubility on temperature at high pressures and the slightly retrograde solubility at low pressures allows CO2–rich hydrothermal fluids to carry a great amount of tungsten far away from its sources. This may be one of reasons why some scheelite deposits occur at greater distances (>500 m) from the granite or extend along its strike for several kilometers. Similar to the cases in NaCl–H2O systems, two mechanisms for scheelite replacing wolframite in CO2–rich fluids are identified, a single decrease in fluid pressure or simple cooling plus an increase in the ratios of total Ca contents to total Fe (or Mn) contents in fluids.

Precisely Regulating Asymmetric Charge Distribution by Single-Atom Central Doped Ag-Based Series Clusters for Enhanced Photoreduction of CO2 to Alcohol Fuels.

High efficiently photocatalytic CO2 reduction (CO2RR) into liquid fuels in pure water system remains challenged. Iron polyphthalocyanine (FePPc) with strong light harvesting, unique Fe-N4 structure, abundant pores, and good stability could serve as a promising catalyst for CO2 photoreduction. To further improve the catalytic efficiency, herein, symmetry-breaking Fe sites are constructed by coupling with atomically precise M1Ag24 (M=Ag, Au, Pt) series clusters. Especially, the introduction of Pt1Ag24 causes the most asymmetric charge distribution of Fe in FePPc (followed by Au1Ag24 and Ag25), leading to the favorable CO2 adsorption and activation. In addition, Pt1Ag24-FePPc exhibits the most effective photogenerated carriers transfer and separation. As a result, Pt1Ag24-FePPc shows the methanol/ethanol yield of 48.55/32.97 μmol·gcat-1·h-1 in H2O-CO2 system under visible light irradiation, ~ 1.65/1.25-fold, 1.83/1.37-fold, and 3.6/1.61-fold higher than that of Au1Ag24-FePPc, Ag25-FePPc, and FePPc, respectively. This work provides a concept for precisely construction and regulation symmetry-breaking sites of cluster-based catalysts for effective CO2 conversion.

Calculations of solubilities of pure noble gases and He–CO2/CH4/N2 gas mixtures in aqueous solutions with accurate thermodynamic models

Determining solubilities of pure noble gases and He–CO2/CH4/N2 gas mixtures in aqueous solutions is essential for various applications of noble gases in geological processes and for understanding the migration and accumulation of helium. This study developed two thermodynamic models for calculations of solubilities of five pure noble gases (i.e. He, Ne, Ar, Kr, and Xe) and He–CO2/CH4/N2 gas mixtures in water and in aqueous NaCl solution. The first model is constructed by extending the improved SAFT-LJ equation of state (EOS) to five binary H2O-noble gas systems and four ternary systems (i.e. H2O–He–NaCl, H2O–He–CO2, H2O–He–CH4, and H2O–He–N2). Both the non-ideality of aqueous phase and that of vapor phase of these systems were described using the improved SAFT-LJ EOS (φ-φ model). The second model is developed by modifying the gas solubility model proposed by Duan and his coworkers (one type of γ-φ model). The Pitzer theory was used to describe the non-ideality of aqueous phase and the improved SAFT-LJ EOS was used to describe the non-ideality of vapor phase. Both binary adjustable parameters of the improved SAFT-LJ EOS and parameters of the modified solubility model for pure gas were evaluated from experimental solubility data for pure gas. Both models are predictive for solubilities of gas mixtures since there is no need to evaluate their parameters from solubility data of gas mixtures.Comparisons of calculations of two models with experimental data show that both models can well represent solubilities and Henry's coefficients of five noble gases in pure water, as well as the solubility of He in aqueous NaCl solutions over a wide P-T range (273–600 K, 1–2000 bar for the solubility of He in water). The absolute average deviation of the improved SAFT-LJ EOS from experimental solubility data for five noble gases in pure water is 3.14% and that of the modified solubility model is 2.21%. Predictions of the improved SAFT-LJ EOS for Henry's coefficients for He in the He–CO2–H2O system are consistent with available experimental data. According to predictions of the improved SAFT-LJ EOS, Henry's coefficient for He in the He–CO2–H2O system is always lower than that in the He–H2O system at the same depth. Within 0–5 km depth, He solubility of He–CO2 gas mixture is much greater than that of pure He at the same depth and He partial pressure, He solubility of He–N2 mixture is a little greater than that of pure He, and He solubility of He–CH4 mixture is between that of He–CO2 mixture and that of He–N2 mixture. A computer program for calculations of solubilities of pure noble gases and He–CO2/CH4/N2 gas mixtures in pure water and in aqueous NaCl solutions can be obtained from the corresponding author via email.

Molecular dynamics insights into gas-water interfacial tension: Optimizing hydrogen storage in subsurface conditions

This study presents a comprehensive analysis of interfacial tension (IFT) between pore water and hydrogen-cushion gas mixtures in subsurface porous media, a key variable in the distribution of gas mixtures for hydrogen storage. Employing molecular dynamics simulations, we developed two IFT models at 20 MPa and 373 K: one for an H2–CO2–H2O system and another for an H2–CH4–H2O system. The models reveal that increasing cushion gas concentration reduces gas-water IFT. Notably, for H2–CO2–H2O mixtures, the IFT substantially decreases with CO2 concentration up to 40%, after which the reduction rate diminishes. In H2–CH4–H2O mixtures, the IFT decreases linearly with CH4 concentration. The study attributes these variations to local density distributions and molecular orientation effects. Specifically, CO2 adsorption at the interface up to 40% concentration significantly lowers IFT, while CH4 adsorption proportionally decreases IFT. The influence of CO2 on water molecule orientation at the interface, in contrast to the non-effect of CH4, is also critical in enhancing IFT reduction. Our results also highlight the reduction of H2 self-diffusion at the interface caused by CO2 and CH4, an essential factor in optimizing subsurface hydrogen storage operations.

Combined experimental and computational study for the electrode process of electrochemically mediated amine regeneration (EMAR) CO2 capture

The electrochemically mediated amine regeneration (EMAR) for CO2 capture presents a promising CO2 capture approach. However, there is a lack of systematic research on the EMAR electrode process, particularly regarding the diffusion of Cu2+ and [Cu-Am]2+, the characteristics of electrode reactions, and the impact of desorbed CO2 bubbles on electrode process. In this work, we investigated the Cu-EDA based EMAR process by the combination of electrochemical measurements and multi-physics simulation. The experimental results revealed that the anode process is controlled by both mass transfer and charge transfer process, while the mass transfer process in the cathode process is the rate-controlling step. A lower anode copper loading and a higher cathode copper loading are conducive to the EMAR process. A reasonable simplification method for the electrode process was proposed by referencing the equilibrium reactive model results of Cu(II)–EDA–CO2–H2O system. A multi-physics model was constructed using COMSOL software, which coupled the Tertiary Nernst-Planck model and the Bubbly Flow model to simulate the complex electrode process and its effectiveness has been verified. Simulation results show that the formation of CO2 bubbles has a negative impact on the electrode process, while the disturbance caused by the bubbles may have a certain promotion effect on the electrode process. The CO2 desorption and the desorption rate is greatly affected by the the applied potential, and the desorption energy consumption mainly keeps a linear relationship with the applied potential. This work supposes to provide an effective guidance for the improvement of the vital electrodes process of the EMAR system.

Thermodynamic Model of the Fluid System H2O–CO2–NaCl–CaCl2 at P-T Parameters of the Middle and Lower Crust

Based on the earlier obtained equations of state for the ternary systems H2O–CO2–CaCl2 and H2O–CO2–NaCl, an equation of state for the four-component fluid system H2O–CO2–NaCl–CaCl2 is derived in terms of the Gibbs excess free energy. A corresponding numerical thermodynamic model is built. The main part of the numerical parameters of the model coincides with the corresponding parameters of the ternary systems. The NaCl–CaCl2 interaction parameter was obtained from the experimental liquidus of the salt mixture. Similar to the thermodynamic models for H2O–CO2–CaCl2 and H2O–CO2–NaCl, the range of applicability of the model is pressure 1–20 kbar and temperature from 500 to 1400°C. The model makes it possible to predict the physicochemical properties of the fluid involved in most processes of deep petrogenesis: the phase state of the system (homogeneous or multiphase fluid, presence or absence of solid salts), chemical activities of the components, densities of the fluid phases, and concentrations of the components in the coexisting phases. The model was used for a detailed study of the phase state and activity of water on the H2O–CO2–salt sections when changing the ratio {{{{x}_{{{text{NaCl}}}}}} mathord{left/ {vphantom {{{{x}_{{{text{NaCl}}}}}} {({{x}_{{{text{NaCl}}}}} + {{x}_{{{text{CaC}}{{{text{l}}}_{{text{2}}}}}}})}}} right. kern-0em} {({{x}_{{{text{NaCl}}}}} + {{x}_{{{text{CaC}}{{{text{l}}}_{{text{2}}}}}}})}} from 1 to 0. Changes in the composition and density of coexisting fluid phases at a constant activity of water and changes in the total composition of the system are studied. A set of phase diagrams on sections H2O–NaCl–CaCl2 for different mole fractions of CO2 is obtained. Pressure dependencies of the maximal activity of water in the field of coexisting unmixable fluid phases are obtained for several salt compositions of the system. Due to removal of restrictions resulting from a smaller number of components in ternary systems, the thermodynamic behavior of systems with a mixed composition of the salt significantly differs from the behavior of those with a single salt component.

Thermodynamic Model of the Fluid System H<sub>2</sub>O–CO<sub>2</sub>–NaCl–CaCl<sub>2</sub> at <i>P-T</i> Parameters of the Middle and Lower Crust

Based on the earlier obtained equations of state for the ternary systems H2O–CO2–CaCl2 and H2O–CO2–NaCl, an equation of state for the four-component fluid system H2O–CO2–NaCl–CaCl2 is derived in terms of the Gibbs excess free energy. A corresponding numerical thermodynamic model is build. The main part of the numerical parameters of the model coincides with the corresponding parameters of the ternary systems. The NaCl–CaCl2 interaction parameter was obtained from the experimental liquidus of the salt mixture. Similar to the thermodynamic models for H2O–CO2–CaCl2 and H2O–CO2–NaCl, the range of applicability of the model is pressure 1–20 kbar and temperature from 500°C to 1400°C. The model makes it possible to predict the physicochemical properties of the fluid involved in most processes of deep petrogenesis: the phase state of the system (homogeneous or multiphase fluid, presence or absence of solid salts), chemical activities of the components, densities of the fluid phases, and concentrations of the components in the coexisting phases. The model was used for a detailed study of the phase state and activity of water on the H2O–CO2–salt sections when changing the ratio \( {{{{x}_{{{\text{NaCl}}}}}} \mathord{\left/ {\vphantom {{{{x}_{{{\text{NaCl}}}}}} {\left( {{{x}_{{{\text{NaCl}}}}} + {{x}_{{{\text{CaC}}{{{\text{l}}}_{{\text{2}}}}}}}} \right)}}} \right.} {\left( {{{x}_{{{\text{NaCl}}}}} + {{x}_{{{\text{CaC}}{{{\text{l}}}_{{\text{2}}}}}}}} \right)}} \) from 1 to 0. Changes in the composition and density of coexisting fluid phases at a constant activity of water and changes in the total composition of the system are studied. A set of phase diagrams on sections H2O–NaCl–CaCl2 for different mole fractions of CO2 is obtained. Pressure dependencies of the maximal activity of water in the field of coexisting unmixable fluid phases are obtained for several salt compositions of the system. Due to removal of restrictions resulting from a smaller number of components in ternary systems, the thermodynamic behavior of systems with a mixed composition of the salt is significantly differ from the behavior of those with a single salt component.

Direct Measurement of the Four-Phase Equilibrium Coexistence Vapor-Aqueous Solution-Ice-Gas Hydrate in Water-Carbon Dioxide System.

Precise data on the non-variant equilibrium of the four phases (vapor-aqueous solution-ice-gas hydrate) in P-T coordinates are highly desired for developing accurate thermodynamic models and can be used as reference points (similar to the triple point of water). Using the two-component hydrate-forming system CO2-H2O, we have proposed and validated a new express procedure for determining the temperature and pressure of the lower quadruple point Q1. The essence of the method is the direct measurement of these parameters after the successive formation of the gas hydrate and ice phases in the initial two-phase gas-water solution system under intense agitation of the fluids. After relaxation, the system occurs in the same equilibrium state (T = 271.60 K, P = 1.044 MPa), regardless of the initial parameters and the order of crystallization of the CO2 hydrate and ice phases. Considering the combined standard uncertainties (±0.023 K, ±0.021 MPa), the determined P and T values agree with the results of other authors obtained by a more sophisticated indirect method. Validating the developed approach for systems with other hydrate-forming gases is of great interest.

High-Pressure Synthesis, Synchrotron Single-Crystal XRD and Raman Spectroscopy of Synthetic K–Ba Minerals of Magnetoplumbite, Crichtonite and Hollandite Group Indicatory of Mantle Metasomatism

The paper summarizes the results of an experimental study of the formation of K–Ba high-Ti (and Cr) oxides synthesized in the chromite–rutile/ilmenite–K2CO3/BaCO3–H2O–CO2 systems at 1.8–5.0 GPa. Experiments confirm the conclusion that the formation of K–Ba high-Ti oxides characterizes the most advanced or repeated metasomatic stages in upper mantle peridotites, which lead first to the formation of simple Ti oxides and then to the formation of K–Ba high-Ti and Cr oxides. Relations between the oxides is a function of the activity of the K and Ba components in the fluid. The appearance of priderite corresponds to the highest activity of K in the mineral-forming media. Redledgeite is formed only in the Fe-poor chromite–rutile–H2O–CO2–BaCO3 system, and, in the system with ilmenite, minerals of the magnetoplumbite group preferably crystallize. A direct dependence of the Cr content in oxides on pressure is revealed. Raman spectra of K–Ba high-titanium oxides are presented. The structure of a potassium compound of a magnetoplumbite group with the chemical formula K0.90Ti5.16Cr2.94Fe2.54Mg0.87Al0.22Mn0.30O19 is studied by single-crystal X-ray diffraction using a synchrotron radiation. The obtained data can be used to specify the nomenclature of the magnetoplumbite mineral group.

A High-pressure Filled Ice in the H2O–CO2–CH4 System, with Possible Consequences for the CO2–CH4 Biosignature Pair

Here we constrain the speciation of carbon that may outgas in ocean exoplanets. Ocean exoplanets likely have at least a few percent by mass of water, which is sufficient to build a high-pressure ice layer between a rocky interior and the outer hydrosphere. We study the possible formation of a filled ice in the ternary system H2O–CO2–CH4. The incorporation of CH4 and CO2 in filled ice would be an important mechanism for transporting carbon across a high-pressure ice mantle into the atmosphere. The CH4–CO2 pair is also important as a potential biosignature. We find that a filled ice in the system H2O–CO2–CH4 is possible though enriched in CH4. CO2 cannot account for more than 15% by mole of the carbon content of the filled ice. Such a filled ice is less dense than an overlying ocean and would therefore discharge into the ocean, depressurize, and outgas its carbon content into the atmosphere. A high-pressure, water-rich mantle in ocean worlds may therefore support the transport of carbon from the interior into the atmosphere. More than 75% by mole of this carbon would be reduced. As long as CH4 exists/is produced in the interior and the ice mantle convects, thus transporting chemical species outward, a flux of carbon enriched in CH4 would outgas. If this persists over geological time it would negate atmospheric sinks for CH4, and explain low concentrations of atmospheric CO2. If the contrary is correct than the interior of the planet may be oxidizing.

Atomic Bridging of Sn Single Atom with Nitrogen and Oxygen Atoms for the Selective Electrocatalytic Reduction of CO 2

Open AccessCCS ChemistryRESEARCH ARTICLES9 Dec 2022Atomic bridging of Sn single atom with nitrogen and oxygen atoms for selectively electrocatalytic reduction of CO2 Bari Wulan, Xueying Cao, Dongxing Tan, Xinxin Shu, Jizhen Ma, Shaoqi Hou and Jintao Zhang Bari Wulan Google Scholar More articles by this author , Xueying Cao Google Scholar More articles by this author , Dongxing Tan Google Scholar More articles by this author , Xinxin Shu Google Scholar More articles by this author , Jizhen Ma Google Scholar More articles by this author , Shaoqi Hou Google Scholar More articles by this author and Jintao Zhang Google Scholar More articles by this author https://doi.org/10.31635/ccschem.022.202202464 SectionsSupplemental MaterialAboutPDF ToolsAdd to favoritesDownload CitationsTrack Citations ShareFacebookTwitterLinked InEmail The atomic coordination structure of single atom catalysts is crucial to modulate electrocatalytic reduction of CO2 into desirable products. However, there remains limited insight into their roles and catalytic mechanisms. In comparison with commonly proposed metal-N4 moieties, herein the atomic bridging structure of nitrogen-tin-oxygen (N2-Sn-O2) confined in porous carbon fibers is firstly presented for selective reduction of CO2. With the detailed identification of such unique structure, the in-situ experimental results and theory calculations demonstrate that the bridging structure with reactive oxygen species enable the favorable surface electronic status to form adsorbed intermediate, *COOH for the selective CO generation. Typically, the electrocatalytst displayed the high Faradaic efficiency for reducing CO2 into CO, but formate production on the traditional Sn-based catalysts. Additionally, the solar-driven CO2-H2O system displays the desirable solar-to-CO conversion efficiency of 12.9%. This work provides fundamental guidance for the rational regulation of atomic coordination structure to improve the production selectivity. Download figure Download PowerPoint Previous articleNext article FiguresReferencesRelatedDetails Issue AssignmentVolume 0Issue jaPage: 1-24Supporting Information Copyright & Permissions© 2022 Chinese Chemical Society Downloaded 57 times PDF downloadLoading ...

Experimental study on the competition between carbon dioxide hydrate and ice below the freezing point

As climate change and industrial requirements intensify, the potential of CO2 hydrates for carbon storage has attracted increasing attention. However, despite continuous progress, the subzero phase behavior of the CO2-H2O system is not well understood and merits further research. To investigate the competing and coexisting growth mechanisms of CO2 gas hydrate and ice below the quadruple point, we conducted experiments at both the micrometer-scale and mesoscale scales. The growth morphology of hydrate and ice at large and small subcooling temperatures was observed in situ in a high-pressure optical cell, and the thermodynamic behavior of the competitive process after hydrate formation was investigated in a high-pressure reactor with sands. When hydrates and ice are formed together at small subcooling temperatures, preferential hydrate formation leads to ice dissolution or even disappearance. At large subcooling temperatures, ice forms first, and the hydrate mainly forms a fibrous envelope. A small decrease in the subzero temperature after hydrate formation partially decomposes the hydrates owing to ice formation, followed by more rapid hydrate production. This study provides a thorough and expanded understanding of the competition between ice and hydrates by connecting the evolution of crystal frameworks with the thermodynamic features of the process.

Biaxial Hard Compression, Anisotropic Elastic Property, and Pressure-Induced Isosymmetric Phase Transition in Ammonium Bicarbonate

The elastic property, exceptional anisotropic compression, and pressure-induced isosymmetric phase transition in ammonium bicarbonate (AB) are studied by in situ synchrotron X-ray diffraction, Raman spectroscopy, and computational methods. The exceptional anisotropic compression as a result of biaxial hard compression is induced by stiff hydrogen-bonding “double-wine-rack” geometric motifs. The large values of elastic anisotropy such as Young’s moduli, Shear moduli, and Poisson’s ratio verify the anisotropic nature in AB. The biaxial hard compression further induces an isosymmetric phase transition at 2 GPa through the generation of new N–H···O hydrogen bonds. Our work first demonstrates the stiff mechanical study of “double-wine-rack” geometric hydrogen-bonding networks and its influence on the phase transition, which can be used as a model to investigate the robust nature of hydrogen bonds and the structural origin of isosymmetric phase transition. Moreover, the hydrogen-bonding “double-wine-rack” geometric mechanism also provides an inspiration to construct a covalent-bonding “double-wine-rack” geometric model favoring anomalous biaxial mechanical/thermal responses. The determination of the high-pressure phase of AB provides new information to understand the composition of the ternary system H2O–CO2–NH3.

Anisotropic rate-dependent saturation functions for compositional simulation of sandstone composites

Determination of representative saturation functions for permeable reservoir sandstones requires consideration of mm-cm scale laminations and crossbedding common in these heterogeneous porous media. Modelling selected laminated sandstones from CO2CRC's Otway International Test Centre in Victoria, Australia as bimodal composites of different rock types, we analyse drainage relative permeability parallel and perpendicular to the laminae for a range of driving gradients. The results from these numeric drainage experiments are curve fit across a continuous range of flow rates between the capillary and viscous limits. Our analysis shows that laminae-related small, but spatially correlated grainsize and permeability variations give rise to flow-rate dependent drainage behaviour at the bed scale. The flow direction- and rate-dependent behaviour is captured by a new set of anisotropic extended saturation functions that are implemented and presented in a form that is suitable for compositional simulation in the system CO2–H2O–NaCl. For the first time, these new constitutive relationships permit an investigation of feedbacks between the reservoir-scale flow regime and bed-scale phase mobility. To illustrate the application of these functions in reservoir simulation, meter-scale plume spreading simulations are presented for a suite of ten homogenised fluvial-to-estuarine sandstones from the Otway facility.

Relative Contributions of Mg Hydration and Molecular Structural Restraints to the Barrier of Dolomite Crystallization: A Comparison of Aqueous and Non-Aqueous Crystallization in (BaMg)CO3 and (CaMg)CO3 Systems

Carbonate mineralization is reasonably well-understood in the Ca–CO2–H2O system but continuously poses difficulties to grasp when Mg is present. One of the outstanding questions is the lack of success in dolomite MgCa(CO3)2 crystallization at atmospheric conditions. The conventional view holds that hydration retards the reactivity of Mg2+ and is supported by solvation shell chemistry. This theory however is at odds with the easy formation of norsethite MgBa(CO3)2, a structural analogue of dolomite, leading to the premise that crystal or molecular structural constrains may also be at play. The present study represents our attempts to evaluate the separate contributions of the two barriers. Crystallization in the Mg–Ba–CO2 system was examined in a non-aqueous environment and in H2O to isolate the effect of hydration by determining the minimal relative abundance of Mg required for norsethite formation. The results, showing an increase from 1:5 to 6:4 in the solution Mg/Ba ratio, represented a ~88% reduction in Mg2+ reactivity, presumably due to the hydration effect. Further analyses in the context of transition state theory indicated that the decreased Mg2+ reactivity in aqueous solutions was equivalent to an approximately 5 kJ/mol energy penalty for the formation of the activated complex. Assuming the inability of dolomite to crystallizes in aqueous solutions originates from the ~40 kJ/mol higher (relative to norsethite) Gibbs energy of formation for the activated complex, a hydration effect was estimated to account for ~12% of the energy barrier. The analyses present here may be simplistic but nevertheless consistent with the available thermodynamic data that show the activated complex of dolomite crystallization reaction is entropically favored in comparison with that of norsethite formation but is significantly less stable due to the weak chemical bonding state.

Phase State and Thermodynamic Parameters of the Fluid System H2O–CO2–CH4 at P-T Conditions of the Crust and Lithosphere Mantle

Phase State and Thermodynamic Parameters of the Fluid System H2O–CO2–CH4 at P-T Conditions of the Crust and Lithosphere Mantle

Fluid inclusions in amethyst quartz of different geological environments from Brazil

Abstract Fluid-inclusion studies were conducted on amethyst quartz from three different geological environments: basalt cavities; hydrothermal veins; and granitic pegmatites of Eastern Brazil, to understand the conditions of amethyst crystallisation in each of these environments. In samples from basalt cavities, fluid inclusions are exclusively one-phase aqueous types suggesting a low-temperature formation environment. Crystals from the two other environments show that fluid inclusions can be either one-phase aqueous, two-phase aqueous, three-phase aqueous carbonic, or three-phase aqueous with the presence of precipitated solid halite. The carbonic composition of the system H2O–CO2–NaCl was confirmed by Raman spectroscopic analysis and suggests a metamorphic or magmatic fluid source. Fluid inclusions trapped in samples from hydrothermal veins reveal at least two different fluid generations based on homogenisation temperatures. The first generation has minimum trapping temperatures between 249°C and 391°C. The second generation of lower temperature fluids has minimum trapping temperatures varying from 82°C to 203°C. Fluid inclusions of this group record eutectic temperatures that indicate the presence of Ca and Fe cations in addition to Na. Fluid inclusions trapped in amethyst from a pegmatite body have moderate salinity values between 15 and 25 eq. wt.% NaCl, thus reflecting the elevated salt content in pegmatite-forming fluids. In this sample, the first fluid generation is represented by aqueous fluid inclusions with minimum trapping temperatures ranging from 268°C to 375°C. The estimated eutectic temperatures, generally below –50°C, indicate the presence of Ca cations in addition to Na. Minimum trapping temperatures correspond to temperatures of late-to-post-pegmatitic hydrothermal stages. The second generation records minimum trapping temperatures between 125°C and 247°C. Amethyst from both hydrothermal veins and pegmatite environments contain solid inclusions of hematite, an indication that the mineralising fluid was Fe rich and thus, possibly magmatic in origin.

Stable Abiotic Production of Ammonia from Nitrate in Komatiite-Hosted Hydrothermal Systems in the Hadean and Archean Oceans

Abiotic fixation of atmospheric dinitrogen to ammonia is important in prebiotic chemistry and biological evolution in the Hadean and Archean oceans. Though it is widely accepted that nitrate (NO3−) was generated in the early atmospheres, the stable pathways of ammonia production from nitrate deposited in the early oceans remain unknown. This paper reports results of the first experiments simulating high-temperature, high-pressure reactions between nitrate and komatiite to find probable chemical pathways to deliver ammonia to the vent–ocean interface of komatiite-hosted hydrothermal systems and the global ocean on geological timescales. The fluid chemistry and mineralogy of the komatiite–H2O–NO3− system show iron-mediated production of ammonia from nitrate with yields of 10% at 250 °C and 350 °C, 500 bars. The komatiite–H2O–NO3– system also generated H2-rich and alkaline fluids, well-known prerequisites for prebiotic and primordial metabolisms, at lower temperatures than the komatiite–H2O–CO2 system. We estimate the ammonia flux from the komatiite-hosted systems to be 105–1010 mol/y in the early oceans. If the nitrate concentration in the early oceans was greater than 10 μmol/kg, the long-term production of ammonia through thermochemical nitrate reduction for the first billion years might have allowed the subsequent development of an early biosphere in the global surface ocean. Our results imply that komatiite-hosted systems might have impacted not only H2-based chemosynthetic ecosystems at the vent-ocean interface but also photosynthetic ecosystems on the early Earth.

Fluid inclusions, H-O-S-Pb isotopes and metallogenic implications of Triassic Hua'naote Ag-Pb-Zn deposit (Inner Mongolia, China) in the eastern Central Asian Orogenic Belt

The Hua'naote Ag-Pb-Zn deposit (Inner Mongolia, northern China) is a hydrothermal vein-type deposit in the Erlianhot-Dongwuqi Metallogenic Belt (EDMB), which is situated in the eastern Central Asian Orogenic Belt (CAOB). Mineralization occurs in the contact between monzogranite and the Devonian Angeer Yinwula Formation (Fm.) silty slate, and is also closely related to syenogranite. The mineralization can be divided into three stages: (I) arsenopyrite + pyrite + quartz, (II) pyrite + galena + sphalerite + chalcopyrite + quartz, and (III) galena + sphalerite + calcite + quartz. Fluid inclusions (FIs) from Hua'naote are liquid-rich (L-type), vapor-rich (V-type), CH4 + CO2 (C1-type), CO2-bearing (C2-type), and daughter-mineral-bearing three-phase (S-type). Laser Raman spectral analysis shows that the gas phase in Stage I and II C2-type FIs is mainly composed of H2O, CO2, N2 and CH4, while that in Stage III FIs contains predominantly H2O. Stage I FIs are of L-, V-, C1-, C2- and S-types. These FIs homogenized mainly at 300–380 °C, and their salinities are bimodal (1.7–8.4 wt% and 35.2–45.8 wt% NaCl eqv.). Our results suggest that Stage I fluids belong to a NaCl–H2O–CO2 ± CH4 system characterized by medium-to-high temperature and salinity. Stage II FIs are of L-, V- and C2-types, with homogenization temperatures and salinities of 180.4–302.8 °C and 2.23–5.70 wt% NaCl eqv., respectively. Stage II fluids belong to a NaCl–H2O–CO2 system featured by medium-to-low temperature and low salinity. Stage III FIs contain only L-type, with homogenization temperatures and salinities of 125.5–244.6 °C and 2.56–4.94 wt% NaCl eqv., respectively. Stage III fluids belong to a NaCl-H2O system characterized by low temperature and salinity. The δ18Ofluid and δDfluid values of quartz and calcite are of −4.70 to 5.50‰ and − 144.8 to −121.8‰, respectively, indicating that the Hua'naote early-ore fluids were mainly derived from the magma with minor meteoric water input. The Hua'naote sulfides have δ34SCDT = −0.3 to 8.2‰ (mainly 0–2‰ and 5–8‰), and 206Pb/204Pb = 18.304–18.483, 207Pb/204Pb = 15.552–15.683 and 208Pb/204Pb = 38.104–38.350. The sulfur and lead isotope evidence suggests that the ore metals were sourced primarily from deep-seated magma with minor upper crustal input. We suggest that the Hua'naote Ag-Pb-Zn deposit is best classified as intrusion-related, fractures-controlled medium-temperature hydrothermal vein-type deposit.