Thermodynamic modelling of a cooling C–O–H fluid–graphite system: implications for hydrothermal graphite precipitation

Carbon-saturated crustal fluids in the C–O–H system comprise H₂O, CO₂ and CH₄ as the most important fluid species. Graphite precipitation from a cooling C–O–H is discussed for two different systems, namely for a fluid–rock system in which no transfer of atomic oxygen and hydrogen between the fluid and the rock is possible (closed fluid system), and for an open fluid system. Thermodynamic model calculations show that the graphite-forming reactions and the graphite precipitation potential are different for these two systems. Furthermore, the calculations demonstrate that for both systems, the following factors play a role in determining the graphite precipitation potential, i.e. (1) the redox state of the fluid, (2) the initial pressure and temperature conditions and (3) whether cooling is combined with decompression. Open and closed fluid system graphite precipitation can be distinguished from each other using fluid inclusion and stable carbon isotope studies. The results of this study provide insight in the formation of hydrothermal graphite deposits.     

Experimental study of the apatite–carbonate–H2O system at P = 0.5 GPa and T = 1200°C: Efficiency of fluid transport in carbonatite

Partitioning of more than 35 elements between coexisting phases in the apatite (Apt)–carbonate (Carb)–H₂O system was studied experimentally at P = 0.5 GPa and T = 1200°C for estimation of the efficiency of fluid transport during the formation of carbonatite in platform alkaline intrusions. The interphase partition coefficients of elements (D) range from n × 10^–2 to 100 and higher, which provides evidence for their effective fractionation in the system. The following elements were distinguished: (1) Apt-compatible (REE, Y, Th, Cu, and W), which are concentrated in apatite; (2) hydrophile (Na, K, Mg, Ba, S, Mn, Pb, U, W, and Re), which are preferably distributed into fluid or the carbonate melt. The high hydrophilicity of alkali metals controls the alkaline character of postmagmatic fluids and related metasomatic rocks, whereas the high D(Fl/Apt) and D(Fl/L_Carb) for S, Zr, W, Re, and U show their high potential in relation to U–W–Re mineralization.

     

Stability of methane in reduced C–O–H fluid at 6.3 GPa and 1300–1400°C

The composition of a reduced C–O–H fluid was studied by the method of chromatography–mass spectrometry under the conditions of 6.3 GPa, 1300–1400°C, and fO₂ typical of the base of the subcratonic lithosphere. Fluids containing water (4.4–96.3 rel. %), methane (37.6–0.06 rel. %), and variable concentrations of ethane, propane, and butane were obtained in experiments. With increasing fO₂, the proportion of the CH₄/C₂H₆ peak areas on chromatograms first increases and then decreases, whereas the CH₄/C₃H₈ and CH₄/C₄H₁₀ ratios continually decrease. The new data show that ethane and heavier HCs may be more stable to oxidation, than previously thought. Therefore, when reduced fluids pass the “redox-front,” carbon is not completely released from the fluid and may be involved in diamond formation.     

Diamond formation in the system MgO–SiO2–H2O–C at 7.5 GPa and 1,600°C

Diamond crystallization has been studied in the SiO₂–H₂O–С, Mg₂SiO₄–H₂O–С and H₂O–С subsystems at 7.5 GPa and 1,600°C. We found that dissolution of initial graphite is followed by spontaneous nucleation of diamond and growth of diamond on seed crystals. In 15-h runs, the degree of graphite to diamond transformation [α = M_Dm/(M_Dm + M_Gr)100, where M_Dm is mass of obtained diamond and M_Gr mass of residual graphite] reached 100% in H₂O-rich fluids but was only 35–50% in water-saturated silicate melts. In 40-h runs, an abrupt decrease of α has been established at the weight ratio H₂O/(H₂O + SiO₂) ≤ 0.16 or H₂O/(H₂O + Mg₂SiO₄) ≤ 0.15. Our results indicate that α is a function of the concentration of water, which controls both the kinetics of diamond nucleation and the intensity of carbon mass transfer in the systems. The most favorable conditions for diamond crystallization in the mantle silicate environment at reliable PT-parameters occur in the fluid phase with low concentration of silicates solute. In H₂O-poor silicate melts diamond formation is questionable.     

Experimental Study of Dissolution Rates of Fluorite in HCl–H2O Solutions

The experiments of the dissolution kinetics of fluorite were performed in aqueous HCl solutions over the temperature range of 25–100 °C using a flow-through experimental apparatus. With a constant input of aqueous HCl solution through the reactor, output concentrations of the dissolved species Ca, F, Cl vary with flow rate, as well as with the surface compositions. Measured output concentrations of dissolved species and the pH can be used to determine a rate law for fluorite dissolution. Fluorite dissolution rates are found to be pH dependent. Usually, dissolution rates of fluorite decreases with increasing dissolved Ca in the output solution at 25 and 100 °C. Dissolution rate can be expressed as

Experimental study of the system H3BO3–NaF–SiO2-H2O at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions

The phase state of fluid in the system H₃BO₃–NaF–SiO₂–H₂O was studied at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions. The increase in the solubility of quartz and the high reciprocal solubility of H₃BO₃ and NaF in water fluid at high temperatures are due to the formation of complexes containing B, F, Si, and Na. At 800 °C and 2 kbar, both liquid and gas immiscible phases (viscous silicate-water-salt liquid and three water fluids with different contents of B and F) are dispersed within each other. The Raman spectra of aqueous solutions and viscous liquid show not only a peak of [B(OH)₃]⁰ but also peaks of complexes [B(OH)₄]^–, polyborates [B₄O₅(OH)₄]^2–, [B₃O₃(OH)₄]^–, and [B₅O₆(OH)₄]^–, and/or fluoroborates [B₃F₆O₃]^3–, [BF₂(OH)₂]^–, [BF₃(OH)]^–, and [BF₄]^–. The high viscosity of nonfreezing fluid is due to the polymerization of complexes of polyborates and fluorine-substituted polyborates containing Si and Na. Solutions in fluid inclusions belong to P–Q type complicated by a metastable or stable immiscibility region. Metastable fluid equilibria transform into stable ones owing to the formation of new complexes at 800 ºC and 2 kbar as a result of the interaction of quartz with B-F-containing fluid. At high concentrations of F and B in natural fluids, complexes containing B, F, Si, and alkaline metals and silicate-water-salt dispersed phases might be produced and concentrate many elements, including ore-forming ones. Their transformation into vitreous masses or viscous liquids (gels, jellies) during cooling and the subsequent crystallization of these products at low temperatures (300–400 °C) should lead to the release of fluid enriched in the above elements.     

Experimental research on a new encapsulated heat-generating hydraulic fracturing fluid system

1 IntroductionFracturing plays an important role in increasingthe production and injection and enhancing the final re-covery of oil and gas. At present, the use of ahydroxypropyl guar gum, borate-crosslinked, hydraulicfracturing fluid systemhas become ext…     

Numerical simulation of carbon dioxide migration in a sandstone aquifer considering the fluid–solid coupling

Very limited investigations have been done on the numerical simulation of carbon dioxide (CO₂) migration in sandstone aquifers taking consideration of the interactions between fluid flow and rock stress. Based on the poroelasticity theory and multiphase flow theory, this study establishes a mathematical model to describe CO₂ migration, coupling the flow and stress fields. Both finite difference method (FDM) and finite element method (FEM) were used to discretize the mathematical model and generate a numerical model. A case study was carried out using the numerical model on the Jiangling sandstone aquifer in the Jianghan basin, China. The rock mechanics parameters of reservoir and overlying strata of Jiangling depression were obtained by triaxial tests. A two-dimensional model was then built to simulate carbon dioxide migration in the sandstone aquifer. The numerical simulation analyzes the carbon dioxide migration distribution rule with and without considering capillary pressure. Time-dependent migration of CO₂ in the sandstone aquifer was analyzed, and the result from the coupled model was compared with that from a traditional non-coupled model. The calculation result indicates a good consistency between the coupled model and the non-coupled model. At the injection point, the CO₂ saturation given by the coupled model is 15.39 % higher than that given by the non-coupled model; while the pore pressure given by the coupled model is 4.8 % lower than that given by the non-coupled model. Therefore, it is necessary to consider the coupling of flow and stress fields while simulating CO₂ migration for CO₂ disposal in sandstone aquifers. The result from the coupled model was also sensitized to several parameters including reservoir permeability, porosity, and CO₂ injection rate. Sensitivity analyses show that CO₂ saturation is increased non-linearly with CO₂ injection rate and decreased non-linearly with reservoir porosity. Pore pressure is decreased non-linearly with reservoir porosity and permeability, and increased non-linearly with CO₂ injection rate. When the capillary pressure was considered, the computed gas saturation of carbon dioxide was increased by 10.75 % and the pore pressure was reduced by 0.615 %.     

Transport and Crystallization of Noble Platinum in Supercritical C–O–H Fluid

Experimental data is provided for the transport of platinum in a supercritical C–O–H fluid system. The transfer of platinum in space with its condensation on the surface of native carbon (diamond and amorphous carbon) in the form of micro- and nanocrystals, shapeless particles, and filamentous formations is established for the first time. The dominant participation of platinum in the formation of carbon micro- and nanotubes is demonstrated. The results are important in modeling the formation of noble metal deposits with deep fluid carbon systems.     

Phases of the Fe–C–N system as hosts of mantle carbon and nitrogen: Experimental studies at 7.8 GPa and 1350°C

Parts of the Fe–C–N system were studied in experiments at 7.8 GPa and 1350°C. It was shown that the admixture of nitrogen extends considerably the domain of melt stability in the system at temperatures close to the Fe–Fe₃C eutectic temperatures. Nitrogen solubility in cementite in equilibrium with the nitrogen- rich melt is below the detection limit of the EMPA technique applied. The metal melt is the only nitrogen concentrator (up to 4 wt % of N) in the range of compositions considered. The data obtained permit the conclusion that, in the case of complete dissolution of carbon and nitrogen, which might occur in the enriched mantle, native iron at ~250 km depth should either be completely molten or consist of a melt and carbide of iron.     

Oxygen isotope exchange and disequilibrium between calcite and tremolite in the absence and presence of an experimental C–O–H fluid

Oxygen isotope exchange between minerals during metamorphism can occur in either the presence or the absence of aqueous fluids. Oxygen isotope partitioning among minerals and fluid is governed by both chemical and isotopic equilibria during these processes, which progress by intragranular and intergranular diffusion as well as by surface reactions. We have carried out isotope exchange experiments in two- and three-phase systems, respectively, between calcite and tremolite at high temperatures and pressures. The two-phase system experiments were conducted without fluid either at 1 GPa and 680 °C for 7 days or at 500 MPa and 560 °C for 20 days. Extrapolated equilibrium fractionations between calcite and tremolite are significantly lower than existing empirical estimates and experimental determinations in the presence of small amounts of fluid, but closely match calculated fractionations by means of the increment method for framework oxygen in tremolite. The small fractionations measured in the direct calcite–tremolite exchange experiments are interpreted by different rates of oxygen isotope exchange between hydroxyl oxygen, framework oxygen and calcite during the solid–solid reactions where significant recrystallization occurs. The three-phase system experiments were accomplished in the presence of a large amount of fluid (CO₂+H₂O) at 500 MPa and 560 °C under conditions of phase equilibrium for 5, 10, 20, 40, 80, 120, 160, and 200 days. The results show that oxygen isotope exchange between minerals and fluid proceeds in two stages: first, through a mechanism of dissolution-recrystallization and very rapidly; second, through a mechanism of diffusion and very slowly. Synthetic calcite shows a greater rate of isotopic exchange with fluid than natural calcite in the first stage. The rate of oxygen diffusion in calcite is approximately equal to or slightly greater than that in tremolite in the second stage. A calculation using available diffusion coefficients for calcite suggests that grain boundary diffusion, rather than volume diffusion, has been the dominant mechanism of oxygen transport between the fluid and the mineral grains in the later stage.Editorial responsibility: T.L. Grove     

The Fe–C–O–H–N system at 6.3–7.8 GPa and 1200–1400 °C: implications for deep carbon and nitrogen cycles

Interactions in a Fe–C–O–H–N system that controls the mobility of siderophile nitrogen and carbon in the Fe⁰-saturated upper mantle are investigated in experiments at 6.3–7.8 GPa and 1200–1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe₃C with an N-rich fluid in a graphite-saturated system produce the ε-Fe₃N phase (space group P6₃/mmc or P6₃22) at subsolidus conditions of 1200–1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity (fH₂), fluids vary from NH₃- to H₂O-rich compositions (NH₃/N₂?>?1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H₂O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH₂ and carboxylic acids at unbuffered fH₂ conditions. In unbuffered conditions, N₂ is the principal nitrogen host (NH₃/N₂?≤?0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe₃N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.     

Formation of gold–silver sulfides and native gold in Fe–Ag–Au–S system

We carried out experiments on crystallization of Fe-containing melts FeS₂Ag_0.1–0.1xAu_0.1x (x = 0.05, 0.2, 0.4, and 0.8) with Ag/Au weight ratios from 10 to 0.1. Mixtures prepared from elements in corresponding proportions were heated in evacuated quartz ampoules to 1050 ºC and kept at this temperature for 12 h; then they were cooled to 150 ºC, annealed for 30 days, and cooled to room temperature. The solid-phase products were studied by optical and electron microscopy and X-ray spectroscopy. The crystallization products were mainly from iron sulfides: monoclinic pyrrhotite (Fe_0.47S_0.53 or Fe₇S₈) and pyrite (Fe_0.99S_2.01). Gold–silver sulfides (low-temperature modifications) are present in all synthesized samples. Depending on Ag/Au, the following sulfides are produced: acanthite (Ag/Au = 10), solid solutions Ag_2–xAu_xS (Ag/Au = 10, 2), uytenbogaardtite (Ag/Au = 2, 0.75), and petrovskaite (Ag/Au = 0.75, 0.12). They contain iron impurities (up to 3.3 wt.%). Xenomorphic micro- (<1–5 μm) and macrograins (5–50 μm) of Au–Ag sulfides are localized in pyrite or between the grains of pyrite and pyrrhotite. High-fineness gold was detected in the samples with initial ratio Ag/Au ≤ 2. It is present as fine and large rounded microinclusions or as intergrowths with Au–Ag sulfides in pyrite or, more seldom, at the boundary of pyrite and pyrrhotite grains. This gold contains up to 5.7 wt.% Fe. Based on the sample textures and phase relations, a sequence of their crystallization was determined. At ~1050 ºC, there are probably iron sulfide melt L₁ (Fe,S ? Ag,Au), gold–silver sulfide melt L₂ (Au,Ag,S ? Fe), and liquid sulfur L_S. On cooling, melt L₁ produces pyrrhotite; further cooling leads to the crystallization of high-fineness gold (macrograins from L₁ and micrograins from L₂) and Au–Ag sulfides (micrograins from L₁ and macrograins from L₂). Pyrite crystallizes after gold–silver sulfides by the peritectic reaction FeS + L_S = FeS₂ at ~743 ºC. Elemental sulfur is the last to crystallize. Gold–silver sulfides are stable and dominate over native gold and silver, especially in pyrite-containing ores with high Ag/Au ratios.     

Hydrogen incorporation in enstatite in the system MgO–SiO2–H2O–NaCl

The incorporation of hydrogen in enstatite in a hydrous system containing various amounts of NaCl was investigated at 25 kbar. The hydrogen content in enstatite shows a clear negative correlation to the NaCl-concentration in the system. The most favourable explanation is the reduction of water fugacity due to dilution. Other reasons for the limited hydrogen incorporation at high NaCl levels, such as a significant influence of Na⁺ on the defect chemistry or an exchange between OH^- and Cl⁻in enstatite, appear much less important. A partition coefficient D _Na ^En/Fluid = 0.0013 could be determined, demonstrating that Na is less incompatible in enstatite than H. The new results support the idea that dissolved components have to be considered when the total hydrogen storage capacity in nominally anhydrous minerals is estimated, especially in geological settings with high levels of halogens, such as subduction zones.     

Thermodynamic modeling of binary CH4–CO2 fluid inclusions

An equation of state (EOS) explicit in Helmholtz free energy has been improved to calculate the PVTx and vapor–liquid phase equilibrium properties of CH₄–CO₂ fluid mixture. This EOS, where four mixing parameters are used, is based on highly accurate EOSs recommended by NIST for pure components (CH₄ and CO₂) and contains a simple generalized departure function presented by Lemmon and Jacobsen (1999). Comparison with experimental data available indicates that the EOS can calculate both vapor–liquid phase equilibrium and volumetric properties of this binary fluid system with accuracy close to that of experimental data up to high temperature and pressure within full range of composition. The EOS of CH₄–CO₂ fluid, together with the updated Gibbs free energy model of solid CO₂ (dry ice), is applied to calculate the CH₄ content (x_CH4) and molar volume (V_m) of the CH₄–CO₂ fluid inclusion based on the assumption that the volume of an inclusion keeps constant during heating and cooling. $V_{\text{m}}-x_{{\text{CH}}_4}$ diagrams are presented, which describe phase transitions involving vapor, liquid and CO₂ solid phases of CH₄–CO₂ fluid inclusions. Isochores of CH₄–CO₂ inclusions at given $x_{{\text{CH}}_4}$ and V_m can be easily calculated from the improved EOS.     

Genesis of the Fuxing porphyry Cu deposit in Eastern Tianshan,China: Evidence from fluid inclusions and C–H–O–S–Pb isotope systematics

The Fuxing porphyry Cu deposit is a recently discovered deposit in Eastern Tianshan, Xinjiang, northwestern China. The Cu mineralization is associated with the Fuxing plagiogranite porphyry and monzogranite, mainly presenting as various types of hydrothermal veins or veinlets in alerted wall rocks, with potassic, chlorite, phyllic, and propylitic alteration developed. The ore-forming process can be divided into four stages: stage I barren quartz veins, stage II quartz–chalcopyrite–pyrite veins, stage III quartz–polymetallic sulfide veins and stage IV quartz–calcite veins. Four types of fluid inclusions (FIs) can be distinguished in the Fuxing deposit, including hypersline (H-type), vapor-rich two-phase (V-type), liquid-rich two-phase (L-type), and trace amounts of pure vapor inclusions (P-type), but only the stage I quartz contains all types of FIs. The stages II and III quartz have two types of FIs, with exception of H- and P-types. In stage IV quartz minerals, only the L-type inclusions can be observed. The FIs in quartz of stages I, II, III and IV are mainly homogenized at temperatures of 357–518 °C, 255–393 °C, 234–322 °C and 145–240 °C, with salinities of 1.9–11.6 wt.% NaCl equiv., 1.6–9.6 wt.% NaCl equiv., 1.4–7.7 wt.% NaCl equiv. and 0.9–3.7 wt.% NaCl equiv., respectively. The ore-forming fluids of the Fuxing deposit are characterized by high temperature, moderate salinity and relatively oxidized condition. Carbon, hydrogen and oxygen isotopic compositions of quartz indicate that the ore-forming fluids were gradually evolved from magmatic to meteoric in origin. Sulfur and lead isotopes suggest that the ore-forming materials were derived from a deep-seated magma source. The Cu mineralization in the Fuxing deposit occurred at a depth of ~ 1 km, and the changes of oxygen fugacity, decompression boiling, and local mixing with meteoric water were most likely critical for the formation of the Fuxing Cu deposit.     

An experimental study of dissolution–reprecipitation in fluorapatite: fluid infiltration and the formation of monazite

In a series of timed experiments, monazite inclusions are induced to form in the Durango fluorapatite using 1 and 2 N HCl and H₂SO₄ solutions at temperatures of 300, 600, and 900°C and pressures of 500 and 1,000 MPa. The monazite inclusions form only in reacted areas, i.e. depleted in (Y+REE)+Si+Na+S+Cl. In the HCl experiments, the reaction front between the reacted and unreacted regions is sharp, whereas in the H₂SO₄ experiments it ranges from sharp to diffuse. In the 1 N HCl experiments, Ostwald ripening of the monazite inclusions took place both as a function of increased reaction time as well as increased temperature and pressure. Monazite growth was more sluggish in the H₂SO₄ experiments. Transmission electron microscopic (TEM) investigation of foils cut across the reaction boundary in a fluorapatite from the 1 N HCl experiment (600°C and 500 MPa) indicate that the reacted region along the reaction front is characterized by numerous, sub-parallel, 10–20 nm diameter nano-channels. TEM investigation of foils cut from a reacted region in a fluorapatite from the 1 N H₂SO₄ experiment at 900°C and 1,000 MPa indicates a pervasive nano-porosity, with the monazite inclusions being in direct contact with the surrounding fluorapatite. For either set of experiments, reacted areas in the fluorapatite are interpreted as replacement reactions, which proceed via a moving interface or reaction front associated with what is essentially a simultaneous dissolution–reprecipitation process. The formation of a micro- and nano-porosity in the metasomatised regions of the fluorapatite allows fluids to permeate the reacted areas. This permits rapid mass transfer in the form of fluid-aided diffusion of cations to and from the growing monazite inclusions. Nano-channels and nano-pores also serve as sites for nucleation and the subsequent growth of the monazite inclusions.