Experimental study of the alteration process of labradorite in acid hydrothermal solutions

Labradorite was altered artificially by HC1 solution ranging from M = 1 to M = 0.003 at 245 and 230°C. The products of alteration were examined by X-ray diffraction, electron microscopy, electron diffraction, infrared spectroscopy and the electron microprobe and the solution was analyzed chemically.Amorphous silica only was formed in solutions with M_HCl = 1 and M_HCl = 0.3. In a solution with M_HCl = 0.2, amorphous silica was initially formed, later dissolved and replaced by kaolinite. A mixture of microcrystalline boehmite and amorphous aluminosilicate was formed, altering to kaolinite in solutions with M_HCl = 0.1 and 0.3. Small amounts of kaolinite were initially formed but the alteration soon stopped in solution with M_HCl = 0.003. Relationships between the alteration processes and pH of the solutions can be roughly explained by using solubility diagrams assuming the congruent dissolution of labradorite and precipitation of the products in partial equilibrium. However, these assumptions are not valid with strongly acid solutions.The rate of dissolution of labradorite is controlled not only by its surface area, but also by the diffusion of matter through the layer of alteration products.     

Sulfur speciation in natural hydrothermal waters, Iceland

The speciation of aqueous dissolved sulfur was determined in hydrothermal waters in Iceland. The waters sampled included hot springs, acid-sulfate pools and mud pots, sub-boiling well discharges and two-phase wells. The water temperatures ranged from 4 to 210 °C, the pH_T was between 2.20 and 9.30 at the discharge temperature and the SO₄ and Cl concentrations were 0.020-52.7 and <0.01-10.0 mmol kg⁻¹, respectively. The analyses were carried out on-site within ∼10 min of sampling using ion chromatography (IC) for sulfate (SO₄²⁻), thiosulfate (S₂O₃²⁻) and polythionates (S_xO₆²⁻) and titration and/or colorimetry for total dissolved sulfide (S²⁻). Sulfite (SO₃²⁻) could also be determined in a few cases using IC. Alternatively, for few samples in remote locations the sulfur oxyanions were stabilized on a resin on site following elution and analysis by IC in the laboratory. Dissolved sulfate and with few exceptions also S²⁻ were detected in all samples with concentrations of 0.02-52.7 mmol kg⁻¹ and <1-4100 μmol kg⁻¹, respectively. Thiosulfate was detected in 49 samples of the 73 analyzed with concentrations in the range of <1-394 μmol kg⁻¹ (S-equivalents). Sulfite was detected in few samples with concentrations in the range of <1-3 μmol kg⁻¹. Thiosulfate and SO₃²⁻ were not detected in <100 °C well waters and S₂O₃²⁻ was observed only at low concentrations (<1-8 μmol kg⁻¹) in ∼200 °C well waters. In alkaline and neutral pH hot springs, S₂O₃²⁻ was present in significant concentrations sometimes corresponding to up to 23% of total dissolved sulfur (S_TOT). In steam-heated acid-sulfate waters, S₂O₃²⁻ was not a significant sulfur species. The results demonstrate that S₂O₃²⁻ and SO₃²⁻ do not occur in the deeper parts of <150 °C hydrothermal systems and only in trace concentrations in ∼200-300 °C systems. Upon ascent to the surface and mixing with oxygenated ground and surface waters and/or dissolution of atmospheric O₂, S²⁻ is degassed and oxidized to SO₃²⁻ and S₂O₃²⁻ and eventually to SO₄²⁻ at pH >8. In near-neutral hydrothermal waters the oxidation of S²⁻ and the interaction of S²⁻ and S⁰ resulting in the formation of S_x²⁻ are considered important. At lower pH values the reactions seemed to proceed relatively rapidly to SO₄²⁻ and the sulfur chemistry of acid-sulfate pools was dominated by SO₄²⁻, which corresponded to >99% of S_TOT. The results suggest that the aqueous speciation of sulfur in natural hydrothermal waters is dynamic and both kinetically and source-controlled and cannot be estimated from thermodynamic speciation calculations.     

Experimental study of natural pyrochlore and niobium oxide solubility in Alkaline hydrothermal solutions

The concentration and temperature dependences of pyrochlore and Nb oxide solubility in Na₂CO₃ and Na₂СO₃ + NaF aqueous solutions with concentrations from 0.01 to 2.0 m at 300–550°C and 50 and 100 MPa (the Co–CoO buffer) are studied. It is established that the Nb equilibrium content in the solution increases at 550°C and 100 MPa with an increase in mNa₂CO₃ and reaches the value of 10^–4 m. The Nb₂O₅ solubility almost does not change as the concentration of Na₂CO₃ increases and is found within 10^–6 to 10^–5.5 m.     

Experimental determination of the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions to 400°C

The solubility of silver sulphide (acanthite/argentite) has been measured in aqueous sulphide solutions between 25 and 400°C at saturated water vapour pressure and 500 bar to determine the stability and stoichiometry of sulphide complexes of silver(I) in hydrothermal solutions. The experiments were carried out in a flow-through autoclave, connected to a high-performance liquid chromatographic pump, titanium sampling loop, and a back-pressure regulator on line. Samples for silver determination were collected via the titanium sampling loop at experimental temperatures and pressures. The solubilities, measured as total dissolved silver, were in the range 1.0 × 10⁻⁷ to 1.30 × 10⁻⁴ mol kg⁻¹ (0.01 to 14.0 ppm), in solutions of total reduced sulphur between 0.007 and 0.176 mol kg⁻¹ and pH_T,p of 3.7 to 12.7. A nonlinear least squares treatment of the data demonstrates that the solubility of silver sulphide in aqueous sulphide solutions of acidic to alkaline pH is accurately described by the reactions0.5Ag₂S(s) + 0.5H₂S(aq) = AgHS(aq) K_s,1110.5Ag₂S(s) + 0.5H₂S(aq) + HS⁻ = Ag(HS)2− K_s,122Ag₂S(s) + 2HS⁻ = Ag₂S(HS)22− K_s,232where AgHS(aq) is the dominant species in acidic solutions, Ag(HS)2− under neutral pH conditions and Ag₂S(HS)22− in alkaline solutions. With increasing temperature the stability field of Ag(HS)2− increases and shifts to more alkaline pH in accordance with the change in the first ionisation constant of H₂S(aq). Consequently, Ag₂S(HS)22− is not an important species above 200°C. The solubility constant for the first reaction is independent of temperature to 300°C, with values in the range logK_s,111 = −5.79 (±0.07) to −5.59 (±0.09), and decreases to −5.92 (±0.16) at 400°C. The solubility constant for the second reaction increases almost linearly with inverse temperature from logK_s,122 = −3.97 (±0.04) at 25°C to −1.89 (±0.03) at 400°C. The solubility constant for the third reaction increases with temperature from logK_s,232 = −4.78 (±0.04) at 25°C to −4.57 (±0.18) at 200°C. All solubility constants were found to be independent of pressure within experimental uncertainties. The interaction between Ag⁺ and HS⁻ at 25°C and 1 bar to form AgHS(aq) has appreciable covalent character, as reflected in the exothermic enthalpy and small entropy of formation. With increasing temperature, the stepwise formation reactions become progressively more endothermic and are accompanied by large positive entropies, indicating greater electrostatic interaction. The aqueous speciation of silver is very sensitive to fluid composition and temperature. Below 100°C silver(I) sulphide complexes predominate in reduced sulphide solutions, whereas Ag⁺ and AgClOH⁻ are the dominant species in oxidised waters. In high-temperature hydrothermal solutions of seawater salinity, chloride complexes of silver(I) are most important, whereas in dilute hydrothermal fluids of meteoric origin typically found in active geothermal systems, sulphide complexes predominate. Adiabatic boiling of dilute and saline geothermal waters leads to precipitation of silver sulphide and removal of silver from solution. Conductive cooling has insignificant effects on silver mobility in dilute fluids, whereas it leads to quantitative loss of silver for geothermal fluids of seawater salinity.     

在热液内金属铅的物种形式原位观测实验

文章应用高温高压腔连接紫外_可见谱仪研究了150℃条件下铅在含氯溶液里的物种形式。实验的体系是Pbs_NaCl_HCl_H2O。实验结果表明,铅在含氯溶液里的物种形成有2个步骤:Pb2 Cl-→PbCl ,PbCl Cl-→PbCl2,处于平衡态时为PbCl2。溶液的氯浓度、温度、反应延续时间影响物种形式。     

Solubility of gold in hydrothermal chloride solutions

The solubility of gold has been determined in chloride solutions in the temperature range 300–500°C corresponding to the inferred range for the formation of “hypothermal” gold deposits. The solutions were buffered with respect to HC1 by a K-feldspar-muscovite-quartz assemblage, and to oxygen by the assemblage haematite-magnetite. Solubilities increased rapidly with temperature from about 10 p.p.m. at 300°C, to 500 and 1000 p.p.m. at 500°C at 1000 and 2000 bar, respectively.These results are discussed in terms of possible solution species in this high-temperature region where molecular behaviour predominates in the solution equilibria. It is suggested that gold and other metals may be transported to the site of ore-deposition in undersaturated high-temperature solutions. Ore deposition may take place at lower temperatures where ionic gold chloride or sulfide species dominate the chemistry of the ore solutions.     

Experimental study of hydrothermal alteration of carbonate rocks by Na-F solutions under flow conditions

Na-F solutions with different pH were allowed to react under flow conditions with limestone, dolomite and siderite at 300 and 400°C at 500 bars, in order to understand the geochemical characteristics of the interaction between rock and F-bearing hydrothermal solutions. The mineralogical and chemical composition of these carbonate rocks was studied by chemical analysis, XRD and SEM/EDAX before and after reaction with Na-F solutions. Based on an approximate thermodynamic calculation the formation of alteration phases is discussed. The pH value at room conditions and the contents of K, Na, Ca, Mg, Fe, F, SiO₂ and total dissolved CO₂ in solution after interaction with carbonate rocks were determined. From solution chemistry data, it is found that the amount of Na and F in the reacted solutions seemed to have roughly similar fluctuations with time, and hence, carbonate might be an effective precipitating agent for Fe in hydrothermal solutions. The present experimental study demonstrates that hydrothermal metasomatism played a very important role in the formation of the Baiyun Ebo iron deposit.     

Marcasite precipitation from hydrothermal solutions

Pyrite and marcasite were precipitated by both slow addition of aqueous Fe²⁺ and SiO₃²⁻ to an H₂S solution and by mixing aqueous Fe²⁺ and Na₂S₄ solutions at 75°C. H₂S₂ or HS₂⁻ and H₂S₄ or HS₄⁻ were formed in the S₂O₃²⁻ and Na₂S₄ experiments, respectively. Marcasite formed at pH < pK₁ of the polysulfide species present (for H₂S₂, pK₁ = 5.0; for H₂S₄, pK₁ = 3.8 at 25°C). Marcasite forms when the neutral sulfane is the dominant polysulfide, whereas pyrite forms when mono-or divalent polysulfides are dominant. In natural solutions where H₂S₂ and HS₂ are likely to be the dominant polysulfides, marcasite will form only below pH 5 at all temperatures.

The pH-dependent precipitation of pyrite and marcasite may be caused by electrostatic interactions between polysulfide species and pyrite or marcasite growth surfaces: the protonated ends of H₂S₂ and HS₂ are repelled from pyrite growth sites but not from marcasite growth sites. The negative ions HS₂ and S₂²⁻ are strongly attracted to the positive pyrite growth sites. Masking of 1π_g^* electrons in the S₂ group by the protons makes HS₂ and H₂S₂ isoelectronic with AsS²⁻ and As₂²⁻, respectively ( et al., 1981). Thus, the loellingitederivative structure (marcasite) results when both ends of the polysulfide are protonated.

Marcasite occurs abundantly only for conditions below pH 5 and where H₂S₂ was formed near the site of deposition by either partial oxidation of aqueous H₂S by O₂ or by the reaction of higher oxidation state sulfur species that are reactive with H₂S at the conditions of formation e.g., S₂O₃²⁻ but not SO₄²⁻. The temperature of formation of natural marcasite may be as high as 240°C ( and , 1985), but preservation on a multimillion-year scale seems to require post-depositional temperatures of below about 160°C ( , 1973; and , 1985).     

Experimental study of the interaction of mineral-forming hydrothermal solutions with oil and their joint migration

Interaction between oil and hydrothermal solutions of different compositions was experimentally studied in a wide range of temperature (260–490°C) and pressures (8–150 MPa). This study was based on a new technique involving simultaneous occurrence of water-hydrocarbon interaction and growth of quartz, calcite, and fluorite crystals with fluid inclusions from the same solution. Fluid inclusions were studied to characterize the behavior of oil and aqueous solutions at elevated and high temperatures and pressures. It was shown that, owing to interaction with hydrothermal solutions, oil is intensely removed from the source rock and accumulated in the frontal part of hydrothermal convective flow. During this process, the oil is partially transformed into hydrocarbons, light oil, semiliquid and solid bitumens. At temperatures of 300–350°C and pressures of 50–100 MPa, oil and its fractionation products migrate in hydrothermal solution mainly in a drop-liquid state. At higher temperatures (360–395°C), when the oil/water ratio in the initial mixture is no higher than 1/70–1/35, liquid and gaseous hydrocarbons are completely dissolved in hydrothermal solutions forming a complex homogenous water-hydrocarbon fluid. The fluid can exist and migrate in this state, but it becomes heterogeneous with decreasing P-T parameters. Under favourable structural and lithological conditions, this can lead to the formation of displaced oil-and-gas deposits, with oil enriched in light components. The experiments unambiguously confirmed the concept that bitumen inclusions in minerals can serve as indicators of hydrocarbon migration paths in the Earth’s crust.     

Experimental study of brucite dissolution and precipitation in aqueous solutions: surface speciation and chemical affinity control

Dissolution and precipitation rates of brucite (Mg(OH)₂) were measured at 25°C in a mixed-flow reactor as a function of pH (2.5 to 12), ionic strength (10⁻⁴ to 3 M), saturation index (−12 < log Ω < 0.4) and aqueous magnesium concentrations (10⁻⁶ to 5·10⁻⁴ M). Brucite surface charge and isoelectric point (pH_IEP) were determined by surface titrations in a limited residence time reactor and electrophoretic measurements, respectively. The pH of zero charge and pH_IEP were close to 11. A two-pK, one site surface speciation model which assumes a constant capacitance of the electric double layer (5 F/m²) and lack of dependence on ionic strength predicts the dominance of >MgOH₂⁺ species at pH < 8 and their progressive replacement by >MgOH° and >MgO⁻ as pH increases to 10-12. Rates are proportional to the square of >MgOH₂⁺ surface concentration at pH from 2.5 to 12. In accord with surface speciation predictions, dissolution rates do not depend on ionic strength at pH 6.5 to 11. Brucite dissolution and precipitation rates at close to equilibrium conditions obeyed TST-derived rate laws. At constant saturation indices, brucite precipitation rates were proportional to the square of >MgOH₂⁺ concentration. The following rate equation, consistent with transition state theory, describes brucite dissolution and precipitation kinetics over a wide range of solution composition and chemical affinity:

     

The speciation of mercury in hydrothermal systems,with applications to ore deposition

Hg in hydrothermal systems is generally thought to be transported as Hg-S complexes. However, the abundance of Hg⁰_vap, in geothermal emissions suggests that Hg⁰_eq, is present in the liquid phase of geothermal systems. Calculations for reducing fluids (HS^? dominant over SO⁼₄) in equilibrium with cinnabar indicate that Hg⁰_eq, can be quite abundant relative to other species at temperatures above 200°C. Increasing pH and temperature, and decreasing total S, ionic strength, and pO₂ all promote the abundance of Hg⁰_eq. When a vapor phase develops from a geothermal liquid, Hg partitions strongly into the vapor as Hg⁰_vap. Vapor transport at shallow level then results in the formation of Hg halos around shallow aquifers as well as in a flux of Hg to the atmosphere. Hg deposition may occur in response to mixing with oxidizing or acidic water, turning Hg⁰_eq, into Hg⁺⁺, with subsequent cinnabar precipitation. When pyrite is the stable Fe-sulfide, cinnabar solubility is at its lowest, so cinnabar + pyrite assemblages are common. Cinnabar + hematite ± pyrite can precipitate from more oxidized or S-poor water. Hg⁰_liq, can occur as a primary mineral, in coexistence with all common Fe-sulfides and oxides. Cinnabar ± Hg⁰_liq cannot coexist with pyrrhotite or magnetite at temperatures between 100° and 250°C. Evidence from Hg deposits indicates that many formed from dilute hydrothermal fluids in which Hg probably occurred as Hg⁰_eq. In S-rich systems, Hg may occur as Hg-S complexes, and in saline waters it can occur as Hg-Cl complexes.     

Thermodynamics of NaOH(aq) in hydrothermal solutions

Apparent molar volumes and osmotic coefficients of NaOH solutions, calculated from critically evaluated literature data on volumes and vapor pressures, were used to fit the Pitzer equations to yield ion-interaction parameters as a function of temperature and pressure. These parameters allow the calculation of osmotic and activity coefficients from 0–350°C, saturation pressure to about 400 bars and 0–10 molal NaOH, and volumetric properties at saturation pressure over the same temperature and concentration range. Because the parameters for osmotic and activity coefficients above 300°C are based on less precise data, and because of possible ion-pairing above this temperature, calculated values above 300°C are considered only as best estimates available at this time. Partial molar volumes at infinite dilution calculated for NaOH are combined with literature data for NaCl, HCl, and H₂O to yield the pressure dependence of the ionization of water to 200°C, and are also combined with the potentiometric data of Sweeton et al. (1974) on the ionization of water to calculate the infinitely dilute partial molar volume of HCl to 300°C. Specific volumes of NaOH solutions at saturation pressure and up to 350°C are also calculated and tabulated.     

Transfers of titanium,zirconium, and hafnium in high-temperature solutions

At 500–600°C and 500–800 atm, in alkaline solutions, two mechanisms of the migrations of Ti, Zr, and Hf are experimentally indicated: a) in the absence of fluorine and other halogens, these metals migrate as titanates, zirconates, and hafnates of K and Na, the forms which are conducive to their dissipation but not deposition-accumulation in the rocks, within a wide range of temperature, as long as the pH of the solution remains alkaline; b) in the presence of fluorine, Ti, Zr, and Hf migrate as fluoride complexes (with Na and K) from which they may be liberated by hydrolysis and deposited at decreasing temperature, as the corresponding oxides.     

Experimental study of aluminum speciation in fluoride-rich supercritical fluids

The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)₄⁻ dominates Al speciation and is formed according to the reaction 0.5 NaAl₃Si₃O₁₂H_2(cr)+2 H₂O = 0.5 NaAlSi₃O_8(cr)+Al(OH)₄⁻+H⁺. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)₄⁰_(aq) or NaAl(OH)₃Cl_(aq)⁰. The calculated constant for the reaction Al(OH)₄⁻+Na⁺=NaAl(OH)₄⁰_(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)₃F_(aq)⁰ and NaAl(OH)₂F₂⁰_(aq), according to 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+HF_(aq)⁰+H₂O = 0.5 NaAlSi₃O_8(cr)+ NaAl(OH)₃F_(aq)⁰+H⁺, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl₃Si₃O₁₂H_2(cr)+Na⁺+2 HF_(aq)⁰ = 0.5 NaAlSi₃O_8(cr)+NaAl(OH)₂F₂⁰_(aq)+H⁺, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)₂F₂⁰_(aq) in low-density fluids also increases relative to NaAl(OH)₃F_(aq)⁰. These complexes, together with Al(OH)₂F_(aq)⁰ and AlOHF₂⁰_(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.     

Experimental study of the stability of aluminate-borate complexes in hydrothermal solutions

Formation of aqueous aluminate-borate complexes was characterized at 25°C using ²⁷Al NMR spectroscopy, and at 50-200°C via measurements of gibbsite and boehmite solubility in the presence of boric acid. ²⁷Al spectra performed at pH = 9 in Al-B solution with m(B) = 0.02 show the presence of two peaks at 80.5 and 74.5 ppm which correspond to Al(OH)₄⁻ and a single Al-substituted Q¹_Al dimer, Al(OH)₃OB(OH)₂⁻, respectively. In 0.08 m and 0.2 m borate solution, a third peak appears at 68.5 ppm which can be assigned to the Q²_Al trimer Al(OH)₂O₂(B(OH)₂)₂⁻. These chemical shifts are close to those measured for Al(OH)₃OSi(OH)₃⁻ and Al(OH)₂O₂(Si(OH)₃)₂⁻ (74 and 69.5 ppm, respectively; Pokrovski et al., Min. Mag.62a (1998), 1194) which demonstrates the similar structure of Al-B and Al-Si complexes formed in alkaline solutions. Gibbsite and boehmite solubility were measured in weakly basic solutions as a function of boric acid concentration at 50°C and 78 to 200°C, respectively. Equilibrium was reached within several days at m(B) = 0.01-0.1, but more slowly at higher boron concentrations, and at 50°C and m(B) = 0.2, Al concentration increased continuously during at least 3 months as a result of the sluggish formation of Al-polyborates. The equilibrium constant of the reaction Al(OH)₄⁻ + B(OH)₃⁰_(aq) = Al(OH)₃OB(OH)₂⁻ + H₂O decreases very slowly with increasing temperature to 200°C. The log K values are 1.58 ± 0.10, 1.46 ± 0.10, 1.52 ± 0.15, and 1.25 ± 0.15 at 50, 78, 150 and 200°C, respectively, which result in the following values of the standard thermodynamic properties for this reaction: Δ_rG⁰ = −9.22 ± 3.25 kJ/mol, Δ_rH⁰ = −4.6 ± 2.5 kJ/mol, Δ_rS⁰ = 15.5 ± 6.9 J/mol K. The thermodynamic data generated in this study indicate that Al-B complexes can dominate aqueous aluminum speciation in solutions containing ≥0.7 g/L of boron at temperature to at least 400°C.     

The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.