Experimental study of Pd hydrolysis in aqueous solutions at 25–70°C

The hydrolysis of the Pd²⁺ ion in HClO₄ solutions was examined at 25–70°C, and the thermodynamic constants of equilibrium K ₍₁₎⁰ and K ₍₂₎⁰were determined for the reactions Pd²⁺ + H₂O = PdOH⁺ + H⁺ and Pd²⁺ + 2H₂O = Pd(OH)₂⁰ + 2H⁺, respectively. The values of log K ₍₁₎⁰ = −1.66 ± 0.5 (25°C) and −0.65 ± 0.25 (50°C) and log K ₍₂₎⁰ = −4.34 ± 0.3 (25°C) and −3.80 ± 0.3 (50°C) were derived using the solubility technique at 0.95 confidence level. The values of log K ₍₁₎⁰ = −1.9 ± 0.6 (25°C), −1.0 ± 0.4 (50°C), and −0.5 ± 0.3 (70°C) were obtained by spectrophotometric techniques. The palladium ion is significantly hydrolyzed at elevated temperatures (50–70°C) even in strongly acidic solutions (pH 1–1.5), and its hydrolysis is enhanced with increasing temperature.     

Experimental study of the influence of sulfur on gold sorption by bitumen at 200–400°C and 1 kbar Pressure

The effect of sulfur on the sorption of gold by carbonaceous matter (CM) was investigated under hydrothermal conditions (200–400°C and 1 kbar) using the autoclave-ampoule method. The model CM was represented by asphaltenes fractionated from the lignite of the Pavlovskoe coal field. The source of gold was the walls of the Au container, which were dissolved in water under the experimental conditions. Sulfur was added as finely ground pyrite (C-S-Fe-O-H-Au system) or elemental sulfur powder (C-S-O-H-Au system). The contents of Au were measured by atomic absorption spectrometry with electrothermal atomization in quenched aqueous solutions (WF), soluble organic fraction (SF), and insoluble residue (kerogen). The lowest Au concentration was detected in the WF, −8.96 < logmAu < −6.32. The Au concentration is higher in the SF (−5.02 < logmAu < −4.34) and increases by more then an order of magnitude in the kerogen, −3.94 < logmAu < −2.33. The IR spectra of the experimental products showed that sulfur was accumulated in the kerogen, whereas no C-S functional groups were observed in the SF. This is the reason for the negligible influence of sulfur in this system on Au concentration in the SF. The maximum Au concentration was detected in the kerogen in the presence of pyrite, which was transformed into pyrrhotite at 400°C. Thus, iron sulfides promote Au uptake by kerogen from ore-bearing hydrothermal fluids.     

Experimental calibration of vanadium partitioning and stable isotope fractionation between hydrous granitic melt and magnetite at 800 °C and 0.5 GPa

Vanadium has multiple oxidation states in silicate melts and minerals, a property that also promotes fractionation of its isotopes. As a result, vanadium isotopes vary during magmatic differentiation, and can be powerful indicators of redox processes at high temperatures if their partitioning behaviour can be determined. To quantify the partitioning and isotope fractionation factor of V between magnetite and melt, piston cylinder experiments were performed in which magnetite and a hydrous, haplogranitic melt were equilibrated at 800 °C and 0.5 GPa over a range of oxygen fugacities (\({f_{{{\text{O}}_{\text{2}}}}}\)), bracketing those of terrestrial magmas. Magnetite is isotopically light with respect to the coexisting melt, a tendency ascribed to the VI-fold V³⁺ and V⁴⁺ in magnetite, and a mixture of IV- and VI-fold V⁵⁺ and V⁴⁺ in the melt. The magnitude of the fractionation factor systematically increases with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\) relative to the Fayalite–Magnetite–Quartz buffer (FMQ), from ?⁵¹V_mag-gl = ? 0.63?±?0.09‰ at FMQ ? 1 to ? 0.92?±?0.11‰ (SD) at ≈?FMQ?+?5, reflecting constant V³⁺/V⁴⁺ in magnetite but increasing V⁵⁺/V⁴⁺ in the melt with increasing log\({f_{{{\text{O}}_{\text{2}}}}}\). These first mineral-melt measurements of V isotope fractionation factors underline the importance of both oxidation state and co-ordination environment in controlling isotopic fractionation. The fractionation factors determined experimentally are in excellent agreement with those needed to explain natural isotope variations in magmatic suites. Furthermore, these experiments provide a useful framework in which to interpret vanadium isotope variations in natural rocks and magnetites, and may be used as a potential fingerprint the redox state of the magma from which they crystallise.     

Formation of N–С–О–Н molecules and complexes in the basalt–basaltic andesite melts at 1.5 Gpa and 1400°C in the presence of liquid iron alloys

The contents and speciation of nitrogen, carbon, and hydrogen were determined in basalt–basaltic andesite melts in equilibrium with liquid Fe alloys at 1.5 Gpa, 1400°C, and oxygen fugacity (fO₂) 1.4–1.9 log units below that of the Fe–FeO buffer (ΔlogfO₂(IW) =–1.4 …–1.9). Experiments were carried out on a piston- cylinder type apparatus using welded Pt capsules in the presence of excess С (graphite). Starting mixture consisted of natural ferrobasaltic glass and silicon nitride (Si₃N₄) as nitrogen source in the system. Experimental quench products representing glasses with spherical inclusions of iron alloy were analyzed using electron microprobe, Raman, and IR spectroscopy. With increase of Si₃N₄ in the starting mixture and, respectively, decrease of fO₂, silicate melt forming during experiments became depleted in FeO and enriched in SiO₂. It was established that the nitrogen content in the glasses increases from 0.13 to 0.44 wt % with decrease of ΔlogfO₂(IW) from–1.4 to–1.9, whereas C content in the first approximation remains constant within 1.18–1.13 wt %, while the total water content (ОН^– + Н₂О) determined by IR spectroscopy decreases from 4.91 to 1.20 wt %. The N (0.13–0.48 wt %) and C (0.75–2.26 wt %) contents determined in the Fe alloy show no clear correlation with fO₂. The IR and Raman spectroscopic study of the glasses indicates the formation of molecules and complexes with bonds N–H (NH₃, NH₂ ^?, NH₂ ⁺, NH₄ ⁺), Н–О (Н₂О, OH^–), С–Н (СН₄) as well as N₂ and Н₂ molecules in silicate melts. IR spectra also reveal the presence of complexes with С=О, С–N bonds and СО₂ molecules. Obtained data are compared with results of previous studies on the solubility and speciation of N, С, and Н in the model FeO–Na₂O–SiO₂–Al₂O₃ melts in equilibrium with liquid iron alloys at 1.5 GPa (1400°C) and 4 GPa (1550°C) (Kadik et al., 2011, 2015).     

Experimental study on the electrical resistivity of soil–cement admixtures

Recently in China, soil–cement is widely used to improve the soft ground in the highway construction engineering. Literature studies are mainly investigating the mechanical properties of the soil–cement, while its properties of the electrical resistivity are not well addressed. In this paper, the properties of the electrical resistivity of the reconstituted soil-cement and the in situ soil–cement columns are investigated. The test results show that the electrical resistivity of the soil–cement increases with the increase in the cement-mixing ratio and curing time, whereas it decreases with the increase in the water content, degree of saturation and water–cement ratio. A simple equation is proposed to predict the electrical resistivity of soil–cement under the condition of the specified curing time and water–cement ratio. It is found that the electrical resistivity has a good relationship with the unconfined compression strength and blow count of SPT. It is expected that the electrical resistivity method can be widely used for checking/controlling the quality of soil–cement in practice.     

Effect of sulfur concentration on diamond crystallization in the Fe–C–S system at 5.3–5.5 GPa and 1300–1370°C

The paper presents results of experiments aimed at diamond synthesis in the Fe–C–S system at 5.3–5.5 GPa and temperatures of 1300–1370°C and detailed data on the microtextures of the experimental samples and the composition of the accompanying phases (Fe₃C and Fe₇C₃ carbides, graphite, and FeS). It is demonstrated that diamond can be synthesized after temperatures at which carbides are formed are overcome and can crystallize within the temperature range of 1300°C (temperature of the peritectic reaction melt + diamond = Fe₇C₃) to 1370°C (of thermodynamically stable graphite) under the appearance experimental pressure. The possible involvement of natural metal- and sulfur-bearing compounds in the origin of natural diamond is discussed.     

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.     

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.     

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.

     

Details of Interaction between CaCO3 and Fe at 4 GPa and 1400‒1500°C

Doklady Earth Sciences - The issue of the stability of carbonate matter (CaCO3) in subduction zones under reduced conditions remains topical. In addition, carbonates may be one of the key sources...     

Experimental study of uraninite solubility in aqueous HCl solutions at 500°C and 1 kbar

Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It was shown that the following U(IV) species dominate in the aqueous solution: U(OH)₄⁰, U(OH)₂Cl₂⁰, and UOH Cl₃⁰ Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were calculated (kJ/mol): −9865.55 for UO₂(aq), −1374.57 for U(OH)₂ Cl₂⁰, and −1265.49 for UOH Cl₃⁰, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO₂(cr) = UO₂(aq), pK ₀ = 6.64; UO₂(cr) + 2HCl⁰ = U(OH)₂ Cl₂⁰, pK ₂ = 3.56; and UO₂(cr) + 3HCl⁰ = UOHcl₃⁰ + H₂O, pK ₃ = 3.05. The value pK ₁ ≈ 5.0 was obtained as a first approximation for the equilibrium UO₂(cr) + H₂O + HCl⁰ = U(OH)₃Cl⁰. The constant of the reaction UO₂(cr) + 4HCl⁰ = UCl₄⁰ + 2H₂O (pK ₄ = 7.02) was calculated taking into account the ionization constants of U Cl₄⁰ and U(OH)₄⁰, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold (material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested that the UO_{2 + x} /UO₂ redox pair oxidized Au(cr) to Au⁺(aq), which was then reduced under the influence of stronger reducers.     

Application of IR and Raman spectroscopy for the determination of the role of oxygen fugacity in the formation of N–С–О–Н molecules and complexes in the iron-bearing silicate melts at high pressures

Large-scale melting of the Earth’s early mantle under the effect of global impact processes was accompanied by the generation of volatiles, which concentration was mainly controlled by the interaction of main N, C, O, and H gas-forming elements with silicate and metallic melts at low oxygen fugacity (fO₂), which predominated during metallic segregation and self-oxidation of magma ocean. The paper considers the application of Raman and IR (infrared) Fourier spectroscopy for revealing the mechanisms of simultaneous dissolution and relative contents of N, C, O, and H in glasses, which represent the quench products of reduced model FeO–Na₂O–Al₂O₃–SiO₂ melts after experiments at 4 GPa, 1550°C, and fO₂ 1.5–3 orders of magnitude below the oxygen fugacity of the iron—wustite buffer equilibrium (fO₂(IW)). Such fO₂ values correspond to those inferred for the origin and evolution of magma ocean. It was established that the silicate melt contains complexes with N–H bonds (NH₃, NH ₂ ⁺ , NH ₂ ^- ), N₂, H₂, and CH₄ molecules, as well as oxidized hydrogen species (OH^– hydroxyl and molecular water H₂O). Spectral characteristics of the glasses indicate significant influence of fO₂ on the N–C–O–H proportion in the melt. They are expressed in a sharp decrease of NH ₂ ⁺ , NH ₂ ^- (O–NH₂), OH^–, H₂O, and CH₄ and simultaneous increase of NH ₂ ^- (≡Si–NH₂) and NH₃ with decreasing fO₂. As a result, NH₃ molecules become the dominant nitrogen compounds among N–C–H components in the melt at fO₂ two orders of magnitude below fO₂(IW), whereas molecular СН₄ prevails at higher fO₂. The noteworthy feature of the redox reactions in the melt is stability of the ОН^– groups and molecular water, in spite of the sufficiently low fO₂. Our study shows that the composition of reduced magmatic gases transferred to the planet surface has been significantly modified under conditions of self-oxidation of mantle and magma ocean.     

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.     

Oxygen isotope fractionation between chlorite and water from 170 to 350°C: a preliminary assessment based on partial exchange and fluid/rock experiments

Oxygen isotope fractionations in laboratory systems have been determined between chlorite and water at 170–350°C. In one series of experiments, the Northrop-Clayton partial exchange method was used where three (sometimes four) isotopically different waters were reacted with chlorite [(∑Fe)/∑Fe+Mg = 0.483] for four durations (132–3282 h) at 350°C and 250 b. The percents of exchange determined for the four times from shortest to longest are 4.4, 6.5, 8.0, and 11.9. The fractionations calculated from the Northrop and Clayton (1966) method are in modest agreement for the four run durations: 0.13, 0.26, −0.46, and −0.55 per mil. Errors associated with each of these fractionations are quite large (e.g., ±1.2 per mil for the longest run). The value determined for the longest run of ∼20 weeks is the most reliable of the group and compares very closely with a value of ∼ −0.7 per mil estimated by Wenner and Taylor (1971) based on natural chlorites. Good agreement is also observed with the estimates, −1.2 and −1.3‰ calculated at 350°C for chlorite compositions with [(∑Fe)/∑Fe+Mg] = 0.313 and 0.444, respectively, from equations given by Savin and Lee (1988) based on their empirical bond-type method.Additional fractionation data have been estimated from hydrothermal granite-fluid experiments where chlorite formed from biotite. Detailed thin section, scanning electron microscope (SEM), x-ray diffraction (XRD), and electron microprobe analyses demonstrate that biotite is altered exclusively to chlorite in 13 granite-fluid experiments conducted at the following conditions: T = 170–300°C, P = vapor saturation − 200 b, salinity = H₂O, 0.1 and 1 m NaCl, fluid/biotite mass ratios = 3−44, run durations = 122−772 h. The amount of chlorite, quantified through point counting and XRD, increased with increasing temperature, salinity, and time. The isotope compositions of chlorite were calculated from mass balance and compared to the final measured δ¹⁸O of the fluids. The 10³ln α values averaged 0.14, 0.8 and 2.9 per mil for 300°, 250°, and 200°C, respectively. A least-squares regression model of the combined data set (all T’s) gives the following expression for fractionation: 1000 ln α_chl-w=2.693 (10⁹/T³)−6.342 (10⁶/T²)+2.969 (10³/T) The curve described by this equation is in very good agreement with empirical curves given by Wenner and Taylor 1971, Savin and Lee 1988 and Zheng (1993).