Pressure-volume-temperature behavior of γ-Fe2SiO4 (spinel) based on static compression measurements at 400° C

Thirteen energy-dispersive x-ray diffraction spectra for -Fe₂SiO₄ (spinel) collected in situ at 400° C and pressures to 24 GPa constitute the basis for an elevated-temperature static compression isotherm for this important high-pressure phase. A Murnaghan regression of these molar volume measurements yields 177.3 (±17.4) GPa and 5.4(±2.5) for the 400° C, room pressure values of the isothermal bulk modulus (K _{P 0}) and its first pressure derivative (K _{P 0}), respectively. When compared to the room-Tdeterminations of K _{P 0} available in the literature, our 400° C K _{P 0} yields -4.1 (±6.2)×10^-2 GPa/degree for the average value of (K/T) _{P 0} over the temperature interval 25° C<><400°>A five-parameter V(P, T) equation for -Fe₂SiO₄ based on simultaneous regression of our data combined with the elevated P-Tdata of Yagi et al. (1987) and the extrapolated thermal expansion values from Suzuki et al. (1979) yields isochores which have very little curvature [(² T/P ²) _v 0], in marked contrast to the isochores for fayalite (Plymate and Stout 1990) which exhibit pronounced negative curvature [(T/P ²) _v <0]. along=" the=">-Fe₂SiO₄ reaction boundary V_Rvaries from a minimum of approximately 8.3% at approximately 450° C to approximately 8.9% at 1200° C. Extrapolation of the fayalite and -Fe₂SiO₄ V(P, T) relationships to the temperature and pressure of the 400 km discontinuity suggests a V _R of approximately 8.4% at that depth, approximately 10% less than the 9.3% V _R at ambient conditions.     

Thermal behavior of almandine at temperatures up to 1,200°C in hydrogen

The thermally induced reductive decomposition of a natural near end-member almandine [^VIII(Fe_2.85Mg_0.11Ca_0.05Mn_0.02)^VI(Al_1.99)^IV(Si_2.99)O₁₂] and possible hydrogen diffusion into its structure have been carried out at temperatures up to 1,200°C, monitored by simultaneous thermogravimetric analysis and differential scanning calorimetry (DSC), infrared and ⁵⁷Fe Mössbauer spectroscopy and X-ray powder diffraction. Below 1,000°C, evidence for hydrogen diffusion into almandine structure was not observed. At temperatures above 1,000°C, reductive decomposition sets in, as displayed by a sharp endothermic peak at 1,055°C on the DSC curve accompanied by a total mass loss of 3.51%. We observe the following decomposition mechanism: almandine + hydrogen → α-Fe + cristobalite + hercynite + water. At higher temperatures, fayalite and sekaninaite are formed by consecutive reaction of α-Fe with cristobalite and water, and cristobalite with hercynite, respectively. The metallic α-Fe phase forms spherical and isolated particles (~1 μm).     

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.     

Effects of water on strength and failure mode of coarse-grained granites at 300°C

Summary Deformation experiments have been performed in a triaxial compression cell at a temperature of 300°C and confining pressures up to 65 MPa using samples of homogeneous, fresh two-mica-granite (RM) and monzogranite (CM). The cylindrical specimens (d=70 mm, h=140 mm, V=540 cm³) were tested undrained under dry (105°C), as received, and water saturated conditions at deformation rates between and . The mechanical behaviour of the two types of coarse-grained, crystalloblastic granites is critically influenced by mineralogical composition, porosity, and the amount of intergranular water present in the samples. The failure stress of the CM granite is at about 65% of that of the RM granite; in both rocks strength decreases with increasing porosity and water content.The presence of interstitial water causes a failure mode of non-localized, homogeneously distributed microcracking in the central parts of the samples, whereas, in runs with dry granites, strain localization along a single shear fracture was observed. When aqueous fluids are present, the macroscopic style of deformation of granites appears to be ductile even at lowP andT conditions. Strength and angle of internal friction are reduced to very low values. The style of deformation, as well as the reduction of strength of the water-saturated rock samples, is due to mechanical and chemical effects of intergranular water at elevated temperatures.The maximum differential stresses measured for these coarse-grained granites are much lower than the strength commonly reported for other granites, e. g. Westerly and Charcoal granites. Our data suggest that the strength of the granitic crust under differential stress is lower than currently deduced from laboratory experiments.     

Pressure-dependent stability of cadmium chloride complexes: Potentiometric measurements at 1–1000 bar and 25°C

Potentiometric measurements were performed in the Cd(NO₃)₂-KCl-H₂O system at 25°C and 1–1000 bar using an isothermal cell with a liquid junction and equipped with a solid contact Cd-selective electrode. At 1 bar, the stepwise equilibrium constant of the fourth cadmium chloride complex CdCl₄²⁻ has been determined (log K₄⁰ = −0.88 ± 0.25). The pressure-dependent stability constants for all cadmium chloride complexes have been experimentally established for the first time. As pressure increases from 1 to 1000 bar, the stability constants for the first, third, and fourth complexes change by less than 0.05 logarithmic units, whereas that for the second complex decreases by 0.33 logarithmic units. On the basis of these data, the partial molar volumes of four cadmium chloride complexes have been determined under standard state conditions: V ⁰(CdCl⁺) = 2.20 ± 3, V ⁰(CdCl_{2 (aq)}) = 42.21 ± 5, V ⁰(CdCl₃⁻) = 63.47 ± 10, and V ⁰(CdCl₄²⁻) = 81.35 ± 15 cm³mol⁻¹. The linear correlation between the nonsolvation contributions of molar volumes and the number of ligands corresponds to the change in coordination from octahedral in Cd²⁺ and CdCl⁺ to tetrahedral in CdCl_{2 (aq)}, CdCl₃⁻, and CdCl₄²⁻ complexes. Using theoretical correlations, the HKF parameters allowing calculation of the volumetric properties of cadmium chloride complexes in a wide range of temperature and pressure have been obtained. The pressure effect on cadmium concentration in sphalerite in equilibrium with the H₂O-NaCl hydrothermal fluid has been estimated. It is shown that the Cd content in sphalerite increases with pressure.     

Silicate melts at magmatic temperatures: in-situ structure determination to 1651°C and effect of temperature and bulk composition on the mixing behavior of structural units

The abundance of coexisting structural units in K-, Na-, and Li-silicate melts and glasses from 25° to 1654°C has been determined with in-situ micro-Raman spectroscopy. From these data an equilibrium constant, K_x, for the disproportionation reaction among the structural units coexisting in the melts, Si₂O₅(2Q³)SiO₃(Q²)+SiO₂(Q⁴), was calculated (K_x is the equilibrium constant derived by using mol fractions rather than activities of the structural units). From ln K_x vs l/T relationships the enthalpy (H_x) for the disproportionation reaction is in the range of-30 to 30 kJ/mol with systematic compositional dependence. In the potassium and sodium systems, where the disproportionation reaction shifts to the right with increasing temperature, the H_x increases with silica content (M/Si decreases, M=Na, K). For melts and supercooled liquids of composition Li₂O·2SiO₂ (Li/Si=1), the H_x is indistinguishable from 0. By decreasing the Li/Si to 0.667 (composition LS3) and beyond (e.g., LS4), the disproportionation reaction shifts to the left as the temperature is increased. For a given ratio of M/Si (M=K, Na, Li), there is a positive, near linear correlation between the H_x and the Z/r² of the metal cation. The slope of the H_x vs Z/r² regression lines increases as the system becomes more silica rich (i.e., M/Si is decreased). Activity coefficients for the individual structural units, _i, were calculated from the structural data combined with liquidus phase relations. These coefficients are linear functions of their mol fraction of the form _i=a lnX _i+b, where a is between 0.6 and 0.87, and X _i is the mol fraction of the unit. The value of the intercept, b, is near 0. The relationship between activity coefficients and abundance of individual structural units is not affected by temperature or the electronic properties of the alkali metal. The activity of the structural units, however, depend on their concentration, type of metal cation, and on temperature.     

Mechanisms of hydrothermal crystallization of quartz at 250°C and 15 kbar

Oxygen isotopic exchange between quartz and water, using a novel technique in which both ¹⁸O/¹⁶O and ¹⁷O/¹⁶O fractionations were measured, yielded an equilibrium fractionation Δ¹⁸ = 9.0 at 250°C and 15 kbar. The reaction proceeds predominantly by solution of fine grains and growth of larger grains. Exchange by solid-state diffusion is immeasurably slow at this temperature. Under the same experimental conditions, cristobalite behaves quite differently, becoming transformed to sub-micron quartz crystals in a few minutes. The phase transformation is accompanied by a kinetic isotope effect yielding quartz in isotopic disequilibrium with water. It is possible that such disequilibrium products are also formed in other experiments involving phase transitions or mineral syntheses.     

Mechanical behaviors of conjugate-flawed rocks subjected to coupled static–dynamic compression

Conjugate flaws widely exist in rock masses and play a significant role in their deformation and strength properties. Understanding the mechanical behaviors of rock masses containing conjugate flaws is conducive to rock engineering stability assessment and the related supporting design. This study experimentally investigates the mechanical properties of conjugate-flawed sandstone specimens under coupled static–dynamic compression, thereby providing insight into how conjugate fractures interact to produce tracing tensional joints. Results indicate that the coupled compressive strength and the dynamic elastic modulus of conjugate-flawed rock specimens show remarkable loading rate dependence. For a fixed strain rate, the specimen with a static pre-stress equal to 60% of its uniaxial compressive strength has the highest coupled strength. Besides, both higher static pre-stress and strain rate can induce smaller mean fragment size and greater fractal dimension of the specimen, corresponding to a more uniform distribution of the broken fragments with smaller sizes. When the static pre-stress is lower than 80%UCS, the flawed specimen under a higher strain rate is characterized by higher absorbed energy. However, when the pre-stress equals 80%UCS, the value of the energy absorbed by the specimen in the dynamic loading process is negative due to the release of the preexisting considerable elastic strain energy input from the static pre-loading. As for the failure modes, cracks always penetrate the preexisting ipsilateral flaw tips to form anti-wing cracks. Under dynamic loading, the conjugate-flawed specimen generally shows tensile failure at a low strain rate, while the shear failure dominates at a high strain rate. In addition, based on progressive failure processes of the conjugate-flawed rock specimens, the evolution of tracing tensional joints in the field is discussed.

     

The effect of added dissolved calcium on calcite dissolution kinetics in aqueous solutions at 25°C

The kinetics of calcite dissolution in solutions containing dissolved Ca²⁺ has been investigated at 25°C, using a rotating disc apparatus. In acid solutions no effect of Ca²⁺ in solution is observed. The rate is dependent on the transport of H⁺ to the surface. In neutral to alkaline solutions the dissolution reaction is controlled by mixed kinetics and the conventional empirical representation of the dissolution rate results through the interaction of chemical and transport gradients in the diffusion boundary layer. The chemical reaction rate is a function of the gradient between the equilibrium and the surface concentrations of calcium carbonate, whereas the transport reaction can be described in terms of a series of gradients between the surface and the bulk of dissolved calcium and carbonate species. The presence of dissolved Ca²⁺ decreases the rate of the transport reaction, making the dissolution process more transport-controlled. The chemical rate constant is independent of the Ca²⁺ concentration in solution. The chemical rate constant for Carrara marble dissolution is determined to ∼2·10⁻² cm s⁻¹ and the diffusion coefficient for the transport reaction to ∼7.6·10⁻⁶ cm² s⁻¹.In natural systems with high Ca²⁺ concentrations and in absence of inhibitors of the surface chemical reaction, the dissolution of calcite may approach a transport-controlled reaction, especially in environments with restricted flow.     

The thermoelastic behavior of clintonite up to 10?GPa and 1,000°C

The thermoelastic behavior of a natural clintonite-1M [with composition: Ca_1.01(Mg_2.29Al_0.59Fe_0.12)_Σ3.00(Si_1.20Al_2.80)_Σ4.00O₁₀(OH)₂] has been investigated up to 10 GPa (at room temperature) and up to 960°C (at room pressure) by means of in situ synchrotron single-crystal and powder diffraction, respectively. No evidence of phase transition has been observed within the pressure and temperature range investigated. P–V data fitted with an isothermal third-order Birch–Murnaghan equation of state (BM-EoS) give V ₀ = 457.1(2) ?³, K _T0 = 76(3)GPa, and K′ = 10.6(15). The evolution of the “Eulerian finite strain” versus “normalized stress” shows a linear positive trend. The linear regression yields Fe(0) = 76(3) GPa as intercept value, and the slope of the regression line leads to a K′ value of 10.6(8). The evolution of the lattice parameters with pressure is significantly anisotropic [β(a) = 1/3K _T0(a) = 0.0023(1) GPa⁻¹; β(b) = 1/3K _T0(b) = 0.0018(1) GPa⁻¹; β(c) = 1/K _T0(c) = 0.0072(3) GPa⁻¹]. The β-angle increases in response to the applied P, with: β_P = β₀ + 0.033(4)P (P in GPa). The structure refinements of clintonite up to 10.1 GPa show that, under hydrostatic pressure, the structure rearranges by compressing mainly isotropically the inter-layer Ca-polyhedron. The bulk modulus of the Ca-polyhedron, described using a second-order BM-EoS, is K _T0(Ca-polyhedron) = 41(2) GPa. The compression of the bond distances between calcium and the basal oxygens of the tetrahedral sheet leads, in turn, to an increase in the ditrigonal distortion of the tetrahedral ring, with ∂α/∂P ≈ 0.1°/GPa within the P-range investigated. The Mg-rich octahedra appear to compress in response to the applied pressure, whereas the tetrahedron appears to behave as a rigid unit. The evolution of axial and volume thermal expansion coefficient α with temperature was described by the polynomial α(T) = α₀ + α₁ T ^−1/2. The refined parameters for clintonite are as follows: α₀ = 2.78(4) 10⁻⁵°C⁻¹ and α₁ = −4.4(6) 10⁻⁵°C^1/2 for the unit-cell volume; α₀(a) = 1.01(2) 10⁻⁵°C⁻¹ and α₁(a) = −1.8(3) 10⁻⁵°C^1/2 for the a-axis; α₀(b) = 1.07(1) 10⁻⁵°C⁻¹ and α₁(b) = −2.3(2) 10⁻⁵°C^1/2 for the b-axis; and α₀(c) = 0.64(2) 10⁻⁵°C⁻¹ and α₁(c) = −7.3(30) 10⁻⁶°C^1/2for the c-axis. The β-angle appears to be almost constant within the given T-range. No structure collapsing in response to the T-induced dehydroxylation was found up to 960°C. The HP- and HT-data of this study show that in clintonite, the most and the less expandable directions do not correspond to the most and the less compressible directions, respectively. A comparison between the thermoelastic parameters of clintonite and those of true micas was carried out.     

Studies of smectite membrane behavior: Temperature dependence, 20–180°C

A brine 5.0 molal in NaCl and 0.45 molal in CaCl₂ was forced through random-fabric clay cakes, 1.0 to 1.6 cm thick, prepared from the 0.25–2.7 μm diameter size fraction of Cheto montmorillonite from Chambers, Arizona. Runs were made at 20°, 95°, 140° and 180°C using a compaction pressure of 34.5 MPa (5000 psi), an upstream fluid pressure of 22.8 MPa (3300 psi), and a downstream fluid pressure of 8.96 MPa (1300 psi). An additional run was made at 140°C, a compaction pressure of 68.9 MPa (10,000 psi), an upstream fluid pressure of 39.0 MPa (5650 psi), and a downstream fluid pressure of 25.3 MPa (3650 psi). At constant fluid flow rate, the molal filtration efficiencies of both Na⁺ and Ca²⁺ increase with temperature, the latter more rapidly. The effect of compaction pressure is shown by comparing the two runs at 140°C: the filtration efficiency for Ca²⁺ at the higher compaction pressure was twice that at the lower compaction pressure; for Na⁺, it was 60% greater. At the slower flow rates found in nature, it appears that Ca²⁺ must be retained preferentially relative to Na⁺ in virtually all sedimentary environments, with the Ca²⁺ preference increasing with increasing temperature. The apparent membrane enrichment for the heavy oxygen isotopes of throughput water molecules observed at 140°C is 0.15%. and that at 180°C is 0.05%., values that are opposite in sign to those reported in the literature for 20°C. This apparent shift in enrichment with temperature is 4 to 5 times the room-temperature salinity correction, but the reliability of the shift value is reduced by the possibility in the high-temperature runs of exchange between brine and clay, which would also make the brine isotopically heavier. Observed changes in filtration efficiency of Ca²⁺ and Na⁺ with temperature and fluid velocity can be explained qualitatively using arguments involving fluid viscosity and hydraulic drag. The newly-designed membrane press used in the study performed adequately at temperatures up to 180°C, but failed in several respects at 220°C.     

Dependence of albite dissolution kinetics on ph and time at 25°c and 70°c

The dissolution rate of albite has been measured as a function of pH and time at 25°C and 70°C in a single-pass flow-through leaching apparatus. Run times extended to 50 days in each experiment. Limited data were obtained at 25°C in the pH range 4–10. More extensive data were obtained at 70°C over the pH range 1.39–11.75.Dissolution rates were defined by release of Si, and in some cases also by Al and Na releases. Speciationsolubility calculations indicate the solutions were well undersaturated for all the likely possible secondary minerals. The fluid was maintained far from equilibrium with albite in all runs. Analysis of the data shows a general consistency with the transition state theory model of Helgesonet al. (1984).Feldspars leached at low and high pH at 70°C showed extensive development of prismatic etch pits demonstrating a surface reaction-controlled dissolution process.     

Phase Chemistry Study of the Zabuye Salt Lake Brine: Isothermal Evaporation at 15°C and 25°C

Zabuye Salt Lake in Tibet, China is a carbonate-type salt lake, which has some unique characteristics that make it different from other types of salt lakes. The lake is at the latter period in its evolution and contains liquid and solid resources. Its brine is rich in Li, B, K and other useful minor elements that are of great economic value. We studied the concentration behavior of these elements and the crystallization paths of salts during isothermal evaporation of brine at 15°C and 25°C. The crystallization sequence of the primary salts from the brine at 25°C is halite (NaCl) → aphthitalite (3K2SO4·Na2SO4) → zabuyelite (Li2CO3)→ trona (Na2CO3·NaHCO3·2H2O) → thermonatrite (Na2CO3·H2O) → sylvite (KCl), while the sequence is halite (NaCl) → sylvite (KCl) → trona (Na2CO3·NaHCO3·2H2O) → zabuyelite (Li2CO3) → thermonatrite (Na2CO3·H2O) → aphthitalite (3K2SO4·Na2SO4) at 15°C. They are in accordance with the metastable phase diagram of the Na+, K+-Cl?, CO32?, SO42?-H2O quinary system at 25°C, except for Na2CO3·7H2O which is replaced by trona and thermonatrite. In the 25°C experiment, zabuyelite (Li2CO3) was precipitated in the early stage because Li2CO3 is supersaturated in the brine at 25°C, in contrast with that at 15°C, it precipitated in the later stage. Potash was precipitated in the middle and late stages in both experiments, while boron was concentrated in the early and middle stages and precipitated in the late stage.     

Study of hidden factors affecting the mechanical behavior of soil–rock mixtures based on abstraction idea

Because of spatial variability and complex compositions, the mechanical test results of natural soil–rock mixtures (SRMs) are often discrete and lack reproducibility, which has greatly restricted the practical application of the experimental findings. The objective of this study was to examine the general mechanical behavior of SRMs under the influences of some hidden factors (e.g., structural parameters, parent rock type and weathering degree). To that end, the abstraction idea was adopted to prepare purified SRM samples. Large-scale triaxial tests were performed on these purified materials. On this basis, the influences of three structural parameters on the mechanical behavior of SRMs were studied. Moreover, the relationship between the shear strength and parent rock type and that between the shear strength and the spatial distribution of rock blocks were quantified. Some additional intrinsic behavior was distinguished from individual experimental phenomena through the comparative analysis of the test data in this study and those reported in the literature. The results show that the hidden factors had significant influences on the mechanical behavior of SRMs. A greater saturated uniaxial compressive strength of rock blocks generally led to a larger shear strength of SRMs. According to the significance of their influences on the shear strength parameters of SRMs, the structural parameters are ordered as: the gradation of rock blocks, the initial dry density of sample and the spatial distribution of rock blocks. The deformation and failure feature of SRMs were considerably affected by the spatial distribution of rock blocks and shear rate. And the shear strength parameters of SRMs were mainly influenced by the content of grains between 40 and 60 mm. The findings of this study would provide useful guidance for engineering practice.