An experimental study of interaction between pure water and alkaline feldspar at high temperatures and pressures

Due to the important scientific significance of the interaction between alkaline feldspar and high-temperature and high-pressure fluids. We have conducted a series of autoclave experiments of feldspar dissolution and secondary mineral precipitation in conditions of 250–500 °C, 8–50 MPa, and pH = 3.0 and 5.5. Based on the interaction experiments between alkaline feldspar and fluid of high-temperatures and high-pressures, we get the main results as follows: (1) The law that people have grasped below the critical point about the influence of temperature, pressure, and pH value on the alkaline feldspar dissolution behavior is still held above the critical point. (2) Due to the experimental techniques of autoclave flip 180°—sharp quenching and based on electron microprobe analysis of mineral new formed, theoretical analysis has determined that the new altered minerals distributed on the island dissolution surface of feldspar are products of precipitation on a feldspar surface after saturation of the relative ion concentration in water fluid.     

The stability of hercynite at high pressures and temperatures

The stability of hercynite (FeAl₂O₄) has been investigated experimentally between 7 and 24 GPa and 900 and 1,700°C. Hercynite breaks down to its constituent oxides at 7–8.5 GPa and temperatures >1,000°C. The incorporation of a small magnetite component in the hercynite necessitated a small correction to fix the location of the endmember reaction: FeAl₂O₄  = Al₂O₃ + FeO in P–T space. After making this correction, the position of the phase boundary was used to evaluate thermodynamic data for hercynite. Our results support a relatively large S ₂₉₈^° for hercynite, on the order of 115 J mol⁻¹ K⁻¹. Experiments up to 24 GPa and 1,400°C failed to detect any high-pressure polymorph of FeAl₂O₄; only corundum + wüstite were detected. This behaviour contrasts with that observed for the analogous MgAl₂O₄ system where the constituent oxides recombine at high pressure to produce “post-spinel” phases with CaFe₂O₄-type and CaTi₂O₄-type structures.     

Oxygen chemical diffusion in three basaltic liquids at elevated temperatures and pressures

The diffusivity of oxygen has been measured in three basaltic liquids from 1280 to 1450°C and 4 to 21 kilobars using a solid media piston-cylinder apparatus. The measurements were done by monitoring the reduction of ferric iron in previously oxidized spheres of basalt melt. The compositions studied were olivine nephelinite, alkali basalt, and 1921 Kilauea tholeiite.The isobaric temperature dependence of oxygen diffusivity is adequately described by Arrhenius relationships for the three liquids studied. Arrhenius activation energies were determined at 12 kilobars for olivine nephelinite (62± 6 kcal/mole) and tholeiite (51 ± 4 kcal/mole) and at 4, 12, and 20 kilobars for alkali basalt (70 ± 7, 86 ± 6, and 71 ± 14 kcal/mole, respectively). The Arrhenius parameters for the three compositions define a compensation law which is indistinguishable from those for oxygen diffusion in simple silicate melts (DUNN, 1982) and for divalent cation diffusion in basaltic melts (Hofmann, 1980). These results suggest that the principal species contributing to the total diffusivity of oxygen is the oxide anion (O^2?).The isothermal pressure dependence of oxygen diffusion is complex and quite different from that observed for cationic diffusion in silicate melts. All three compositions show a sharp decrease in oxygen diffusivity at approximately the same pressure as the change in the liquidus phase from olivine to pyroxene, but otherwise the pressure dependence can be described by Arrhenius type equations. The equations yield negative activation volumes for the olivine nehpelinite and the alkali basalt. The activation volumes determined for the tholeiite are near zero at low pressure and positive at high pressure. A negative activation volume represents a decrease in the average size of the principal diffusing species.The results of this study are consistent with a melt model which includes both continuous changes in the relative proportions of the various anionic species in the melt with pressure and the occurrence of anionic disproportionation reactions within narrow pressure ranges.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

In pelitic rocks, under conditions of low f _{O 2} and low f _{H 2 O}, the stability of the mineral pair cordierite-garnet is limited by five univariant reactions. In sequence from high pressure and low temperature to high temperature and low pressure these are: cordierite+garnet hypersthene+sillimanite+quartz, cordierite+garnet hypersthene+sapphirine+quartz, cordierite+garnet hypersthene+spinel+quartz and cordierite+garnet olivine+spinel +quartz. In this sequence of reactions the Mg/Mg+Fe²⁺ ratio of all ferro-magnesian minerals involved decreases continuously from the first reaction to the fifth. The five univariant boundaries delimit a wide P-T range over which cordierite and garnet may coexist.Two divariant equilibria in which the Mg/Mg+ Fe²⁺ ratio of the coexisting phases are uniquely determined by pressure and temperature have been studied in detail. P-T-X grids for the reactions cordierite garnet+sillimanite+quartz and cordierite+hypersthene garnet+quartz are used to obtain pressure-temperature estimates for several high grade metamorphic areas. The results suggest temperatures of formation of 700–850° C and load pressures of 5–10 kb. In rare occasions temperatures of 950–1000° C appear to have been reached during granulite metamorphism.On the basis of melting experiments in pelitic compositions it is suggested that Ca-poor garnet xenocrysts found in calc-alkaline magmas derive from admixed pelitic rocks and did not equilibrate with the calc-alkaline magma.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet relative to their anhydrous breakdown products, i.e. hypersthene, sapphirine, olivine, spinel, sillimanite and quartz, has been studied experimentally in model pelitic compositions (system MgO-FeO-Al₂O₃-CaO-K₂O-SiO₂). Below 1000° C cordierite breaks down according to the divariant reaction cordierite garnet+sillimanite+quartz (1) for most values of the MgO/MgO + FeO ratio (X). At very high values of X (ca. X0.9) garnet in reaction (1) is replaced by hypersthene. The position and width of the divariant field (in terms of pressure and temperature) in which cordierite and garnet coexist, is a function of the MgO/MgO + FeO ratio. If this ratio is increased then the stability field of garnet is reduced and that of cordierite extended towards higher pressure. Compositions of coexisting cordierite and garnet in divariant equilibrium have been analysed by electron probe micro-analyser. These compositions are unique functions of pressure and temperature. Above ca. 1000° C the breakdown of cordierite involves the phases sapphirine and hercynite-rich spinel in Mg-rich and Fe-rich compositions respectively.     

Experimental study of the stability of cordierite and garnet in pelitic compositions at high pressures and temperatures

The stability of cordierite and garnet has been studied experimentally in complex, silica oversaturated compositions (in the systems MgO-FeO-Al₂O-CaO₃-Na₂O-K₂OSiO₂) in which the molecular ratio Al₂O₃/FeO+MgO<1. Compositions with 100 Mg/Mg+Fe²⁺ ratios (X) of 0, 30, 50, 70 and 100 have been used to investigate the role of this ratio in determining phase assemblages and P, T coordinates of reactions. The minimum pressure for appearance of garnet at a given temperature is strongly dependent on X _{total rock}.The X-values of co-existing phases (chiefly garnet, cordierite, hypersthene) in divariant equilibrium are a function of temperature and pressure and have been experimentally determined at 900° C, 1000° C and 1100° C. At high temperature (>1050° C) the phases sapphirine and spinel are stable with quartz in Mg-rich and Fe-rich compositions respectively. Experiments in the system MgO-FeO-Al₂O₃-SiO₂ show that for a given X-value and temperature the pressure required to produce Ca-free garnet from hypersthene-cordierite assemblages is 1–2 kb greater than that required to produce garnet containing 6±2 mol percent grossular solid solution in the more complex Ca-bearing system.     

An Experimental Melting—crystallization Study on Basalt at High Pressures

A series of melting-crystallization experiments on alkali basalt samples from Minqing, Fujian Province was carried out in dry and waterbearing systems at high pressures. A high-pressure melting curve was obtained. The results indicate that clinopyroxene crystallized from basalt melt at 13.5–23.7 kbar. spinel at 23.7–28.6 kbar and garnet at > 28.6 kbar. With increasing pressure, the CaSiO₃ contents of clinopyroxenes increase; and the FeSiO₃ decreases, but the chemical composition of garnet does not show any significant difference. The minerals are larger and euhedral in the water-bearing system. Therefore, we consider that natural megacrysts of the basalt can crystallize from the water-bearing basalt magma at high pressure. So the megacrysts may be derived from the upper mantle as a result of magmatic crystallization-fractionation under high pressure. This project was financially supported by the National Natural Science Foundation of China.     

The solubility and speciation of molybdenum in water vapour at elevated temperatures and pressures: Implications for ore genesis

The solubility of molybdenum trioxide in liquid-undersaturated water vapour has been investigated experimentally at 300, 320, and 360 °C and 39-154 bars. Results of these experiments show that the solubility of MoO₃ in water vapour is between 1 and 29 ppm, which is 19-20 orders of magnitude higher than the vapour pressure of MoO₃(g). Molybdenum solubility increases exponentially with f_H2O, suggesting the formation of a gaseous hydrated complex of the type MoO₃·nH₂O by the reaction:

(A.1)     

针铁矿-四方纤铁矿-水体系氧同位素分馏的实验研究

针铁矿是非常重要的三价铁氧化物之一,其氧同位素组成对于古环境再造具有很大的价值。以4种不同的铁化合物作为Fe3+离子的源物质,于30～120℃范围内,采用强迫水解方法,在不同同位素组成的水中分别实验合成针铁矿和四方纤铁矿。结果表明,以Fe(NO3)3·9H2O、NH4Fe(SO4)2·12H2O、Fe(SO4)3·7H2O为Fe3+源物质合成的是纯针铁矿,而以FeCl3·6H2O为Fe3+源物质合成的是四方纤铁矿。氧同位素分析显示,在30～120℃范围内实验测定的针铁矿-水体系和四方纤铁矿-水体系氧同位素分馏几乎不可区分,并且满足下列分馏关系:103lnα针铁矿-水=9.59×103/T-26.39103lnα四方纤铁矿-水=8.85×103/T-24.44实验测定的针铁矿-水体系氧同位素分馏不仅与前人实验结果一致,而且与增量方法理论计算相近。由于实验采用不同反应途径得到了一致的分馏结果,因此所测定的针铁矿-水体系氧同位素分馏代表了热力学平衡。     

A spectrophotometric study of samarium (III) speciation in chloride solutions at elevated temperatures

The speciation of samarium (III) in chloride-bearing solutions was investigated spectrophotometrically at temperatures of 100-250 °C and a pressure of 100 bars. The simple hydrated ion, Sm³⁺, is predominant at ambient temperature, but chloride complexes are the dominant species at elevated temperatures. Cumulative formation constants for samarium chloride species were calculated for the following reactions:

     

An experimental study of oxygen isotope fractionation between inorganically precipitated aragonite and water at low temperatures

To determine oxygen isotope fractionation between aragonite and water, aragonite was slowly precipitated from Ca(HCO₃)₂ solution at 0 to 50°C in the presence of Mg²⁺ or SO₄²⁻. The phase compositions and morphologies of synthetic minerals were detected by X-ray diffraction (XRD) and scanning electron microscopy (SEM) techniques. The effects of aragonite precipitation rate and excess dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution on oxygen isotope fractionation between aragonite and water were investigated. For the CaCO₃ minerals slowly precipitated by the CaCO₃ or NaHCO₃ dissolution method at 0 to 50°C, the XRD and SEM analyses show that the rate of aragonite precipitation increased with temperature. Correspondingly, oxygen isotope fractionations between aragonite and water deviated progressively farther from equilibrium. Additionally, an excess of dissolved CO₂ gas in the initial Ca(HCO₃)₂ solution results in an increase in apparent oxygen isotope fractionations. As a consequence, the experimentally determined oxygen isotope fractionations at 50°C indicate disequilibrium, whereas the relatively lower fractionation values obtained at 0 and 25°C from the solution with less dissolved CO₂ gas and low precipitation rates indicate a closer approach to equilibrium. Combining the lower values at 0 and 25°C with previous data derived from a two-step overgrowth technique at 50 and 70°C, a fractionation equation for the aragonite-water system at 0 to 70°C is obtained as follows:

     

Raman spectroscopic study of K-lingunite at various pressures and temperatures

K-lingunite is a high-pressure modification of K-feldspar that possesses the tetragonal hollandite structure. Variations of the Raman spectra of K-lingunite were studied up to ~31.5 GPa at room temperature, and in the range 79–823 K at atmospheric pressure. The Raman frequencies of all bands were observed to increase with increasing pressure, and decrease with increasing temperature for K-lingunite. This behavior is in line with those observed for most of other materials. New sharp Raman bands appear at pressures greater than 13–15 GPa, suggesting a phase transition in K-lingunite with increasing pressure. The transition is reversible when pressure was released. The appearance of these new Raman bands may correspond to the phase transition revealed earlier at around 20 GPa by X-ray diffraction studies. Instead of transforming back to its stable minerals, such as orthoclase, microcline or sanidine, K-lingunite became amorphous in the temperature range 803–823 K at atmospheric pressure.     

Raman spectroscopic study of hydroxyl-clinohumite at various pressures and temperatures

 Variations of Raman spectra of hydroxyl-clinohumite were studied up to ∼370 kbar at room temperature, and in the range 81–873 K at atmospheric pressure. With the exception of the symmetric OH-stretch bands, the Raman frequencies of all bands were observed to increase monotonically with increasing pressure, and decrease with increasing temperature. This behavior is in line with those observed for other humite members (norbergite and chondrodite) so far studied. The symmetric OH-stretching band shows a mode softening with increasing pressure, and splits into two bands at either high pressure or low temperature. In the quasihydrostatic experiment, the compression and decompression paths of one of the asymmetric OH-stretch bands form a hysteresis loop, but the same behavior was not observed in the nonhydrostatic experiment. These results indicate that the two kinds of OH groups in hydroxyl-clinohumite have nonequivalent movement paths on compression, and with one OH group experiencing a release of spatial hindrance during compression. This behavior appears to be modified by shear stress. The same complication of the OH groups was not observed in the temperature variation study. The pressure and temperature variations of the Raman frequencies for the various vibrations involving the SiO₄ tetrahedra and MgO₆ octahedra below ∼1000 cm⁻¹ for clinohumite behave similarly to other hydrous magnesium silicates. On the basis of the relationship between isothermal bulk modulus and Raman data, it is suggested that the linear pressure dependences of vibrational frequencies of various Raman bands reported in the literature are inadequate. Received: 20 March 1999 / Revised, accepted: 24 August 1999     

Strength and stability of frictional sliding of gabbro gouge at elevated temperatures

To investigate the strength of frictional sliding and stability of mafic lower crust, we conducted experiments on oven-dried gabbro gouge of 1 mm thick sandwiched between country rock pieces (with gouge inclined 35° to the sample axis) at slip rates of 1.22 × 10^− 3 mm/s and 1.22 × 10^− 4 mm/s and elevated temperatures up to 615 °C. Special attention has been paid to whether transition from velocity weakening to velocity strengthening occurs due to the elevation of temperature.Two series of experiments were conducted with normal stresses of 200 MPa and 300 MPa, respectively. For both normal stresses, the friction strengths are comparable at least up to 510 °C, with no significant weakening effect of increasing temperature. Comparison of our results with Byerlee's rule on a strike slip fault with a specific temperature profile in the Zhangbei region of North China shows that the strength given by experiments are around that given by Byerlee's rule and a little greater in the high temperature range.At 200 MPa normal stress, the steady-state rate dependence a − b shows only positive values, probably still in the “run-in” process where velocity strengthening is a common feature. With a normal stress of 300 MPa, the values of steady-state rate dependence decreases systematically with increasing temperature, and stick-slip occurred at 615 °C. Considering the limited displacement, limited normal stress applied and the effect of normal stress for the temperatures above 420 °C, it is inferred here that velocity weakening may be the typical behaviour at higher normal stress for temperature above 420 °C and at least up to 615 °C, which covers most of the temperature range in the lower crust of geologically stable continental interior. For a dry mafic lower crust in cool continental interiors where frictional sliding prevails over plastic flow, unstable slip nucleation may occur to generate earthquakes.     

The distribution of strontium between coexisting silicate and carbonate liquids at elevated pressures and temperatures

Strontium is characteristically enriched in carbonatites and associated igneous rocks. Experiments between 600 and 800°C at 5 and 10 kb show that Sr fractionates strongly toward both liquid phases of a carbonate liquid-silicate liquid-solid assemblage, with the crystalline phases depleted in Sr. Considering that the alkalic igneous rocks associated with carbonatites are not significantly depleted in Sr compared with the carbonatites, it is concluded that these complexes are formed by a pair of immiscible magmas, rather than the carbonatites being late-stage fractionation products of the alkalic silicate magmas.     

Raman spectroscopic study of PbCO3 at high pressures and temperatures

Cerussite (PbCO₃) has been investigated by high-pressure and high-temperature Raman spectroscopy up to pressures of 17.2 GPa and temperatures of 723 K. Two pressure induced phase transitions were observed at about 8.0(2) and 16.0(2) GPa, respectively. The post-aragonite transition (PbCO₃-II) at 8.0(2) GPa is accompanied by softening of the v ₂-out-of-plane mode of the CO ₃ ^2? group and disappearance of the B_1g (v ₄-in-plane band of the CO ₃ ^2? group) mode. Stronger shifts of the carbonate group modes after the phase transition suggest that the new structure is more compressible. The formation of a second high-pressure polymorph begins at about 10 GPa. It is accompanied by the occurrence of three new bands at different pressures and splitting of the v ₁-symmetric C–O stretching mode of the CO ₃ ^2? group. The transitions are reversible on pressure release. A semi-quantitative phase diagram for PbCO₃ as a function of pressure and temperature is proposed.     

Dehydration Temperature of Serpentine at Elevated Temperatures and Pressures by Electrical Conductivity Method and Its Implications

Dehydration temperatures of serpentine were measured in the pressure range between 1.0GPa and 5.0GPa by using the electrical conductivity metod simultaneously at high temperatures and high pressures.The results show that with increasing pressure th dehydration temperature of antigorite increases slightly below 2.0GPa ,but drops markedly above2.0GPa .This strongly suggests that high pressure would favor the dehydration of serpentine minerals and the water released thereby would be an important source of fluids involved in magmatism in a subduction zone and mantle metasomatism,Meanwhile,the greatly enhanced electric conductivity in the presence of water may be one of the reasons underlying the occurrence of a high-conductivity zone in the lower crust.     

The electrical conductivities at elevated temperatures and pressures of polycrystalline manganese,cobalt and nickel orthosilicates

Electrical conductivities of synthetic manganese, cobalt and nickel orthosilicates, also of mixed-cation orthosilicates containing together magnesium, iron and manganese, also magnesium, iron and nickel, have been studied as polycrystalline samples at temperatures up to 770°C and pressures up to 62 kbar.Electrical conductivities of these materials appear to depend on the presence of trivalent cations formed by partial oxidation; conductivities are less, by a factor of approximately 10⁴ than for ferrous orthosilicate.The mechanism of electronic semiconduction in these materials is discussed; it is suggested that the effective carrier centres are an association of bivalent cation vacancy and trivalent cations. An activation energy in the range 0.4–1.2 eV is required; its variation with pressure is examined. Ionic conduction is also present, particularly with the cobalt compound.It is concluded that small amounts of manganese or nickel are unlikely to enhance significantly the conductivities of ferromagnesian orthosilicates in the mantle of the Earth, and that a more significant factor is the extent of oxidation of bivalent iron cation.