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.     

Phase Equilibria in the Ternary Systems KBr–K2B4O7–H2O and KCl–K2B4O7–H2O at 373 K

According to the compositions of the underground gasfield brines in the west of Sichuan Basin,the phase equilibria in the ternary systems KBr-K2B4O7-H2O and KCl-K2B4O7-H2O at 373 K were studied using the isothermal dissolution equilibrium method.The solubilities of salts and the densities of saturated solutions in these ternary systems were determined.Using the experimental data,phase diagrams and density-composition diagrams were constructed.The two phase diagrams were simple co-saturation type,each having an invariant point,two univariant curves and two crystallization regions.The equilibrium solid phases in the ternary system KBr-K2B4O7-H2O are potassium bromide （KBr） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）,and those in the ternary system KCl-K2B4O7-H2O are potassium chloride （KCl） and potassium tetraborate tetrahydrate （K2B4O7·4H2O）.Comparisons of the phase diagrams of the two systems at different temperatures show that there is no change in the crystallization phases,but there are changes in the size of the crystallization regions.As temperature increases,the solubility of K2B4O7·4H2O increases rapidly,so the crystallization field of K2B4O7·4H2O becomes smaller.     

Shear modulus, heat capacity, viscosity and structural relaxation time of Na2O–Al2O3–SiO2 and Na2O–Fe2O3–Al2O3–SiO2 melts

The configurational heat capacity, shear modulus and shear viscosity of a series of Na₂O–Fe₂O₃–Al₂O₃–SiO₂ melts have been determined as a function of composition. A change in composition dependence of each of the physical properties is observed as Na₂O/(Na₂O + Al₂O₃) is decreased, and the peralkaline melts become peraluminous and a new charge-balanced Al-structure appears in the melts. Of special interest are the frequency dependent (1 mHz–1 Hz) measurements of the shear modulus. These forced oscillation measurements determine the lifetimes of Si–O bonds and Na–O bonds in the melt. The lifetime of the Al–O bonds could not, however, be resolved from the mechanical spectrum. Therefore, it appears that the lifetime of Al–O bonds in these melts is similar to that of Si–O bonds with the Al–O relaxation peak being subsumed by the Si–O relaxation peak. The appearance of a new Al-structure in the peraluminous melts also cannot be resolved from the mechanical spectra, although a change in elastic shear modulus is determined as a function of composition. The structural shear-relaxation time of some of these melts is not that which is predicted by the Maxwell equation, but up to 1.5 orders of magnitude faster. Although the configurational heat capacity, density and shear modulus of the melts show a change in trend as a function of composition at the boundary between peralkaline and peraluminous, the deviation in relaxation time from the Maxwell equation occurs in the peralkaline regime. The measured relaxation times for both the very peralkaline melts and the peraluminous melts are identical with the calculated Maxwell relaxation time. As the Maxwell equation was created to describe the timescale of flow of a mono-structure material, a deviation from the prediction would indicate that the structure of the melt is too complex to be described by this simple flow equation. One possibility is that Al-rich channels form and then disappear with decreasing Si/Al, and that the flow is dominated by the lifetime of Si–O bonds in the Al-poor peralkaline melts, and by the lifetime of Al–O bonds in the relatively Si-poor peralkaline and peraluminous melts with a complex flow mechanism occurring in the mid-compositions. This anomalous deviation from the calculated relaxation time appears to be independent of the change in structure expected to occur at the peralkaline/peraluminous boundary due to the lack of charge-balancing cations for the Al-tetrahedra.     

Equilibrium experiments in the system MgO–SiO2–H2O (MSH): stability fields of clinohumite-OH [Mg9Si4O16(OH)2], chondrodite-OH [Mg5Si2O8(OH)2] and phase A (Mg7Si2O8(OH)6)

The water-pressure and temperature stability fields of clinohumite-OH, chondrodite-OH and phase A were determined in reversed equilibrium experiments up to 100 kbar within the system MgO–SiO₂–H₂O. Their PT-fields differ from results from former synthesis experiments. Bracketing experiments on the reaction phase A + low P-clinoenstatite ⇆ forsterite + water resulted in a slightly steeper dP/dT-slope compared to earlier experiments for this equilibrium. Clinohumite-OH and chondrodite-OH both have large stability fields which extend over pressure ranges of more than 80 kbar. However, they are hardly relevant as hydrous minerals within the subducted oceanic lithosphere. Both are too Mg-rich for a typical mantle bulk composition. In addition, the dehydration of subducted oceanic lithosphere – due to (forsterite + water)-forming reactions – will occur before the two humite-group phases even become stable. Restricted to the cool region of cold subducting slabs, phase A, however, might be formed via the reactions phase A + low P-/high P-clinoenstatite ⇆ forsterite + water or antigorite + brucite ⇆ phase A + water, before dehydration of the oceanic lithosphere occurs. Received: 22 July 1997 / Accepted: 12 March 1998     

Solid-liquid Equilibria for the Quaternary NaCl–Na2SO4–Na2B4O7–H2O System at 348 K

正1 Introduction China has very abundant liquid mineral resources.Especially,the brine resources in the west of Sichuan Basin are pushed into the first place in China,whose K and B contents are unusually high.These rare liquid mineral resources have very good exploitation prospect(Lin,2001;2006).Generally speaking,phase equilibrium     

Melt–Fluid and Fluid–Fluid Immiscibility in a Na2SO4–SiO2–H2O System and Implications for the Formation of Rare Earth Deposits

Liquid–liquid immiscibility has crucial influences on geological processes, such as magma degassing and formation of ore deposits. Sulfate, as an important component, associates with many kinds of deposits. Two types of immiscibility, including (i) fluid–melt immiscibility between an aqueous solution and a sulfate melt, and (ii) fluid–fluid immiscibility between two aqueous fluids with different sulfate concentrations, have been identified for sulfate–water systems. In this study, we investigated the immiscibility behaviors of a sulfate- and quartz-saturated Na2SO4–SiO2–H2O system at elevated temperature, to explore the phase relationships involving both types of immiscibility. The fluid–melt immiscibility appeared first when the Na2SO4–SiO2–H2O sample was heated to ~270°C, and then fluid–fluid immiscibility emerged while the sample was further heated to ~450°C. At this stage, the coexistence of one water-saturated sulfate melt and two aqueous fluids with distinct sulfate concentrations was observed. The three immiscible phases remain stable over a wide pressure–temperature range, and the appearance temperature of the fluid–fluid immiscibility increases with the increased pressure. Considering that sulfate components occur extensively in carbonatite-related deposits, the fluid–fluid immiscibility can result in significant sulfate fractionation and provides implications for understanding the formation of carbonatite-related rare earth deposits.     

高温高压下Mg2SiO4-MgAlO4体系相变的实验研究

采用多顶砧高压实验装置研究了Mg2SiO4-MgAl2O4体系在压力为22 GPa,温度为1550～1750℃条件下的相变,并考查了Al2O3在γ相中的固溶度.结果表明,随着体系中MgAl2O4组分含量的增加,相组合发生了变化,依次为γ相+镁铝硅酸盐固溶体+方镁石→镁铝硅酸盐固溶体+方镁石→镁铝硅酸盐固溶体+方镁石+刚玉固溶体;镁铝硅酸盐固溶体具有石榴子石结构,其化学成分随着体系中共存相的改变而有所变化;Al2O3在γ相中的固溶度很低(其重量百分比＜0.8%),因此,在Mg2SiO4-MgAl2O4体系中Al2O3可能对γ相超尖晶石分解转变的压力不会有很大的影响.     

Solubility and partitioning of water in synthetic forsterite and enstatite in the system MgO–SiO2–H2O±Al2O3

The solubility of water in coexisting enstatite and forsterite was investigated by simultaneously synthesizing the two phases in a series of high pressure and temperature piston cylinder experiments. Experiments were performed at 1.0 and 2.0 GPa at temperatures between 1,100 and 1,420°C. Integrated OH absorbances were determined using polarized infrared spectroscopy on orientated single crystals of each phase. Phase water contents were estimated using the calibration of Libowitzky and Rossman (Am Mineral 82:1111–1115, 1997). Enstatite crystals, synthesized in equilibrium with forsterite and an aqueous phase at 1,350°C and 2.0 GPa, contain 114 ppm H₂O. This is reduced to 59 ppm at 1,100°C, under otherwise identical conditions, suggesting a strong temperature dependence. At 1,350°C and 1.0 GPa water solubility in enstatite is 89 ppm, significantly lower than that at 2.0 GPa. In contrast water solubility in forsterite is essentially constant, being in the range 36–41 ppm for all conditions studied. These data give partition coefficients in the range 2.28–3.31 for all experiments at 1,350°C and 1.34 for one experiment at 1,100°C. The incorporation of Al₂O₃ in enstatite modifies the OH stretching spectrum in a systematic way, and slightly increases the water solubility.     

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.     

Solid-liquid Equilibria for the System KBr–K2SO4–H2O at 348 K

正1 Introduction The underground brine resources distributing widely in Sichuan Basin,China have drawn worldwide attention due to their unusual element abundance and excellent quality.     

Experimental determination of activity-composition relations in Ni2SiO4− Mg2SiO4 and Co2SiO4-Mg2SiO4 olivine solid solutions at 1200 K and 0.1 MPa and 1573 K and 0.5 GPa

Activity-composition relations in the olivine solid solutions Ni₂SiO₄⁻ -Mg₂SiO₄ and Co₂SiO₄-Mg₂SiO₄ have been determined at 1200 K and 0.1 MPa and at 1573 K and 0.5 GPa by equilibration with the corresponding oxide solutions. Both olivine solutions show small positive deviations from ideal (two site) mixing, which, within the limits of accuracy of the method, may be described by the simple regular solution model with parameters W_Ni+Mg^ol= 0.35 ± 1.0 kJ/g-atom and W_Co-Mg^ol = 1.37 ± 0.9 kJ/g-atom. The requirements of internal consistency between the two systems also show that the recent determination by Brousse et al. (1984) of the enthalpy of formation of Mg₂SiO₄is to be preferred over earlier work, and that their value is also probably more accurate than the uncertainty in their own measurements indicates; activities in the NiO-MgO system are close to ideal.     

The thermal stability of sideronatrite and its decomposition products in the system Na2O–Fe2O3–SO2–H2O

The thermal stability of sideronatrite, ideally Na₂Fe³⁺(SO₄)₂(OH)·3(H₂O), and its decomposition products were investigated by combining thermogravimetric and differential thermal analysis, in situ high-temperature X-ray powder diffraction (HT-XRPD) and Fourier transform infrared spectroscopy (HT-FTIR). The data show that for increasing temperature there are four main dehydration/transformation steps in sideronatrite: (a) between 30 and 40 °C sideronatrite transforms into metasideronatrite after the loss of two water molecules; both XRD and FTIR suggest that this transformation occurs via minor adjustments in the building block. (b) between 120 and 300 °C metasideronatrite transforms into metasideronatrite II, a still poorly characterized phase with possible orthorhombic symmetry, consequently to the loss of an additional water molecule; X-ray diffraction data suggest that metasideronatrite disappears from the assemblage above 175 °C. (c) between 315 and 415 °C metasideronatrite II transforms into the anhydrous Na₃Fe(SO₄)₃ compound. This step occurs via the loss of hydroxyl groups that involves the breakdown of the [Fe³⁺(SO₄)₂(OH)] _∞ ^2? chains and the formation of an intermediate transient amorphous phase precursor of Na₃Fe(SO₄)₃. (d) for T > 500 °C, the Na₃Fe(SO₄)₃ compound is replaced by the Na-sulfate thenardite, Na₂SO₄, plus Fe-oxides, according to the Na₃Fe³⁺(SO₄)₃ → 3/2 Na₂(SO₄) + 1/2 Fe₂O₃ + SO_x reaction products. The Na–Fe sulfate disappears around 540 °C. For higher temperatures, the Na-sulfates decomposes and only hematite survives in the final product. The understanding of the thermal behavior of minerals such as sideronatrite and related sulfates is important both from an environmental point of view, due to the presence of these phases in evaporitic deposits, soils and sediments including extraterrestrial occurrences, and from the technological point of view, due to the use of these materials in many industrial applications.     

Fe–Mg Interdiffusion in (Mg,Fe)O

We have performed a series of interdiffusion experiments on magnesiowüstite samples at room pressure, temperatures from 1,320° to 1,400°C, and oxygen fugacities from 10^?1.0 Pa to 10^?4.3 Pa, using mixed CO/CO₂ or H₂/CO₂ gases. The interdiffusion couples were composed of a single-crystal of MgO lightly pressed against a single-crystal of (Mg_1-x Fe _x )_1-δO with 0.07<x<0.27. The interdiffusion coefficient was calculated using the Boltzmann–Matano analysis as a function of iron content, oxygen fugacity, temperature, and water fugacity. For the entire range of conditions tested and for compositions with 0.01<x<0.27, the interdiffusion coefficient varies as $$\tilde D\, =\,2.9\times10^{ - 6}\,f_{{\text{O}}_2 }^{0.19}\,x^{0.73}\,{\text{e}}^{ - (209,000\, -\,96,000\,x)/RT}\,\,{\text{m}}^{\text{2}} {\text{s}}^{ -1} $$ These dependencies on oxygen fugacity and composition are reasonably consistent with interdiffusion mediated by unassociated cation vacancies. For the limited range of water activity that could be investigated using mixed gases at room pressure, no effect of water on interdiffusion could be observed. The dependence of the interdiffusion coefficient on iron content decreased with increasing iron concentration at constant oxygen fugacity and temperature. There is a close agreement between our activation energy for interdiffusion extrapolated to zero iron content (x=0) and that of previous researchers who used electrical conductivity experiments to determine vacancy diffusivities in lightly doped MgO.     

In situ Raman observation of the crystallization in NaNO3–Na2SO4–H2O solution droplets

Several double salts have been detected in building materials and most of these salts are incongruently soluble compounds. In contrast to single salts, however, no systematic investigations of the crystallization behavior and deleterious effects of incongruently soluble double salts exist. To assess the damage potential of these salts, a systematic investigation of their highly complex behavior is desirable. This paper deals with the crystallization behavior of various solids in the ternary mixed NaNO₃–Na₂SO₄ system including the formation of the double salt darapskite, Na₃NO₃SO₄·H₂O. The crystallization sequence during droplet evaporation experiments at room conditions was determined using Raman and polarization microscopy. The basic idea of this research is to use deviations of the crystallization sequence of a salt or a mixed salt solution from the equilibrium pathway as an indicator to detect the degree of supersaturation. The observed crystallization pathway includes the formation of the metastable phases Na₂SO₄(III), Na₂SO₄(V) and darapskite. The experimental observations are discussed on the basis of the NaNO₃–Na₂SO₄–H₂O phase diagram and the results provide evidence for crystal growth from highly supersaturated solutions in both systems. If the crystals growing under these conditions are confined, these supersaturations result in substantial crystallization pressures.     

Raman study of MgCr2O4–Fe2+Cr2O4 and MgCr2O4–MgFe2 3+O4 synthetic series: the effects of Fe2+ and Fe3+ on Raman shifts

Two synthetic series of spinels, MgCr₂O₄–Fe²⁺Cr₂O₄ and MgCr₂O₄–MgFe₂ ³⁺O₄ have been studied by Raman spectroscopy to investigate the effects of Fe²⁺ and Fe³⁺ on their structure. In the first case, where Fe²⁺ substitutes Mg within the tetrahedral site, there is a continuous and monotonic shift of the Raman modes A_1g and E_g toward lower wavenumbers with the increase of the chromite component into the spinel, while the F_2g modes remain nearly in the same position. In the second series, for low Mg-ferrite content, Fe³⁺ substitutes for Cr in the octahedral site; when the Mg-ferrite content nears 40 %, a drastic change in the Raman spectra occurs as Fe³⁺ starts entering the tetrahedral site as well, consequently pushing Mg to occupy the octahedral one. The Raman spectral region between 620 and 700 cm^?1 is associated to the octahedral site, where three peaks are present and it is possible to observe the Cr–Fe³⁺ substitution and the effects of order–disorder in the tetrahedral site. The spectral range at 500–620 cm^?1 region shows that there is a shift of modes toward lower values with the increase of the Mg-ferrite content. The peaks in the region at 200–500 cm^?1, when observed, show little or negligible Raman shift.     

Cordierite-garnet-sillimanite-quartz equilibrium: I. New experimental calibration in the system FeO−Al2O3−SiO2−H2O and certain P-T-X H2O relations

The equilibrium in which hydrous Fe-cordierite breaks down to almandine, sillimanite, quartz, and water was previously experimentally determined by Richardson (1968) and Holdaway and Lee (1977) using QMF buffer and by Weisbrod (1973) using QIF buffer. All these studies yielded similar results — a negative dP/dT slope for the equilibrium curve. However, based on theoretical arguments, Martignole and Sisi (1981), and based on Fe-Mg partitioning experiments on coexisting cordierite and garnet in equilibrium with sillimanite and quartz, Aranovich and Podlesskii (1983) suggested that this equilibrium curve has a positive dP/dT slope and its position depends on the water content of the equilibrium cordierite. We have redetermined this equilibrium using a much improved tecnique of detecting reaction direction, and cordierite starting material that contained virtually no hercynite. Hercynite was present as a contaminant in the cordierites of previous experimental studies and possibly reacted with quartz during the experimental runs to expand the apparent stability field of Fe-cordierite. We synthesized Fe-cordierite from reagent grade oxides at 710°C and 2 kbar (using QMF buffer) with two intermediate stages of grinding and mixing. The cordierite has a unit cell volume of 1574.60 ų (molar volume=23.706 J/bar) and no Fe³⁺ as indicated by X-ray diffraction and room temperature Mössbauer studies respectively. Reaction direction was concluded by noting20% change of the ratios of intensities of two key X-ray diffraction peaks of cordierite and almandine. Our results show that the four-phase equilibrium curve passes through the points 2.1 kbar, 650°C and 2.5 kbar, 750°C. This disagrees with all previous experimental studies. H₂O in the Fe-cordierite, equilibrated at 2.2 kbar and 700°C and determined by H-extraction line in the stable isotope laboratory, is 1.13 wt% (n=0.41 moles). H₂O content of pure Mg-cordierite equilibrated under identical conditions and determined by thermogravimentric conditions and determined by thermogravimetric analysis is 1.22 wt% (n=0.40). Similar determinations on Fe-cordierite and Mg-cordierite equilibrated at 2.0 kbar and 650°C show 1.27 wt% (n=0.46) and 1.47 wt% (n=0.48) of H₂O respectively. Thus, H₂O content appears to be independent of Fe/Mg ratio in cordierite, a conclusion which supports previous experimental determinations. The experimentally determined equilibrium curve represents conditions of P_H2O=P_total. From this we calculated the anhydrous curve representing equilibrium under conditions of X _H2O ^V =0.0. A family of calculated equilibrium curves of constant n _H2O ^Cord cut the experimentally determined curve at a very small angle indicating a slight variation in n _H2O ^Cord in cordierite in equilibrium with almandine, sillimanite, and quartz under the conditions of constant X _H2O ^V . Ancther set of calculated equilibrium curves, each representing constant a _H2O ^V demonstrate that the slopes of the curves vary with X _H2O ^V , and are all positive in the full range of 0.0X _H2O ^V 1.0.     

Phase equilibria in the silica-undersaturated part of the KAlSiO4– Mg2SiO4– Ca2SiO4– SiO2– F system at 1 atm and the larnite-normative trend of melt evolution

The evolution of nephelinitic melts in equilibrium with mica-bearing liquidus assemblages and melting relations have been studied on two silica-undersaturated joins of the KAlSiO₄– Mg₂SiO₄– Ca₂SiO₄– SiO₂– F system at atmospheric pressure by quench runs in sealed platinum capsules. Fluorine has been added to the batch compositions by the direct exchange of fluorine for oxygen (2F⁻ = O²⁻). The first join is the pseudo-ternary Forsterite – Diopside – KAlSiO₃F₂ system. Forsterite, diopside, F-phlogopite and leucite crystallisation fields and a fluoride-silicate liquid immiscibility solvus are present on the liquidus surface of the join. Sub-liquidus and sub-solidus phases include akermanite, cuspidine, spinel, fluorite and some other minor fluorine phases. The second system is the pseudo-binary Akermanite – F-phlogopite join that intersects the Forsterite – Diopside – KAlSiO₃F₂ join. Akermanite, forsterite, diopside, F-phlogopite, leucite and cuspidine are found to crystallise on the join. Forsterite (fo) and leucite (lc) are related to F-phlogopite (phl) by a reaction with the fluorine-bearing liquid: fo + lc + l = phl, and the reaction proceeds until forsterite or leucite are completely consumed. The reaction temperature and resulting phase association depend on batch composition. Thus, leucite is not stable in the sub-solidus of the Akermanite – F-phlogopite join, but is preserved in a part of the Forsterite – Diopside – KAlSiO₃F₂ system where forsterite reacts out, or does not crystallise at all. The phlogopite-in reaction has an important effect on the composition of the coexisting liquid. The liquids initially saturated in forsterite evolve to extremely Ca rich, larnite-normative residuals. The experimental data show that larnite-normative melilitolites can crystallise from evolved melilititic melts generated from “normal” melanephelinitic parental magmas with no normative larnite. The evolution towards melilitites requires fractionation of phlogopite-bearing assemblages under volatile pressure. Received: 3 June 1997 / Accepted: 5 January 1998