Compositional variation in pyrochlores of Amba Dongar carbonatite complex,Gujarat

Pyrochlore is interpreted as a primary magmatic mineral that appeared in early carbonatite phases at Amba Dongar. Later intrusive phases incorporated this early pyrochlore and caused compositional modification, particularly around the rims, in response to changing magma chemistry. Consequently pyrochlore compositions show wide ranges in Nb, Ta, Ca, Ba, Ti and Ce. The final carbonatite phase was ankeritic and rich in hydrothermal fluids, giving rise to extreme compositional zoning and introduction of diverse elements (Si, U, Sr, Th, Fe), in the contained pyrochlore. Enrichment in radioelements such as U lead to metamictization, alteration and A-site vacancy.     

Solubility and near-equilibrium dissolution rates of quartz in dilute NaCl solutions at 398-473 K under alkaline conditions

The dissolution-precipitation of quartz controls porosity and permeability in many lithologies and may be the best studied mineral-water reaction. However, the rate of quartz-water reaction is relatively well characterized far from equilibrium but relatively unexplored near equilibrium. We present kinetic data for quartz as equilibrium is approached from undersaturation and more limited data on the approach from supersaturated conditions in 0.1 molal NaCl + NaOH + NaSiO(OH)₃ solutions with pH 8.2-9.7 at 398, 423, 448, and 473 K. We employed a potentiometric technique that allows precise determination of solution speciation within 2 kJ mol⁻¹ of equilibrium without the need for to perturb the system through physical sampling and chemical analysis. Slightly higher equilibrium solubilities between 423 and 473 K were found than reported in recent compilations. Apparent activation energies of 29 and 37 kJ mol⁻¹ are inferred for rates of dissolution at two surface sites with different values of connectedness: dissolution at Q¹ or Q² silicon sites, respectively. The dissolution mechanism varies with ΔG such that reactions at both sites control dissolution up until a critical free energy value above which only reactions at Q¹ sites are important. When our near-equilibrium dissolution rates are extrapolated far from equilibrium, they agree within propagated uncertainty at 398 K with a recently published model by Bickmore et al. (2008). However, our extrapolated rates become progressively slower than model predictions with increasing temperature. Furthermore, we see no dependence of the postulated Q¹ reaction rate on pH, and a poorly-constrained pH dependence of the postulated Q² rate. Our slow extrapolated rates are presumably related to the increasing contribution of dissolution at Q³ sites far from equilibrium. The use of the potentiometric technique for rate measurement will yield both rate data and insights into the mechanisms of dissolution over a range of chemical affinity. Such measurements are needed to model the evolution of many natural systems quantitatively.     

Solubility of gold in arsenian pyrite

Although Au and As can be enriched up to the weight percent level in arsenian pyrite, there is little knowledge of their limiting concentrations and nature of incorporation. This study reports SIMS and EMPA analyses showing that As and Au contents of arsenian pyrites plot in a wedge-shaped zone with an upper compositional limit defined by the line

CAu=0.02⋅CAs+4×10⁻⁵     

Solubility of corundum in supercritical water

Isothermal (670–700°C) solubility of corundum in supercritical water, within the stability range of corundum as a phase of the system Al₂O₃-H₂O, has been determined by the weight loss method. Experiments were performed in the pressure range 2.5 to 6 kbar in cold seal hydrothermal equipment at 670 ± 5°C using gold tubing. The overall uncertainty of the solubility values obtained was 8%. Experiments in the pressure range 10 to 20 kbar were performed in a piston cylinder apparatus at 700°C using sealed gold capsules held by supporting steel containers. The overall uncertainty of the solubility values obtained was estimated to be 10%.All data could be fitted by the linear equation S_[ppmAl2O3] = ?12.37 + 7.24 · p[_kbar] with correlation coefficient r = 0.9963. Separate fits of hydrothermal and piston cylinder results yielded a small difference between the two data sets, which is due rather to the experimental uncertainty than to the small temperature difference.     

Geobarometry for Mantle Eclogites: Solubility Of Ca-Tschermaks in Clinopyroxene

A garnet-clinopyroxene barometer is proposed for mantle eclogites on the basis of the Ca-Tscher-mack (CaTs) solubility in clinopyroxene coexisting with garnet. This barometer permits estimation of P-T conditions for garnet-clinopyroxene equilibration in the range 650°C ≤ T ≤ 1700°C and 20 ≤ P ≤ 70 kbar, with a total uncertainty of 19%. This model is applicable to pyroxenes that are sodium rich (i.e., have high jadeite contents). Application of this barometer results in high P-T estimates for Monastery and Argyle diamond inclusions. Estimates also are lower for the host Yakutian eclogites than for the diamonds included in them. This suggests differences in re-equilibration between the diamond inclusions and their host xenoliths. The results suggest that eclogite equilibration in the mantle occurs at depths from 60 to 230 km, characterized by two main types of geothermal gradients, lying close to established peridotite geotherms (Boyd, 1973).     

Rb-Sr and U-Th-Pb systematics of alkaline rocks: the alkaline rocks from Italy

The isotopic composition of Pb and Sr and the abundances of Rb, Sr, U, Th, and Pb were determined for whole rock samples from all major volcanic centres of the Cenozoic alkaline volcanism of Central and South Italy, together with some samples from the contemporaneous anatectic Tuscan volcanism. The Sr and Pb isotopic compositions of the alkaline rocks show a negative correlation combined with a regional trend: the ${}^{87}\text{Sr}{}^{86}\text{Sr}$ ratios decrease from 0.711 in the north-west to 0.704 in the south-east, while the ${}^{206}\text{Pb}{}^{204}\text{Pb}$ ratios increase from 18.7 to 20.0. Variations in both isotopic compositions are generally small throughout erupted rock sequences for any volcanic centre.The Pb and Sr isotopic abundance variations are interpreted on the basis of two alternative models, which correspond to two groups of geological processes: variations can result (i) from a time dependent development in subsystems with different $\text{Rb}\text{Sr}$ or $\text{U(Th)}\text{Pb}$ ratios or, (ii) from mixing of Sr or Pb with different isotopic compositions. Combining both Pb and Sr isotope abundance measurements it is shown that the source of each volcanic centre is formed by various degrees of mixing between two components. One component and the most southern Tuscan anatectic rocks most likely have a common source, whereas the other component of the mixing process is suggested to be a liquid fraction derived from a small degree of partial fusion of a hydrous mantle. Thus at least a two-stage evolution of the Italian alkaline rocks is indicated: first a mixing process leading to the formation of the parental material followed by differentiation processes leading to the formation of the erupted rock sequences.The geodynamic model which explains the data best is that of a lateral inhomogeneous mantle. The lateral inhomogeneities in the mantle would be the result of mixing between originally mantle and crustal derived material. The mixing process itself would not have any primary connection with the Quarternary volcanic activity.     

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.     

Solubility of palladium in picritic melts: 1. The effect of iron

In order to improve our understanding of HSE geochemistry, we evaluate the effect of Fe on the solubility of Pd in silicate melts. To date, experimentally determined Pd solubilities in silicate melt are only available for Fe-free anorthite-diopside eutectic compositions. Here we report experiments to study the solubility of Pd in a natural picritic melt as a function of pO₂ at 1300 °C in a one atm furnace. Palladium concentrations in the run products were determined by laser-ablation-ICP-MS. Palladium increases from 1.07 ± 0.26 ppm at FMQ-2, to 306 ± 19 ppm at FMQ+6.6. At a relative pO₂ of FMQ the slope in log Pd concentration vs. log pO₂ space increases considerably, and Pd concentrations are elevated over those established for AnDi melt compositions. In the same pO₂ range, ferric iron significantly increases relative to ferrous iron. Furthermore, at constant pO₂ (FMQ+0.5) Pd concentrations significantly increase with increasing X_FeO-total in the melt. Therefore, we consider ferric Fe to promote the formation of Pd²⁺ enhancing the solubility of Pd in the picrite melt significantly.The presence of FeO in the silicate melt has proven to be an important melt compositional parameter, and should be included and systematically investigated in future experimental studies, since most natural compositions have substantial FeO contents.     

Solubility and migration ability of rhodium in natural conditions: model experimental data

The contents of dissolved rhodium species in the near-neutral environments have been studied for the first time and data on the interaction of Rh with organic matters of natural waters and its sorption behavior during contact with the components of geochemical barriers were obtained. The solubility method was used to analyze the behavior of rhodium hydroxide in the Rh(OH)_x–H₂O and Rh(OH)_x–H₂O–FA (fulvic acids) systems. The possible contents of inorganic species of rhodium and its compounds with humic organic ligands were determined within the pH range typical of surface waters. The solubility of rhodium shows a twoorder- of magnitude increase in the presence of humic matters (FA). The sorption interaction of the soluble rhodium species with the main components of geochemical barriers such as iron oxyhydroxides (III), (including fulvic-acid modified ones), alumosilicates, and precipitates of humic acids in contact with natural waters was studied. It was revealed that rhodium has the high affinity to all studied materials; its species are sorbed by ferrihydrite within several hours. It is suggested that rhodium is mainly transferred as colloid with suspended particulate matters of waters and then is accumulated in bottom sediments. The differences revealed in the sorption behavior of Pt(IV), Pd(II) and Rh(III) may be used to predict the distribution of the considered platinum group elements between the components of ecosystems.     

The Solubility of Sulphur in Hydrous Rhyolitic Melts

Experiments performed at 2 kbar, in the temperature range 800–1000°C,with fO₂ between NNO–2·3 and NNO+2·9 (whereNNO is the nickel–nickel oxide buffer), and varying amountsof sulphur added to hydrous metaluminous rhyolite bulk compositions,were used to constrain the solubility of sulphur in rhyolitemelts. The results show that fS₂ exerts a dominant control onthe sulphur solubility in hydrous silicate melts and that, dependingon fO₂, a rhyolitic melt can reach sulphur contents close to1000 ppm at high fS₂. At fO₂ below NNO+1, the addition of ironto a sulphur-bearing rhyolite magma produces massive crystallizationof pyrrhotite and does not enhance the sulphur solubility ofthe melt. For a given fO₂, the melt-sulphur-content increaseswith fS₂. For fixed fO₂ and fS₂, temperature exerts a positivecontrol on sulphur solubilities, at least for fO₂ below NNO+1.The mole fraction of dissolved sulphur exhibits essentiallylinear dependence on fH₂S at low fO₂ and, although the experimentalevidence is less clear, on fSO₂ at high fO₂. The minimum insulphur solubility corresponds to the redox range where bothfH₂S and fSO₂ are approximately equal. A thermodynamic modelof sulphur solubility in hydrous rhyolite melts is derived assumingthat total dissolved sulphur results from the additive effectsof H₂S and SO₂ dissolution reactions. The model reproduces wellthe minimum of sulphur solubility at around NNO+1, in additionto the variation of the sulphide to sulphate ratio with fO₂.A simple empirical model of sulphur solubility in rhyoliticmelts is derived, and shows good correspondence between modeland observations for high-silica rhyolites. KEY WORDS: sulphur; solubility; rhyolite; thermodynamics; fO₂; fS₂     

Crystalline matrices for immobilization of actinides: Corrosion resistance in water

The rate of leaching of actinide-simulating rare-earth elements from two types of crystalline matrices consisting of titanate and titanozirconate phases was examined. The experiments were carried out at 95°C in distilled water. The rates of REE leaching from the samples were below 10^?3 g/m² day, which satisfied the requirements for the characteristics of matrices for immobilization of actinides. After passing the treated solutions through filters of 450 to 25 nm pore sizes, the REE content was changed slightly or not at all. This fact points to the minor role or to the absence of the colloidal form of REE in the solutions after the experiments.     

尖晶石中的Si含量及其存在形式

自然岩石及简单和复杂体系中实验合成或经重新平衡的尖晶石化学成分显示，在中－低压条件下，与橄榄石共存的尖晶石可含一定量的Ｓｉ，其含量随温度和压力的升高而增大。用最小二乘法对简单体系中 实验数据的热力学模拟发现，Ｓｉ在铬尖晶石中以硅酸盐尖晶石（Ｍｇ２ＳｉＯ４）形式存在，Ｍｇ２ＳｉＯ４组份在铬尖晶石中的活度ａＳＤＭＧ２ＳｉＯ４＝（ＮＳＰＭＧ／２）２＊（ＮＳＰＳｉ）２（ＮＳＰＳｉ代表以４个氧为基础的单位尖     

Crystallization of Chromite and Chromium Solubility in Basaltic Melts

The equilibrium between chromite and melt has been determinedon four basalts at temperatures of 1200–1400?C over arange of oxygen fugacity (f_o2) and pressures of 1 atm and 10kb. The Cr content of chromite-saturated melts at 1300?C and1 atm ranges from 0?05 wt.% Cr₂O₃ at a log f_o2= –3 to1?4 wt.% at a log f_o2=–12?8. The Cr²⁺/Cr³⁺ of melt increaseswith decreasing f_o2 and is estimated by assuming a constantpartitioning of Cr³⁺ between chromite and melt at constant temperature.The estimated values of Cr²⁺/Cr³⁺ in the melt are at f_o2 valuesof 4–5 orders of magnitude lower than the equivalent Fe²⁺/Fe³⁺values. The Cr/(Cr+Al) of chromite coexisting with melt at constanttemperature changes little with variation of f_o2 below log f_o2=–6.Five experiments at 10 kb indicate that Cr₂O₃ dissolved in themelt is slightly higher and the Cr/(Cr + Al) of coexisting chromiteis slightly lower than experiments at 1 atm pressure. Thus variationin total pressure cannot explain the large variations of Cr/(Cr+ Al) that are common to mid-ocean ridge basalt (MORB) chromite. Experiments on a MORB at 1 atm at f_o2 values close to fayalite-magnetite-quartz(FMQ) buffer showed that the Al₂O₃ content of melt is highlysensitive to the crystallization or melting of plagioclase,and consequently coexisting chromite shows a large change inCr/(Cr + Al). It would appear, therefore, that mixing of a MORBmagma containing plagioclase with a hotter MORB magma undersaturatedin plagioclase may give rise to the large range of Cr/(Cr +Al) observed in some MORB chromite.     

Solubility of sulfur in some magmas at 1 atmosphere

In order to understand the distribution of sulfur in igneous rooks, we determined the solubility of sulfur in volcanic rock melts (tholeiite basalt, hawaiite and rhyodacite from Hawaii) at various gas compositions and at 1250° and 1300°C and 1 atm total pressure. The solubility of sulfur in the melt passes through a minimum with change in oxygen partial pressure, if other factors are held constant. For the basaltic liquid at 1200°C, most sulfur in the melt is as dissolved sulfide (S^?2) at oxygen partial pressures below 10^?8 atm and as dissolved sulfate at oxygen partial pressures above 10^?8 atm. Based on the present solubility data, 5 per cent is inferred for volcanic gas at 1 atm total pressure in equilibrium with subaerially extruded Hawaiian tholeiite basalt (Pele's hair with 180 ppm S) at 1200°C and 10^?8 atm P_O2.     

Experimental Studies of Phenakite Solubility in Alkaline Granitoid Melts

Doklady Earth Sciences - The solubility of phenakite in aluminosilicate melts of various alkalinity was studied experimentally at T = 1000°C and P = 1 kbar in dry conditions and in the...     

Sulfur Variations in Glasses from Volcanic Rocks: Effect of Melt Composition on Sulfur Solubility

A worldwide data set of major element and sulfur analyses of undegassed lavas, pumices, and melt inclusions from 14 volcanic locations was selected to investigate the compositional effects on sulfur solubility in magmas. We utilized analyses on calc-alkaline, alkaline, and tholeiitic rocks, with a range of 3400 ppm S variation. There is a strong correlation between chemical composition and the sulfur concentration: the less silicic and the more alkaline the rocks are, the more dissolved sulfur they can carry. Also, sulfur concentration is higher in rocks that represent less polymerized melts. Elemental correlations between FeO and S, well-defined for tholeiites, do not hold for alkaline melts. The compositional effects are at least as important as the better-known pressure, temperature, and f(O₂) dependencies.     

Solubility of Pt in sulphide mattes: Implications for the genesis of PGE-rich horizons in layered intrusions

The partitioning of Pt in sulphide melt (matte) has been studied as a function of fS₂ and fO₂ at 1200 and 1300 °C. The results show that the solubility of Pt in mattes increases strongly with increasing fS₂ and decreases weakly with increasing fO₂. The increase in Pt solubility with increasing fS₂ is attributed to Pt dissolving in the melt as a sulphide species and the weak inverse dependence of Pt solubility on fO₂ to the diluting effect of increasing O in the melt at high fO₂. These results, coupled with measurements of Pt solubility in silicate melts taken from the literature, allow the calculation of Pt matte/silicate-melt partition coefficients () for a range of conditions pertinent to the formation of Pt-rich horizons in layered intrusions. The calculated values range between 10⁷ and 10¹¹, depending on fO₂ and fS₂, several orders of magnitude higher than previously published values. Our preferred value for for conditions appropriate to the Merensky Reef is 10⁷ and for the Stillwater Pt-rich horizon 10⁸. The new results are consistent with the magmatic hypothesis for Pt-rich horizons in layered intrusions.