Effect of anorthite on granite phase relations: Experimental data and models

New experimental data on the effect of anorthite (An) on liquidus phase equilibria in the system Qz–Ab–Or are presented. The data were obtained for 5 wt% An added to variable Qz/Ab/Or compositions at 300 MPa and under H₂O-saturated conditions. Crystal–liquid equilibria were determined for 13 synthetic glass compositions made from gels in experiments performed between 660 and 750 °C in cold-seal pressure vessels. Forward and reversal experiments were systematically conducted on each composition to demonstrate equilibrium. A total of 51 charges was examined. Three crystalline phases, quartz, alkali feldspar and plagioclase appear on the H₂O-saturated liquidus surface. The determined minimum liquidus 5 wt% An “piercing” point (39% Qz, 33% Ab, 28% Or) is shifted away from the Ab apex toward the Qz–Or sideline when compared with the An-free 300 MPa H₂O-saturated minimum. This shift is of the same type as that observed at 100 MPa in the same system and at 200 MPa in a rhyolitic system. The new experimental results are used to test both empirical and thermodynamic models for silicic magmas. Empirical models reproduce reasonably well the new experimental data, although more sophisticated calculations schemes appear to be required to improve their accuracy. The new experimental results in the haplogranodiorite system are not well reproduced with the model of Holland and Powell (2001), mainly because plagioclase stability appears greatly enhanced in the model. Rhyolite-MELTS satisfactorily reproduces the Qz-, Pl- and Af-liquid phase equilibria, but model H₂O solubilities are significantly lower and crystallization temperatures higher than in experiments.     

Analysis of accumulation conditions of minor elements in mineral waters: An example of hydrocarbonate sodic waters of the Nagutskoe mineralized groundwater field

Computer simulations of carbon dioxide leaching of Aptian–Albian sandstone at the Nagutskoe groundwater field, Caucasian Mineral Waters, are compared with laboratory experimental data obtained using a high-pressure autoclave under parameters close to conditions under which mineral waters are formed at the Nagutskoe and Essentuki fields (temperatures 20–25 and 65–70°C, carbon dioxide pressure up to 4.04 MPa). The solvents were distilled water and naturally occurring groundwaters from the Caucasian Mineral Waters (CMW) area, individual experimental runs lasted for 2 h, the starting material (rock) was crushed to 0.25 mm, and the gas phase was carbon dioxide. In most of the experiments, the solid: liquid phase (R/W) ratio was 1: 5 and was varied from 1: 10 to 1: 100 in other experiments. Our simulation results indicate that multiple-cycle (10 cycles) leaching leads to an increase in mineralization from 1.3 g/L to 4 g/L and transformation of the geochemical type of the waters from the hydrocarbonate calcic–sodic one (leaching cycle 1) to chloride–hydrocarbonate sodic (cycles 5 and later). The mineralization increased mostly because the and Na⁺ ions are transferred into solution at an insignificant increase in the Cl concentration and a practically unchanging concentrations of the sulfate, calcium, and magnesium ions. With regard for the averaged mineralogical composition of the sandstone (quartz, feldspars, mica, glauconite, magnetite, ilmenite, garnet, rutile, zircon, and tourmaline) used in our thermodynamic simulations, we arrived at the conclusion that the chemical compositions of the waters, including their minor-element compositions, are controlled by (i) the composition of the cement (clay, calcareous, siliceous, limonitic, chloritic, zeolitic, phosphate, sulfate, or mixed) of the rocks, (ii) weight percentages of minerals containing certain elements, and (iii) temperature, at a given composition of the gas phase of the simulated system (silty sandstone–rainwater–CO₂ gas phase).     

Crystallization of high-Ca chromium garnet upon interaction of serpentine,chromite, and Ca-bearing hydrous fluid

The results of experimental modeling of the conditions of crystallization of high-Ca chromium garnets in the system serpentine–chromite–Ca-Cr-bearing hydrous fluid at a pressure of 5 GPa and temperature of 1300°С are reported. The mineral association including quantitatively predominant high-Mg olivine and diopside-rich clinopyroxene, bright-green garnet, and newly formed chrome spinel was formed. Garnet mostly crystallized around primary chromite grains and was characterized by a high concentration of CaO and Cr₂O₃. According to the chemical composition, garnets obtained are close to the uvarovite–pyrope varieties, which enter the composition of relatively rare natural paragenesis of garnet wehrlite. The experimental data obtained clearly show that high-Ca chromium garnets are formed in the reaction of chromite-bearing peridotite and Ca-rich fluid at high P–T parameters.

     

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.     

Garnet and spinel lherzolite assemblages in MgO–Al2O3–SiO2 and CaO–MgO–Al2O3–SiO2: thermodynamic models and an experimental conflict

The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al₂O₃–SiO₂ (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO₂ (CMS) and MgO–Al₂O₃–SiO₂ (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.     

The physicochemical conditions of diamond formation in the mantle matter: experimental studies

Experimental studies of diamond formation in the alkaline silicate-carbon system Na₂O–K₂O–MgO–CaO–Al₂O₃–SiO₂–C were carried out at 8.5 GPa. In accordance with the diamond nucleation criterion, a high diamond generation efficiency (spontaneous mass diamond crystallization) has been confirmed for the melts of the system Na₂SiO₃–carbon and has been first established for the melts of the systems CaSiO₃–carbon and (NaAlSi₃O₈)₈₀(Na₂SiO₃)₂₀–carbon. It is shown that in completely miscible carbonate-silicate melts oversaturated with dissolved diamond-related carbon, a concentration barrier of diamond nucleation (CBDN) arises at a particular ratio of carbonate and silicate components. Study of different systems (eclogite–K-Na-Mg-Ca-Fe-carbonatite–carbon, albite–K₂CO₃–carbon, etc.) has revealed a dependence of the barrier position on the chemical composition of the system and the inhibiting effect of silicate components on the nucleation density and rate of diamond crystal growth. In multicomponent eclogite-carbonatite solvent, the CBDN is within the range of carbonatite compositions (<50 wt.% silicates). Based on the experimental criterion for the syngenesis of diamond and growth inclusions in them, we studied the syngenesis diagram for the system melanocratic carbonatite–diamond and determined a set of the composition fields and physical parameters of the system that are responsible for the cogeneration of diamond and various mineral and melt parageneses. The experimental results were applied to substantiate a new physicochemical concept of carbonate-silicate (carbonatite) growth media for most of natural diamonds and to elaborate a genetic classification of growth mineral, melt, and fluid inclusions in natural diamonds of mantle genesis.     

Clay minerals in sediments of the hydrothermally active southern trough in the Guaymas Basin (Gulf of California)

The results of the study of clay mineral alterations in Upper Pleistocene sediments of the southern trough in the Guaymas Basin (Gulf of California) due to the influence of hydrothermal solutions and heat produced by sill intrusions are discussed. Core samples from DSDP Holes 477 and 477A were taken for the analysis of clay minerals. Application of the method of modeling X-ray diffraction patterns of oriented specimens of the finely dispersed particles made it possible to establish the phase composition of clay minerals, determine their structural parameters, and obtain reliable quantitative estimates of their contents in natural mixtures. The modeling data allowed us to characterize reliably the transformation of clay minerals in sediments of the hydrothermally active southern trough in the Guaymas Basin. In Upper Pleistocene sandy–clayey sediments of the southern trough, changes in the composition of clay minerals occurred under the influence of a long-living hydrothermal system. Its lower part (interval 170.0–257.5 m) with maximum temperatures (~300°C) was marked by the formation of chlorite. Terrigenous clay minerals are not preserved here. Saponite appears at a depth of 248 m in the chlorite formation zone. Higher in the sedimentary section, the interval 146–170 m is also barren of terrigenous clay minerals. Sediments of this interval yielded two newly formed clay minerals (chlorite and illite), which were formed at lower temperatures (above 180°C and below 300°C, approximately up to ~250°C), while the relatively low-temperature upper part (110–146 m) of the hydrothermal system (from ~140°C to ~180°C) includes the mixture of terrigenous and newly formed clay minerals. Terrigenous illite is preserved here. Illitization of the mixed-layer illite–smectite was subjected to illitization. The terrigenous montmorillonite disappeared, and chlorite–smectite with 5–10% of smectite layers were formed. In the upper interval (down to approximately 110 mbsf), the composition of terrigenous clay minerals remains unchanged. They are composed of the predominant mixed-layer illite–smectite and montmorillonite, the subordinate illite, mixed-layer chlorite–smectite with 5% of smectite layers, mixed-layer kaolinite–smectite with 30% of smectite layers, and kaolinite. This composition of clay minerals changed under the influence of sill intrusions into the sedimentary cover at 58–105 m in the section of Hole 477. The most significant changes are noted in the 8-m-thick member above the sill at 50–58 m. The upper part of this interval is barren of the terrigenous mixed-layer illite–smectite, which is replaced by the newly formed trioctahedral smectite (saponite). At the same time, the terrigenous dioctahedral smectite (montmorillonite) is preserved. The composition of terrigenous clay minerals remains unchanged at the top of the unit underlying the sill base.     

Experimental modeling of native carbon formation in a C–O–H fluid system

Integrated data are presented on structure–morphology features, as well as on the material and phase composition, of a fluid-produced carbonaceous substance (CS) formed under known thermodynamic conditions of the experiment (C–O–H system, 500–800°C, and 500–1000 atm). Solid products of the synthesis were examined by means of X-ray phase and thermal analyses, scanning electron microscopy combined with microprobe analysis, transmission electron microscopy, high-resolution Raman spectroscopy, IR spectroscopy, and CHN-analysis. The characteristics of the experimental CS may be applicable in genetic modeling of natural ore-bearing fluidal carbonaceous systems.     

An experimental study of Cl and S distribution between sodalite and fluid

S and Cl distribution between sodalite and fluid was experimentally studied at temperatures of 300–800°C and pressure of 0.5–3 kbar. It is demonstrated that S is preferably distributed into fluid in equilibrium with sodalite of the composition X _S ^Sod > 0.05 throughout the whole temperature range. The distribution of S in the sodalite-fluid system is nonideal. An equation (derived from experimental data) is presented for evaluating the S mole fraction in fluid from the composition of sodalite at a known temperature. The S mole fractions in the fluid are evaluated for sodalite assemblages from nepheline syenites of the Lovozero Massif as being within the range of 0.036–0.23. The S mole fraction in the fluid is proved to increase with increasing mineral formation temperatures.     

对幔源岩中流体组成的不同测定方法评价

本文对比了上前广泛用于幔源岩中流体组成测定的不同实验方法,讨论了每种方法的优点和适用范围。根据地幔流体所处特殊的地幔环境（高温高压）,认为分步加热质谱法测定的结果较全面地代表了幔源岩中流体的真实组成;在实验过程中进行有效的样品处理,采用合理的实验装置和系统本底,对获取可靠的数据至关重要;且通过控制加热温度可对不同类型的流体组分分别进行研究。     

Geochemistry and petrogenesis of suprasubduction volcanic complexes of the Char shear zone,eastern Kazakhstan

The paper presents new petrographic, geochemical, and petrologic data from volcanic rocks of suprasubduction origin of the Char shear zone in eastern Kazakhstan. We discuss bulk rock composition (concentrations of major and trace elements), types of mantle sources and parameters of their melting, conditions of crystallization of mafic magma, and geodynamic settings of basalt eruption. According to the major element composition, the volcanic rocks are basalt, andesibasalt, and andesite of tholeiitic and transitional, from tholeiitic to calc-alkaline, series. They are characterized by low TiO₂ (0.85 wt.% on average) and crystallization trends in MgO–major elements plots. In terms of trace element composition, the volcanic rocks possess moderately LREE-enriched rare-earth element patterns and are characterized by negative Nb anomalies present on the multi-element spectra (Nb/La_pm = 0.14–0.47; Nb/Th_pm = 0.7–1.6). The distribution of rare-earth elements (La/Sm_n = 0.8–2.3, Gd/Yb_n = 0.7–1.9) and the results of geochemical modeling in the Nb–Yb system suggest high degrees of melting of a depleted mantle source at spinel facies depths. Fractional crystallization of clinopyroxene, plagioclase, and opaque minerals also affected the final composition of the volcanic rocks. Clinopyroxene monomineral thermometry calculations suggest that the melts crystallized within a range of 1020–1180 °C. We think that this volcanic complex formed at a western active margin of the Paleo-Asian Ocean.     

Abnormal composition of carbon isotopes in underground alkaline waters of Kuzbass

The first data on abnormally high δ¹³С values in hydrocarbonates (НСО ₃^-) dissolved in underground waters of coal deposits of Kuzbass (up to +30.9‰) are reported. It is shown that such an unusual isotope composition of waters results from the long, strictly directed interaction in the water–rock–gas–organic material system occurring under the conditions of hindered water exchange. Extensive fractionation of C isotopes is the result of the evolution of the water–rock–gas–coal system after penetration of infiltration waters into the coal deposits and their long interaction with all these components, rather than metamorphism of organic material upon its transformation into coal. With respect to such an approach, the isotope composition of dissolved C may indicate the duration of the evolution in the water–rock–gas–organic material system.     

The Blacktail Creek Tuff: an analytical and experimental study of rhyolites from the Heise volcanic field,Yellowstone hotspot system

The magma storage conditions of the 6.62 Ma Blacktail Creek Tuff eruption, belonging to the Heise volcanic field (6.62–4.45 Ma old) of the Yellowstone hotspot system, have been investigated by combining thermobarometric and experimental approaches. The results from different geothermometers (e.g., Fe–Ti oxides, feldspar pairs, apatite and zircon solubility, and Ti in quartz) indicate a pre-eruptive temperature in the range 825–875 °C. The temperature estimated using two-pyroxene pairs varies in a range of 810–950 °C, but the pyroxenes are probably not in equilibrium with each other, and the analytical results of melt inclusion in pyroxenes indicate a complex history for clinopyroxene, which hosts two compositionally different inclusion types. One natural Blacktail Creek Tuff rock sample has been used to determine experimentally the equilibrium phase assemblages in the pressure range 100–500 MPa and a water activity range 0.1–1.0. The experiments have been performed at fluid-present conditions, with a fluid phase composed of H₂O and CO₂, as well as at fluid-absent conditions. The stability of the quartzo-feldspathic phases is similar in both types of experiments, but the presence of mafic minerals such as biotite and clinopyroxene is strongly dependent on the experimental approach. Possible explanations are given for this discrepancy which may have strong impacts on the choice of appropriate experimental approaches for the determination of magma storage conditions. The comparison of the composition of natural phases and of experimentally synthesized phases confirms magma storage temperatures of 845–875 °C. Melt water contents of 1.5–2.5 wt% H₂O are required to reproduce the natural Blacktail Creek Tuff mineral assemblage at these temperatures. Using the Ti-in-quartz barometer and the Qz–Ab–Or proportions of natural matrix glasses, coexisting with quartz, plagioclase and sanidine, the depth of magma storage is estimated to be in a pressure range between 130 and 250 MPa.     

Intergranular diamonds derived from partial melting of crustal rocks at ultrahigh-pressure metamorphic conditions

By reporting for the first time intergranular diamond in quartz–feldspar (Qtz–Kfs) aggregates, the processes of metamorphic diamond formation have to be reconsidered. Based on their Kfs/Qtz ratio, the texture of these aggregates are proposed to result from ‘granitic’ melt with a calculated composition that corresponds well with that of experimental data for the pelitic system. Taking into account experiments on CO₂ solubility in silicate melt under ultrahigh‐pressure conditions, a granitic melt is further suggested to act as a crystallization medium as well as a transport medium for producing metamorphic diamond.     

Experimental modelling of corona textures

Formation of corona textures along olivine–plagioclase and orthopyroxene–plagioclase interfaces has been experimentally reproduced at 670 and 700 °C and 5 kbar with either a pure H₂O fluid phase or 0.1 and 37 m NaCl–H₂O solution fluid. In these experiments, we investigate the interaction of primary olivine and/or orthopyroxene and plagioclase in powders and polished crystals, and in small samples of a natural gabbro. The experiments result in the formation of corona textures with several layers of different assemblages (according to the experimental conditions) consisting of garnet (grossular), clinopyroxene, orthopyroxene, amphibole, chlorite and phlogopite. The experiments show major differences in the number of layers, the mineral assemblages and mineral composition, and in the trends of composition of plagioclase in coronas around olivine and orthopyroxene. The fluid phase composition influences the corona assemblages and the composition of the minerals in the experimental coronas; for example, garnet appears in the coronas in the second experiment where the NaCl–H₂O ratio is low. Experimental modelling of corona textures confirms a model of simultaneous growth of layers by the mechanism of diffusion metasomatism with participation of a fluid phase through which mass is transferred. Zoning in the experimental coronas shows opposing diffusion of Al and Ca from plagioclase and Mg and Fe from olivine/orthopyroxene; difference in the mobility of the components is inferred from observations in the coronas. The experimental corona textures are compared with natural coronas from the Belomorian belt (Baltic shield), developed at 670–690 °C and 7–8 kbar, and the Marun‐Keu complex (Polar Urals), developed at 670–700 °C and 14–16 kbar, where the corona textures correspond to a transitional stage of the gabbro‐to‐eclogite transformation.     

Hydrogeochemical Features of Thermal Waters of South Trungbo (Central Vietnam)

The results of studying the features of the hydrogeological structure and chemical and isotope composition of thermal waters from the central part of Vietnam that are characterized by intense manifestations of intrusive magmatism are presented. It is established that low–and high–thermal waters with temperature varying within 30–85°C are developed in the area under study. The value of total mineralization of the hydrotherms ranges from 0.05 to 10.05 g/dm³. It is assumed that the circulation of thermal waters that are different in temperature and chemical composition occurs at two levels. The regular change of the hydrotherm composition in the direction from mineralized chloride sodium, including with increased Ca content, to fresh sodium bicarbonate is revealed. The ratio of δ¹⁸O–δ²H isotopes indicates that the water component is based on meteoric water. In the coastal areas, there is an isotope shift towards the ocean waters, which is also confirmed by the hydrogeochemical data. The key factors for forming the chemical composition of the thermal waters in South Trungbo are their genetic type, the interaction processes in the “water–rock–gas–organic substance” system, and their equilibrium–nonequilibrium state.     

Overstepping the garnet isograd: a comparison of QuiG barometry and thermodynamic modeling

The consequences of overstepping the garnet isograd reaction have been investigated by comparing the composition of garnet formed at overstepped P–T conditions (the overstep or “OS” model) with the P–T conditions that would be inferred by assuming garnet nucleated in equilibrium with the matrix assemblage at the isograd (the equilibrium or “EQ” model). The garnet nucleus composition formed at overstepped conditions is calculated as the composition that produces the maximum decrease in Gibbs free energy from the equilibrated, garnet-absent, matrix assemblage for the bulk composition under study. Isopleths were then calculated for this garnet nucleus composition assuming equilibrium with the matrix assemblage (the EQ model). Comparison of the actual P–T conditions of nucleation (the OS model) with those inferred from the EQ model reveals considerable discrepancy between the two. In general, the inferred garnet nucleation P–T conditions (the EQ model) are at a lower temperature and higher or lower pressure (depending on the coexisting calcic phase(s)) than the actual (OS model) nucleation conditions. Moreover, the degree of discrepancy increases with the degree of overstepping. Independent estimates of the pressure of nucleation of garnet were made using the Raman shift of quartz inclusions in garnet (quartz-in-garnet or QuiG barometry). To test the validity of this method, an experimental synthesis of garnet containing quartz inclusions was made at 800 °C, 20 kbar, and the measured Raman shift reproduced the synthesis conditions to within 120 bars. Raman band shifts from three natural samples were then used to calculate an isochore along which garnet was presumed to have nucleated. Model calculations were made at several temperatures along this isochore (the OS model), and these P–T conditions were compared to those computed assuming equilibrium nucleation (the EQ model) to estimate the degree of overstepping displayed by these samples. A sample from the garnet isograd in eastern Vermont is consistent with overstepping of around 10 degrees and 0.6 kbar (affinities of around 2 kJ/mole garnet). A sample from the staurolite–kyanite zone in the same terrane requires overstepping of around 50 °C and 2–5 kbar (affinities of around 10–18 kJ/mole garnet). A similar amount of overstepping was inferred for a blueschist sample from Sifnos, Greece. These results indicate that overstepping of garnet nucleation reactions may be common and pronounced in regionally metamorphosed terranes, and that the P–T conditions and paths inferred from garnet zoning studies may be egregiously in error.     

On yoderite: Using calculated phase equilibria to investigate its rarity in the geological record of whiteschists

A new activity–composition model is presented for green (Mn³⁺‐absent) yoderite for use in the latest internally consistent thermodynamic data set used by THERMOCALC, for calculations primarily in MgO–Al₂O₃–SiO₂–H₂O–O system, where O is a proxy for Fe₂O₃. P–T grids calculated with our model in the MASH and MASHO system feature invariant points and univariant reaction bundles that are consistent with existing experimental results. Using this new model, we have explored the stability of yoderite in whiteschists, a rare type of high‐pressure rock that conforms closely to the MASHO system. Using a series of calculated models in which composition varies, it is shown that yoderite stability is a function of bulk‐rock SiO₂, MgO and Al₂O₃, where the most important component for stabilizing yoderite is a function of pressure and temperature. The rarity of yoderite in naturally occurring whiteschists is largely related to these compositional factors, with most whiteschists having rock compositions that are too SiO₂‐rich and Al₂O₃‐poor to allow yoderite formation. However, in addition to compositional factors, the calculated P–T stability field of yoderite occurs over thermal gradients that are generally too high to occur in modern‐style subduction zones. As nearly all known whiteschist occurrences are Phanerozoic in age, the near‐complete absence of yoderite in late Neoproterozoic–Phanerozoic whiteschists may be at least partially due to modern subduction systems failing to produce the hotter thermal gradients needed to stabilize yoderite. The provision of this new a–x model for green yoderite allows for more rigorous P–T–X investigations of all whiteschists.