Solubility of water-hydrogen fluid in haplogranite,albite, and sodium disilicate melts

Solubility curves of water-hydrogen fluid were studied using a high-pressure gas apparatus at a pressure of 200 MPa under variable fluid composition in haplogranite (Ab ₃₉ Or ₃₂ Qtz ₂₉, 950°C), Na-disilicate (Na₂Si₂O₅, 950°C), and albite melts (1200°C). The mole fraction of hydrogen in experiments was controlled directly by Ar-H₂ mixtures using a specially designed cell with a Shaw membrane. $ X_{H_2 }^{Ar - H_2 } $ X_{H_2 }^{Ar - H_2 } ranged from 0 to 1. In some experiments with haplogranite and Na-disilicate melts under oxidizing conditions, in order to increase the accuracy of experimental parameters, the fugacities of oxygen and hydrogen were controlled using the double-capsule technique and the solid-phase buffer mixtures Ni-NiO (NNO) and Co-CoO (CCO). The addition of H₂ to the H₂O-saturated systems ($ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } ≥ 0.012) results in the appearance of a distinct maximum on the solubility curves at $ X_{H_2 }^{H_2 O - H_2 } $ X_{H_2 }^{H_2 O - H_2 } = 0.05–0.07 (H₂ mole fractions were calculated for real H₂O-H₂ mixtures of real gases), and the maximum content of H₂O-H₂ fluid increases relative to the H₂O-saturated melts by 1.51 wt % for haplogranite melt at $ X_{H_2 } $ X_{H_2 } = 0.063, 2.68 wt % for albite melt at $ X_{H_2 } $ X_{H_2 } = 0.066, and 3.54 wt % for Na-disilicate melt at $ X_{H_2 } $ X_{H_2 } = 0.067. A further increase in H₂ content in the gas mixture decreases the solubility of H₂O-H₂ fluid in the melts, and under pure H₂ pressure, the contents of fluid components are 0.08 wt % in haplogranite melt and 0.06 wt % in albite melt. The ¹H NMR study of aluminosilicate and Na-silicate glasses obtained under the pressure of H₂O and H₂O-H₂ fluids suggests different mechanisms of the dissolution of H₂O and H₂O-H₂ fluids in magmatic melts. In addition to the spectra of dissolved water fluid, the spectra of quenched glasses synthesized under H₂O-H₂ fluid pressure exhibited a narrow line of molecular hydrogen with a width at half height of 1.8–2.0 kHz at $ X_{H_2 } $ X_{H_2 } ≥ 0.653 for albite and $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for Na-disilicate and two lines at $ X_{H_2 } $ X_{H_2 } ≥ 0.063 for the haplogranite composition.     

Petrology of the early Proterozoic platinum-bearing massif of Fedorov Tundra,Kola Peninsula

The massif of Fedorov Tundra was formed as part of the Paleoproterozoic (2.5 Ga) Fedorov-Pana platinum-bearing layered complex as a result of consecutive emplacement of two intrusive phases. The emplacement of the first phase resulted in the formation of a large layered intrusive body composed of amphibole gabbro, gabbronorite, norite, pyroxenite, olivine pyroxenite, and harzburgite. The second phase gave birth to a gabbronorite intrusion smaller in volume and enriched in sulfides and PGM. Magmatic breccia has been observed in the contact zone between two phases. The rocks of the massif are referred to the series of normal alkalinity and to the quartz- and olivine-normative groups differing in saturation with silica. Using isoplethic and isobaric joins of the q-fo-fa-di-hd-ab-an-aq phase diagram, the stages of rock formation are considered. The thermodynamic conditions of rock crystallization were determined as T = 1000−800°C and $ P_{H_2 O} $ P_{H_2 O} = 1000−2500 bar for the first intrusive phase and T = 1000–900°C and $ P_{H_2 O} $ P_{H_2 O} = 800−1000 bar for the second intrusive phase.     

On the problem of transport species of tungsten by hydrothermal solutions

The solubility of pentatungstate of sodium (PTS) Na₂W₅O₁₆ · H₂O and sodium tungsten bronzes (STB) Na_0.16WO₃ in acid chloride solutions containing 0.026, 0.26, and 3.02m NaCl have been studied at 500°C, 1000 bar, given fO₂ (Co-CoO, Ni-NiO, PTS-STB buffers), and constant NaCl/HCl ratio (Ta₂O₅-Na₂Ta₄O₁₁ buffer). Depending on experimental conditions, the tungsten content in the solutions after experiments varied from 10⁻³ to 2 × 10⁻² mol/kg H₂O. Obtained data were used to calculate the formation constants of predominant tungsten complexes (VI, V): H₃W₃^VIO₁₂³⁻, W₃^VO₉³⁻, [W^VW₄^VIO₁₆]³⁻, for reactions

The redox state of the continental lithospheric mantle of the Baikal-Mongolia region

The thermal and redox state of the upper mantle beneath the Baikal-Mongolia region was estimated on the basis of the investigation of the chemical composition (including iron oxidation state) of major minerals (olivine, orthopyroxene, clinopyroxene, and spinel) in spinel and garnet-spinel peridotite xenoliths from the Cenozoic alkali basalts of the volcanic fields of the Dariganga Plateau, Tariat Depression, and Vitim Plateau. At temperatures of 1030–1500°C and pressures of 29–47 kbar, the Δlog$ f_{O_2 } $ f_{O_2 } values relative to the FMQ buffer (calculated using the olivine-spinel oxygen barometer) range from −0.9 to −1.7 for the xenoliths of the Dariganga Plateau, from −0.9 to −1.8 for the Tariat Depression, and from −0.8 to −0.1 for the Vitim Plateau. The oxygen fugacity of peridotites from all of the areas is, in general, lower than that of the WM buffer. Oxygen fugacity is usually below the CCO and EMOD/G buffers in the peridotites of the Dariganga Plateau and the Tariat Depression and higher than these buffers in the peridotites of the Vitim Plateau. The T-PΔlog$ f_{O_2 } $ f_{O_2 } relationships in the xenoliths suggest the existence of spatial heterogeneity in the thermal and redox state of the upper mantle of the Baikal-Mongolia region. This heterogeneity is probably related to the influence of the plume that was responsible for the Late Mesozoic-Cenozoic intraplate magmatism of this region and reflects the different distance of the respective mantle domains from the plume head. The C-O-H fluids in equilibrium with the upper mantle peridotites are composed mainly of water and carbon dioxide. The mantle of the Dariganga Plateau and the Tariat Depression (Δlog$ f_{O_2 } $ f_{O_2 } < −0.9) is characterized by the dominance of H₂O, whereas CO₂-rich fluids are characteristic of the more oxidized mantle of the Vitim Plateau (Δlog$ f_{O_2 } $ f_{O_2 } is mostly higher than −0.8).     

Neotectonics of the Deryugin Basin area (Sea of Okhotsk)

The data of the bottom “summit” surface were used for compiling the schematic structural-neotectonic map and map of the main neotectonic structural elements. Their comparison with the schematic paleogeographic maps of the lithophysical complexes for four periods (K₂-$ _{1 - 2} $ _{1 - 2} , $ \rlap{--} P_3 $ \rlap{--} P_3 -N₁¹, N₁^1–2, and N₁³-N₂) reveals that the largest part of the considered area was characterized by either a continental or relatively shallow-sea environment, except for the western areas occupied at that time by the relatively deep trough with its axis located substantially westward of the neotectonic Deryugin Basin and the Staritskii Trough. In the Late Pliocene, the deep paleotrough ($ \rlap{--} P_3 $ \rlap{--} P_3 -N₂²) and Deryugin Basin were likely occupied by shelf settings with continuing sedimentation. The paleogeographic environments of the area for the period from the terminal Pliocene to the late Riss (Taz) Glaciation (Q₂⁶; MIS6) are unknown so far. The most complete Quaternary section recovered by Core LV 28-34-2 consists of six units; the odd (1, 3, and 5) and even (2, 4, and 6) among them correspond to the warm and cold marine isotopic stages, respectively. Judging from the benthic foraminiferal assemblages, the water depths during cold periods were shallower as compared with the warm stages, which is explained by the respective ascending and descending bottom movements and, partially, by the eustatic sea level fluctuations. In the Late Pleistocene-Holocene (∼17 ka), the bottom of the Deryugin Basin and the summit part of the Institut Okeanologii Rise subsided with average rates of 8 and 3 cm/year, respectively.     

Simulation of the molecular mass distributions of Si anions on the liquidus of the Na<Subscript>2</Subscript>O-SiO<Subscript>2</Subscript> system with regard for the disproportionation of <Emphasis Type="Italic">Q</Emphasis> structons

A new version of the STRUCTON (2009) computer model is proposed for the simulation of the molecular mass distributions (MMD) characterizing the diversity of anions in silicate melts depending on their polymerization and temperature. In contrast to earlier versions, the new version of the model accounts for disproportionation reactions of Q ⁿ species and makes use of their proportions in the statistical simulations of the origin of real Si-O complexes. The new potentialities of the STRUCTON program package are illustrated by its application to studying the structural-chemical characteristics of melts in the Na₂O-SiO₂ system along its liquidus line, including the points of eutectics and phase transitions at 0.333 ≤ $ N_{SiO_2 } $ N_{SiO_2 } < 0.500. This problem is solved with the use of a temperature-composition dependence of polymerization constants K _p ^Na in the Toop-Samis approximation. The variations in K _p ^Na were proved to be as large as three orders of magnitude due to both the temperature effect at a constant composition and the composition effect at a constant temperature. The results of the MMD simulations on the liquidus show that the concentration of the SiO₄⁴⁻ ion strongly decreases, and the proportion of chain species increases compared to those at a stochastic distribution. The concentration of the Si₂O₇⁶⁻ anion reaches its maximum (∼42%) at 40 mol % in the liquid, i.e., the composition of Na₆Si₂O₇. At $ N_{SiO_2 } $ N_{SiO_2 } > 0.40, this ion dominates over the SiO₄⁴⁻ monomer. More silicic melts with $ N_{SiO_2 } $ N_{SiO_2 } ≥ 0.45, are dominated by (Si _n O_3n )³ⁿ⁻ ring species, and the concentrations of these species are related as (Si₃O₉)⁶⁻ > (Si₄O₁₂)⁸⁻ > (Si₅O₁₅)¹⁰⁻. The maximum concentration of these flat rings also occurs near the composition of stoichiometric metasilicate with Si/O = 0.333. The comparison of the dependence of the average size of anions i _av and the average number of their species on depolymerization indicates that a change in the proportion of Q ⁿ species in melt at decreasing temperature results in structural restyling and an increase in the average size of Si-O complexes. The average number of anion species thereby decreases compared to that in a stochastic MMD. The results presented in this publication direct the progress in the thermodynamic theory of silicate melts to a new avenue that makes use of the capabilities and advantages of the ion-polymer model, the theory of associated solutions, spectroscopic data, and the experimental study of variations in oxide activities depending on composition and temperature.     

H,O,S and Pb isotope studies of uranium ore deposits in granitoid rocks of South China

Most altered clay minerals in uranium ore deposits in granites in the selected provinces of South China haveδ ¹⁸O _m values ranging from 6.22 to 7.24,δD_m from −60 to −70,δ ¹⁸O from +3.05 to −3.07, and from −20.2 to −37.5‰. Relative enrichment of³²S in the uranium ore deposits and greater variations in Pb isotopic composition of galenas from them show that uranium ores in the granites were formed in such a way that uranium in shallow-source granites had been mobilized by heated meteoric waters and then migrated to local favourable locations along great faults to form uranium ore deposits. Zhang Shaoli, Yang Wenjin, Tang Chunjing and Xu Wenxin did part of this work.     

The cosmic vacuum and the rotation of galaxies

The rotational effect of the cosmic vacuum is investigated. The induced rotation of elliptical galaxies due to the anti-gravity of the vacuum is found to be 10⁻²¹ s⁻¹ for real elliptical galaxies. The effect of the vacuum rotation of the entire Universe is discussed, and can be described by the invariant ω _ν = ω ₀ ∼ $ \sqrt {G\rho v} $ \sqrt {G\rho v} . The corresponding numerical angular velocity of the Universe is 10⁻¹⁹ s⁻¹, in good agreement with modern data on the temperature fluctuations of the cosmic background radiation.     

Charnockitization and enderbitization of mafic granulites in the Porya Bay area,Lapland Granulite Belt,Southern Kola Peninsula: I. Petrology and geothermobarometry

Charnockitization of mafic Opx-Cpx-Grt-Hbl-Bt-Pl ± Qtz granulites and Hbl-Opx-Bt hornblendites was studied in the southeastern part of the Lapland Granulite Belt. The evolutionary trends of the whole-rock compositions and mineral assemblages indicate that the rocks were affected by Na-K-Si-H₂O-CO₂-Cl brines, which came from outside, alkalinized and debasified the granulites, introduced Na, K, and Si into them, and depleted them in Mg, Fe, and Ca prior to the onset of charnockite melting; the latter began in the granulites only in their most extensively debasified domains. In the course of alkaline metasomatism, pyroxene were replaced by secondary hornblende and biotite with high Ti concentrations, analogous to those in the unaltered granulites. This suggests that the pre-charnockite amphibolization and biotitization were induced not by a temperature decrease but by the effect of Na- and K-bearing fluid during the metamorphic culmination. The metasomatically altered granulites, which were transformed into leucocratic disintegrated amphibolite skialiths, were gradually resorbed and dissolved in the charnockite melt, whose bulk composition corresponded to low-alkaline granites and tonalites. Hence, no contamination took place, and the excess Mg, Fe, and Ca amounts with respect to the eutectic composition were removed from the reaction zone. Variation diagrams indicate that the whole-rock composition of the granulites is gradually shifted toward the composition of charnockitoids. In certain instances, however, melanocratic Hbl-Grt-Opx-Cpx-Pl rims were formed along the granulite-charnockite interface, with the bulk composition of these fringes richer in Mg, Fe, and Ca than that of the ambient granulites. The reason for this was the sporadic redeposition of Mg, Fe, and Ca, which were mobilized from during charnbockitization and redeposited immediately in the reaction zone. In addition, rocks around the charnockite veins bear autonomous melanocratic Grt-Opx-Cpx-Hbl ± Mag ± Ilm ± Scp ± Pl ± Qtz veins whose mineral assemblages and bulk composition are close to those of the melanocratic rims around charnockitoids. The veins were formed via the transportation of Mg, Fe, and Ca for long distances outside the charnockitization zones. TWQ thermobarometric calculations indicate that the pre-charnockite alkaline metasomatism and debasification (amphibolization, biotitization, and feldspathization), anatectic formation of charnockite migma or magma, and the development of the melanocratic veins took place at the peak of the high-pressure granulite metamorphism at the same P-T parameters: approximately 800°C and 9–9.5 kbar. The calculated composition of the charnockitizing fluids suggests that they were homogeneous brines with $ X_{H_2 O} = 0.45 $ X_{H_2 O} = 0.45 , $ X_{CO_2 } = 0.10 $ X_{CO_2 } = 0.10 , X _NaCl = 0.30, and X _KCl = 0.15.     

Oxygen isotope studies of wolframite in tungsten ore deposits of south China

Based on the oxygen isotopic compositions of 133 wolframite samples and 110 quartz samples collected from 30 tungsten ore deposits in south China, in conjunction withδD values and other data, these deposits can be divided into four types.

The Sarylakh and Sentachan gold-antimony deposits,Sakha-Yakutia: A case of combined mesothermal gold-quartz and epithermal stibnite ores

New mineralogical, thermobarometric, isotopic, and geochemical data provide evidence for long and complex formation history of the Sarylakh and Sentachan Au-Sb deposits conditioned by regional geodynamics and various types of ore mineralization, differing in age and source of ore matter combined in the same ore-localizing structural units. The deposits are situated in the Taryn metallogenic zone of the East Yakutian metallogenic belt in the central Verkhoyansk-Kolyma Fold Region. They are controlled by the regional Adycha-Taryn Fault Zone that separates the Kular-Nera Terrane and the western part of the Verkhoyansk Fold-Thrust Belt. The fault extends along the strike of the northwest-trending linear folds and is deep-rooted and repeatedly reactivated. The orebodies are mineralized crush zones accompanied by sulfidated (up to 100 m wide) quartz-sericite metasomatic rocks and replacing dickite-pyrophyllite alteration near stibnite veinlets. Two stages of low-sulfide gold-quartz and stibnite mineralization are distinguished. The formation conditions of the early milk white quartz in orebodies with stibnite mineralization at the Sarylakh and Sentachan deposits are similar: temperature interval 340–280°C, salt concentration in fluids 6.8–1.6 wt % NaCl equiv, fluid pressure 3430–1050 bar, and sodic bicarbonate fluid composition. The ranges of fluid salinity overlapped at both deposits. In the late regenerated quartz that attends stibnite mineralization, fluid inclusions contain an aqueous solution with salinity of 3.2 wt % NaCl equiv and are homogenized into liquid at 304–189°C. Syngenetic gas inclusions contain nitrogen 0.19 g/cm³ in density. The pressure of 300 bar is estimated at 189°C. The composition of the captured fluid is characterized as K-Ca bicarbonatesulfate. The sulfur isotopic composition has been analyzed in pyrite and arsenopyrite from ore and metasomatic zones, as well as in coarse-, medium-, and fine-grained stibnite varieties subjected to dynamometamorphism. The following δ³⁴S values, ‰ have been established at the Sarylakh deposit: −2.0 to −0.9 in arsenopyrite, −5.5 to −1.1 in pyrite, and −5.5 to −3.6 in stibnite. At the Sentachan deposit: −0.8 to +1.0 in arsenopyrite, +0.5 to +2.6 in pyrite, and −3.9 to +0.6 in stibnite. Sulfides from the Sentachan deposit is somewhat enriched in ³⁴S. The ¹⁸O of milk white quartz at the Sarylakh deposit varies from +14.8 to 17.0‰ and from +16.4 to + 19.3‰ at the Sentachan. The δ¹⁸O of regenerated quartz is +16.5‰ at the Sarylakh and +17.6 to +19.8‰ at the Sentachan. The δ¹⁸O of carbonates varies from +15.0 to 16.3% at the Sarylakh and from +16.7 to +18.2‰ at the Sentachan. The δ¹³C of carbonates ranges from −9.5 to −12.1‰ and −7.8 to −8.5‰, respectively. The calculated $ \delta ^{18} O_{H_2 O} $ \delta ^{18} O_{H_2 O} of the early fluid in equilibrium with quartz and dolomite at 300δC are +7.9 to +10.1‰ for the Sarylakh deposit and +9.5 to +12.4‰ for the Sentachan deposit (+4.9 and 6.0‰ at 200°C for the late fluid, respectively). Most estimates fall into the interval characteristic of magmatic water (°¹⁸O = +5.5 to +9.5‰).     

Fluid regime and the behavior of ore, trace, and rare-earth elements during granitization of metagabbro-norites of the Belomorian Group (Gorelyi Island, Kandalaksha Bay)

The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the $ f_{H_2 O} The study of metagabbro-norites of the Belomorian Group metamorphosed under the amphibolite-lower granulite facies conditions (Gorelyi Island, Kandalaksha Bay) showed that at contact with Bt-Hbl-Kfs-Pl-Qtz gneiss-granites they were affected by silicic-alkaline H₂O-Cl-CO₂ brines, which caused the enrichment in alkalis, silica, Rb, Ba, Pb, Zr, LREE and redistribution of Cu, Zn, Cr, Co, V, and Ni along the filtration pathway. The granitization of metagabbro-norite proceeded simultaneously with increase in fluid oxygen fugacity from one log unit below to four log units above QFM. The microprobe determinations of Cl content in biotites and apatites made it possible to calculate variations in the -f _HCl relations in fluid during its percolation through the rock. It was shown that biotite was formed at metamorphic peak in the presence of highly aggressive high-f _HCl fluids (log /f _HCl ≈ 0.8–1.2). Apatite was formed in the presence of less acid and more aqueous residual solutions (log /f _HCl ≈ 2.98−3.91), which presumably lost their salt components at metamorphic peak. The calculations showed that the flux of fluid that percolated through the rock during granitization accounted for q ≈ 4 × 10² to 2 × 10³ cm³/cm². Due to insignificant volume of the fluid, the transformations spanned only marginal part of the metagabbro-norites on Gorelyi Island. Original Russian Text ? L.I. Khodorevskaya, 2009, published in Petrologiya, 2009, Vol. 17, No. 4, pp. 397–414.     

The graphite-COH fluid equilibrium in P,T, f_{O_2 } space

The oxygen fugacity ( ) of a C-O-H fluid in equilibrium with graphite has been determined in the range 10–30 kbar by equilibrating solid -buffer assemblages in graphite capsules containing C-O-H fluid. By using different buffers (Fe_xO-Fe₃O₄, Ni-NiO, Co-CoO, Mo-MoO₂), the of the graphite-saturated fluid is bracketed within a narrow range. This technique produces a calibration for the imposed on a sample contained within a graphite capsule. To achieve a thermodynamically-invariant system at fixed P and T, the was imposed on the system with an external buffer and the double-capsule technique. The experiments were performed in solid-media, high pressure apparatus with 19 mm tale-pyrex assemblies. A series of experiments at 10, 15, 20, 25, and 30 kbar, 800–1600° C, with imposed by the Fe₂O₃-Fe₃O₄-H₂O equilibrium were conducted. The experimental results have been fitted to the following equation:

Mineralogy and formation conditions of ores in the Bereznyakovskoe ore field,the Southern Urals,Russia

The Bereznyakovskoe ore field is situated in the Birgil’da-Tomino ore district of the East Ural volcanic zone. The ore field comprises several centers of hydrothermal mineralization, including the Central Bereznyakovskoe and Southeastern Bereznyakovskoe deposits, which are characterized in this paper. The disseminated and stringer-disseminated orebodies at these deposits are hosted in Upper Devonian-Lower Carboniferous dacitic-andesitic tuff and are accompanied by quartz-sericite hydrothermal alteration. Three ore stages are recognized: early ore (pyrite); main ore (telluride-base-metal, with enargite, fahlore-telluride, and gold telluride substages); and late ore (galena-sphalerite). The early and the main ore stages covered temperature intervals of 320–380 to 180°C and 280–300 to 170°C, respectively; the ore precipitated from fluids with a predominance of NaCl. The mineral zoning of the ore field is expressed in the following change of prevalent mineral assemblages from the Central Bereznyakovskoe deposit toward the Southeastern Bereznyakovskoe deposit: enargite, tennantite, native tellurium, tellurides, and selenides → tennantite-tetrahedrite, tellurides, and sulfoselenides (galenoclausthalite) → tetrahedrite, tellurides, native gold, galena, and sphalerite. The established trend of mineral assemblages was controlled by a decrease in $ f_{S_2 } $ f_{S_2 } , $ f_{Te_2 } $ f_{Te_2 } and $ f_{O_2 } $ f_{O_2 } and an increase in pH of mineral-forming fluids from early to late assemblages and from the Central Bereznyakovskoe deposit toward the Southeastern Bereznyakovskoe deposit. Thus, the Central Bereznyakovskoe deposit was located in the center of an epithermal high-sulfidation ore-forming system. As follows from widespread enargite and digenite, a high Au/Ag ratio, and Au-Cu specialization of this deposit, it is rather deeply eroded. The ore mineralization at the Southeastern Bereznyakovskoe deposit fits the intermediate- or low-sulfidation type and is distinguished by development of tennantite, a low Au/Ag ratio, and enrichment in base metals against a lowered copper content. In general, the Bereznyakovskoe ore field is a hydrothermal system with a wide spectrum of epithermal mineralization styles.     

Petrology, geothermobarometry and C-O-H-S fluid compositions in the environs of Rampura-Agucha Zn-(Pb) ore deposit, Bhilwara District, Rajasthan

The massive Zn-(Pb) sulfide ore body at Rampura-Agucha in Bhilwara district, Rajasthan, occurs within graphitic metapelites surrounded by garnet-biotite-sillimanite gneiss containing concordant bodies of amphibolite. These rocks and the sulfide ores have been studied to estimate the pressure, temperature and fluid composition associated with upper amphibolite facies metamorphism. Geothermobarometric calculations involving garnet-biotite and garnet-hornblende pairs, as well as sphalerite-hexagonal pyrrhotite-pyrite and garnet-plagioclase-sillimanite-quartz assemblages indicate that the most pervasive P-T condition during peak of regional metamorphism was 650°C and 6 kb, and was attained between the first and second deformations in the region. Some temperature-pressure estimates also cluster around 500°C–5.1 kb which probably represent retrograde cooling during unloading. Consideration of devolatilization equilibria in the C-O-H-S system at the pervasive metamorphic conditions mentioned above shows that the metamorphic fluid was H₂O-rich ( ) but also had a substantial component of . and were the other important phases in the fluid. CO (X_CO = 0.002) and were the minor phases in the fluid. It is probable that a part of this aqueous fluid was consumed by re-/neocrystallization of hydrous silicate phases like chlorite during the retrogressive metamorphic path, so that fluid entrapped in quartz below 450°C was rendered CO₂-rich (Holleret al 1996).     

The formation of SiO<Subscript>2</Subscript>-rich melts within the deep oceanic crust by hydrous partial melting of gabbros

Small amounts of felsic, evolved plutonic rocks, often called oceanic plagiogranites, always occur as veins or small stocks within the gabbroic section of the oceanic crust. Four major models are under debate to explain the formation of these rocks: (1) late-stage differentiation of a parental MORB melt, (2) partial melting of gabbroic rocks, (3) immiscibility in an evolved tholeiitic liquid, and (4) assimilation and partial melting of previously altered dikes. Recent experimental data in hydrous MORB-type systems are used to evaluate the petrogenesis of oceanic plagiogranites within the deep oceanic crust. Experiments show that TiO₂ is a key parameter for the discrimination between different processes: TiO₂ is relatively low in melts generated by anatexis of gabbros which is a consequence of the low TiO₂ contents of the protolith, due to the depleted nature of typical cumulate gabbros formed in the oceanic crust. On the other hand, TiO₂ is relatively high in those melts generated by MORB differentiation or liquid immiscibility. Since the TiO₂ content of many oceanic plagiogranites is far below that expected in case of a generation by simple MORB differentiation or immiscibility, these rocks may be regarded as products of anatexis. This may indicate that partial melting processes triggered by water-rich fluids are more common in the deep oceanic crust than believed up to now. At slow-spreading ridges, seawater may be transported via high-temperature shear zones deeply into the crust and thus made available for melting processes.     

Shlykovite KCa[Si4O9(OH)] · 3H2O and cryptophyllite K2Ca[Si4O10] · 5H2O, new mineral species from the Khibiny alkaline pluton, Kola Peninsula, Russia

New minerals, shlykovite and cryptophyllite, hydrous Ca and K phyllosilicates, have been identified in hyperalkaline pegmatite at Mount Rasvumchorr, Khibiny alkaline pluton, Kola Peninsula, Russia. They are the products of low-temperature hydrothermal activity and are associated with aegirine, potassium feldspar, nepheline, lamprophyllite, eudialyte, lomonosovite, lovozerite, tisinalite, shcherbakovite, shafranovskite, ershovite, and megacyclite. Shlykovite occurs as lamellae up to 0.02 × 0.02 × 0.5 mm in size or fibers up to 0.5 mm in length usually combined in aggregates up to 3 mm in size, crusts, and parallel-columnar veinlets. Cryptophyllite occurs as lamellae up to 0.02 × 0.1 × 0.2 mm in size intergrown with shlykovite being oriented parallel to {001} or chaotically arranged. Separate crystals of the new minerals are transparent and colorless; the aggregates are beige, brownish, light cream, and pale yellowish-grayish. The cleavage is parallel to (001) perfect. The Mohs hardness of shlykovite is 2.5–3. The calculated densities of shlykovite and cryptophyllite are 2.444 and 2.185 g/cm³, respectively. Both minerals are biaxial; shlykovite: 2V _meas = −60(20)°; cryptophyllite: 2V _meas > 70°. The refractive indices are: shlykovite: α = 1.500(3), β = 1.509(2), γ = 1.515(2); cryptophyllite: α = 1.520(2), β = 1.523(2), γ = 1.527(2). The chemical composition of shlykovite determined by an electron microprobe (H₂O determined from total deficiency) is as follows, wt %: 0.68 Na₂O, 11.03 K₂O, 13.70 CaO, 59.86 SiO₂, 14.73 H₂O; the total is 100.00. The empirical formula calculated on the basis of 13 O atoms (OH/H₂O calculated from the charge balance) is (K_0.96Na_0.09)_Σ1.05Ca_1.00Si_4.07O_9.32(OH)_0.68 · 3H₂O. The idealized formula is KCa[Si₄O₉(OH)] · 3H₂O. The chemical composition of cryptophyllite determined by an electron microprobe (H₂O determined from the total deficiency) is as follows, wt %: 1.12 Na₂O, 17.73 K₂O, 11.59 CaO, 0.08 Al₂O₃, 50.24 SiO₂, 19.24 H₂O, the total is 100.00. The empirical formula calculated on the basis of (Si,Al)₄(O,OH)₁₀ (OH/H₂O calculated from the charge balance) is (K_1.80Na_0.17)_Σ1.97Ca_0.99Al_0.01Si_3.99O_9.94(OH)_0.06 · 5.07H₂O. The idealized formula is K₂Ca[Si₄O₁₀] · 5H₂O. The crystal structures of both minerals were solved on single crystals using synchrotron radiation. Shlykovite is monoclinic; the space group is P2₁/n; a = 6.4897(4), b = 6.9969(5), c = 26.714(2)?, β = 94.597(8)°, V = 1209.12(15)?³, Z = 4. Cryptophyllite is monoclinic; the space group is P2₁/n; a = 6.4934(14), b = 6.9919(5), c = 32.087(3)?, β = 94.680(12)°, V= 1451.9(4)?, Z = 4. The strongest lines of the X-ray powder patterns (d, ?-I, [hkl] are: shlykovite 13.33–100[002], 6.67–76[004], 6.47–55[100], 3.469–45[021], 3.068–57[$ \bar 1 $ \bar 1 21], 3.042–45[121], 2.945–62[ 23], 2.912–90[025, 12, 211]; cryptophyllite 16.01–100[002], 7.98–24[004], 6.24–48[101], 3.228–22[$ \bar 1 $ \bar 1 09], 3.197–27[0.0.10], 2.995–47[122], 2.903–84[123, 204, $ \bar 1 $ \bar 1 24, 211], 2.623–20[028, 08, 126]. Shlykovite and cryptophyllite are members of new related structural types. Their structures are based on a two-layer packet consisting of tetrahedral Si layers linked with octahedral Ca chains. Mountainite, shlykovite and cryptophyllite could be combined into the mountainite structural family. Shlykovite is named in memory of Russian geologist V. G. Shlykov (1941–2007); the name cryptophyllite is from the Greek words meaning concealed and leaf that allude to its layered structure (phyllosilicate) in combination with a lamellar habit and intimate intergrowths with visually indistinguishable shlykovite. Type specimens of the minerals are deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow.     

The effect of H<Subscript>2</Subscript>O on the olivine liquidus of basaltic melts: experiments and thermodynamic models

We designed and carried out experiments to investigate the effect of H₂O on the liquidus temperature of olivine-saturated primitive melts. The effect of H₂O was isolated from other influences by experimentally determining the liquidus temperatures of the same melt composition with various amounts of H₂O added. Experimental data indicate that the effect of H₂O does not depend on pressure or melt composition in the basaltic compositional range. The influence of H₂O on melting point lowering can be described as a polynomial function This expression can be used to account for the effect of H₂O on olivine-melt thermometers, and can be incorporated into fractionation models for primitive basalts. The non-linear effect of H₂O indicates that incorporation of H₂O in silicate melts is non-ideal, and involves interaction between H₂O and other melt components. The simple speciation approach that seems to account for the influence of H₂O in simple systems (albite-H₂O, diopside-H₂O) fails to describe the mixing behavior of H₂O in multi-component silicate melts. However, a non-ideal solution model that treats the effect of H₂O addition as a positive excess free energy can be fitted to describe the effect of melting point lowering.     

Thermodynamic mixing properties of Mg(Al,Cr)2O4 spinel crystalline solution at high temperatures and pressures

Three Al-Cr exchange isotherms at 1,250°, 1,050°, and 796° between Mg(Al, Cr)₂O₄ spinel and (Al, Cr)₂O₃ corundum crystalline solutions have been studied experimentally at 25 kbar pressure. Starting from gels of suitable bulk compositions, close approach to equilibrium has been demonstrated in each case by time studies. Using the equation of state for (Al, Cr)₂O₃ crystalline solution (Chatterjee et al. 1982a) and assuming that the Mg(Al, Cr)₂O₄ can be treated in terms of the asymmetric Margules relation, the exchange isotherms were solved for Δ G ^*, and . The best constrained data set from the 1,250° C isotherm clearly shows that the latter two quantities do not overlap within three standard deviations, justifying the choice of asymmetric Margules relation for describing the excess mixing properties of Mg(Al, Cr)₂O₄ spinels. Based on these experiments, the following polybaric-polythermal equation of state can be formulated: , P expressed in bars, T in K, G _m ^ex and W _G,i ^Sp in joules/mol. Temperature-dependence of G _m ^ex is best constrained in the range 796–1,250° C; extrapolation beyond that range would have to be done with caution. Such extrapolation to lower temperature shows tentatively that at 1 bar pressure the critical temperature, T _c, of the spinel solvus is 427° C, with dT_c/dP≈1.3 K/kbar. The critical composition, X _c, is 0.42 , and changes barely with pressure. Substantial error in calculated phase diagrams will result if the significant positive deviation from ideality is ignored for Al-Cr mixing in such spinels.     

A radiometric study of polymetamorphism in the Bamble region,Norway

Metamorphism-induced parent-daughter isotopic rearrangement yields information concerning the nature and duration of metamorphism in the Bamble Area, Southern Norway. The thermal maximum of the Bamble Sveconorwegian metamorphism was reached at 1160–1200 m.y. ago, according to zircon and sphene U-Pb, and Rb-Sr whole rock results. Dating of post-kinematic pegmatites suggests that the major kinematic episodes took place not much more than 100 m.y. and that not until more than 200 m.y. after the thermal maximum had uplift and cooling resulted in closure of the K-Ar system in micas. Petrological considerations together with radiometric data on the Levang Gneiss Dome suggest that Rb-Sr whole rock samples show open and closed system behaviour under similar temperatures but possibly different . Variable recrystallization of zircon in the Levang Gneiss Dome (when taken with accompanying radiometric U-Pb data) appears to substantiate the idea that when = P _solid, resetting of both the U-Pb systems in zircon and Rb-Sr whole rock systems is greatly facilitated.