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

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.     

Oceanic plagiogranites as a result of interaction between magmatic and hydrothermal systems in the slow-spreading mid-ocean ridges

The paper considers some petrological and geochemical aspects of the formation of oceanic plagiogranites (OPG)—felsic intrusive rocks, which were found in the plutonic complexes of modern mid-ocean ridges (MOR) and ophiolites of paleo-collisional zones. Based on the multi-equilibrium clinopyroxene-orthopyroxene-amphibole-plagioclase geothermobarometry, typical OPG found in gabbros and peridotites were formed at temperatures of 820–850°C and pressure of 2–2.5 kbar. Close temperature estimates (825 ± 50°C) were obtained from literature data on Ti content in zircon, with allowance for lowered TiO₂ activity in the rock. Under these P-T parameters, OPG can be generated only in the presence of fluid of water activity $ \left( {a_{H_2 O} } \right) $ \left( {a_{H_2 O} } \right) close to 0.9. OPG and associated recrystallized gabbroids contain high-temperature hornblende with significant Cl content (0.5–2 wt %). In addition, the plagiogranites are characterized by particular geochemical features such as extremely high Na₂O/K₂O (up to 135), sharp LREE enrichment ((Ce/Yb)_cn and (La/Sm)_cn up to 10 and 4, respectively), and elevated ⁸⁷Sr/⁸⁶Sr ratio relative to DMM. All these facts point to the key role of hydrothermal fluid, the seawater derivative, in the OPG formation. The fluid with $ a_{H_2 O} = 0.9 $ a_{H_2 O} = 0.9 (approximately 28 wt % NaCl) could be produced from seawater due to hydration reactions at the higher lower temperature horizons of oceanic crust in the course of its percolation to the OPG generation areas. The formation of plagiogranites in the MOR oceanic core complexes possibly reflects the fundamental feature of oceanic accretion: practically simultaneous (at the geological time scale) proceeding of exogenic (neptunic) and endogenous (plutonic) processes.     

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).     

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.     

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‰).     

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.     

Infrared spectroscopic characterization of dehydration and accompanying phase transition behaviors in NAT-topology zeolites

Relative humidity ( P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} , partial pressure of water)-dependent dehydration and accompanying phase transitions in NAT-topology zeolites (natrolite, scolecite, and mesolite) were studied under controlled temperature and known P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions by in situ diffuse-reflectance infrared Fourier transform spectroscopy and parallel X-ray powder diffraction. Dehydration was characterized by the disappearance of internal H₂O vibrational modes. The loss of H₂O molecules caused a sequence of structural transitions in which the host framework transformation path was coupled primarily via the thermal motion of guest Na⁺/Ca²⁺ cations and H₂O molecules. The observation of different interactions of H₂O molecules and Na⁺/Ca²⁺ cations with host aluminosilicate frameworks under high- and low- P_{\textH 2 \textO} P_{{{\text{H}}_{ 2} {\text{O}}}} conditions indicated the development of different local strain fields, arising from cation–H₂O interactions in NAT-type channels. These strain fields influence the Si–O/Al–O bond strength and tilting angles within and between tetrahedra as the dehydration temperature is approached. The newly observed infrared bands (at 2,139 cm⁻¹ in natrolite, 2,276 cm⁻¹ in scolecite, and 2,176 and 2,259 cm⁻¹ in mesolite) result from strong cation–H₂O–Al–Si framework interactions in NAT-type channels, and these bands can be used to evaluate the energetic evolution of Na⁺/Ca²⁺ cations before and after phase transitions, especially for scolecite and mesolite. The 2,176 and 2,259 cm⁻¹ absorption bands in mesolite also appear to be related to Na⁺/Ca²⁺ order–disorder that occur when mesolite loses its Ow4 H₂O molecules.     

Equilibriums between Cu,Fe, and Zn sulfides and oxides in chloride solution: A thermodynamic study

The results of thermodynamic modeling of equilibriums between Cu, Fe, and Zn sulfides and oxides pertaining to the Cu-Fe-Zn-S-O₂ system in water and aqueous chloride solution are presented. The system comprises solid phases of constant composition: pyrite, pyrrhotite, hematite, magnetite, wüstite, γ-iron, chalcocite, covellite, cuprite, native copper, chalcopyrite, and bornite, as well as more than 100 ions, complexes, and molecules in an aqueous solution. The GIBBS program with the UNITHERM thermodynamic dataset used in calculations allows numerical analysis of phase assemblages in a dry system and in equilibrium with an aqueous solution. How the temperature, pressure, and the composition of the solution in the system opened for oxygen and sulfur affects the composition of phase assemblages was considered in temperature and pressure ranges of 50–350 C and 100–1000 bar, respectively. Decrease in temperature leads to a shift in stability fields of the studied phases toward the region of elevated oxygen and sulfur partial pressures. Variation of temperature is an important factor affecting precipitation of ore minerals, primarily, Cu- and Zn-bearing. The calculation results are presented in tables and diagrams. Each point in the $ (\log m_{S_{tot} } - \log f_{O_2 } ) $ (\log m_{S_{tot} } - \log f_{O_2 } ) diagram is characterized by a single possible assemblage of phases equilibrated with a solution of the given composition within the considered temperature and pressure range. Since the composition of the mineral assemblage is controlled by physicochemical conditions at the moment of mineral formation, comparison of the calculation results with mineral assemblages at ore deposits makes it possible to estimate the parameters of ore deposition at the early stage of investigation, including oxygen and sulfur activity and, occasionally, the composition and salinity of the solution. These parameters control the formation of such assemblages.     

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.     

Fluid regime of the amphibolite-facies metamorphism in the Dzhugdzhur-Stanovoy fold area (Far East)

Chromatographic and electrochemical measurements, combined with computer simulation of the natural mineral parageneses and estimation of the stability field of muscovite-bearing assemblages, yielded a consistent model of the fluid regime for the amphibolite-facies metamorphism of the Dzhugdzhur-Stanovoy fold area (DSFA). The model allows the fluid differentiation into “internal” and “external” fluids. The “internal” fluid is formed by the volatiles of the rock, while the “external” fluid arrived from an outer source: the mantle or other reservoir. It is established that the chromatographic and electrochemical measurements refer to the “external” fluid, whereas the redox state estimated from the mineral equilibria is related to the “internal” fluid, whose composition is buffered by the equilibrium mineral assemblage. The “external” fluid trapped by rocks preserves its own redox state only at the regtrograde stage, when the solid-phase reactions slacken and the buffer role of the mineral assemblages is minimized. This aspect explains the contradiction between the wide variations in the oxidation state of the mineral equilibria (log fO₂ from ?15 to ?20), on the one hand, and the persistent oxidation state of the external fluid established by the chromatographic and electrochemical methods, on the other hand. The main reason for the wide development of hornblende-bearing assemblages in the amphibolite-facies metamorphic rocks of the Dzhugdzhur-Stanovoy fold system is the high H₂O pressure in the “external” fluid. According to the obtained data, the composition of the “external” fluid is determined by the conditions $ P_{H_2 O} Chromatographic and electrochemical measurements, combined with computer simulation of the natural mineral parageneses and estimation of the stability field of muscovite-bearing assemblages, yielded a consistent model of the fluid regime for the amphibolite-facies metamorphism of the Dzhugdzhur-Stanovoy fold area (DSFA). The model allows the fluid differentiation into “internal” and “external” fluids. The “internal” fluid is formed by the volatiles of the rock, while the “external” fluid arrived from an outer source: the mantle or other reservoir. It is established that the chromatographic and electrochemical measurements refer to the “external” fluid, whereas the redox state estimated from the mineral equilibria is related to the “internal” fluid, whose composition is buffered by the equilibrium mineral assemblage. The “external” fluid trapped by rocks preserves its own redox state only at the regtrograde stage, when the solid-phase reactions slacken and the buffer role of the mineral assemblages is minimized. This aspect explains the contradiction between the wide variations in the oxidation state of the mineral equilibria (log fO₂ from −15 to −20), on the one hand, and the persistent oxidation state of the external fluid established by the chromatographic and electrochemical methods, on the other hand. The main reason for the wide development of hornblende-bearing assemblages in the amphibolite-facies metamorphic rocks of the Dzhugdzhur-Stanovoy fold system is the high H₂O pressure in the “external” fluid. According to the obtained data, the composition of the “external” fluid is determined by the conditions ≥ 0.7 P_S and = 0.01–0.3. The oxidation potential of the “external” fluid is close to that of the H₂O-C system under carbon-saturated vapor conditions. Original Russian Text ? O.V. Avchenko, I.A. Aleksandrov, V.O. Khudolozhkin, M.A. Mishkin, 2009, published in Tikhookeanskaya Geologiya, 2009, Vol. 28, No. 4, pp. 3–15.     

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.     

The physical properties of the intergalactic gas in rich clusters of galaxies

We perform a statistical analysis of the properties of 170 rich clusters of galaxies. We confirm the existence of correlations between the X-ray luminosity and temperature of the cluster intergalactic medium (IGM) and between the velocity dispersion of the galaxies and the X-ray luminosity of the IGM. In addition, we have found a new anti-correlation between the optical luminosity in Hα and the X-ray luminosity of the cluster IGM: log $ \left( {\frac{{L_{H\alpha } }} {{L_ \odot }}} \right) = a - b\log \left( {\frac{{L_x }} {{L_ \odot }}} \right) $ \left( {\frac{{L_{H\alpha } }} {{L_ \odot }}} \right) = a - b\log \left( {\frac{{L_x }} {{L_ \odot }}} \right) . Clusters form sequences with different values of a but similar values of b.     

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.     

Influence of hydrogen on Fe–Mg interdiffusion in (Mg,Fe)O and implications for Earth’s lower mantle

Interdiffusion of Fe and Mg in (Mg,Fe)O has been investigated experimentally under hydrous conditions. Single crystals of MgO in contact with (Mg_0.73Fe_0.27)O were annealed hydrothermally at 300 MPa between 1,000 and 1,250°C and using a Ni–NiO buffer. After electron microprobe analyses, the dependence of the interdiffusivity on Fe concentration was determined using a Boltzmann–Matano analysis. For a water fugacity of ∼300 MPa, the Fe–Mg interdiffusion coefficient in Fe _x Mg_1−x O with 0.01 ≤ x ≤ 0.25 can be described by with and C = −80 ± 10 kJ mol⁻¹. For x = 0.1 and at 1,000°C, Fe–Mg interdiffusion is a factor of ∼4 faster under hydrous than under anhydrous conditions. This enhanced rate of interdiffusion is attributed to an increased concentration of metal vacancies resulting from the incorporation of hydrogen. Such water-induced enhancement of kinetics may have important implications for the rheological properties of the lower mantle.

Gabbroic intrusions and magmatic metasomatism in harzburgites from the Garrett transform fault: implications for the nature of the mantle–crust transition at fast-spreading ridges

 Mafic and ultramafic rocks sampled in the Garrett transform fault at 13°28′S on the East Pacific Rise (EPR) provide insight on magmatic processes occurring under a fast-spreading ridge system. Serpentinized harzburgite from Garrett have modal, mineral and bulk chemical compositions consistent with being mantle residue of a high degree of partial melting. Along with other EPR localities (Terevaka transform fault and Hess Deep), these harzburgites are among the most residual and depleted in magmatophile elements of the entire mid-ocean ridge system. Geothermometric calculations using olivine-spinel pairs indicate a mean temperature of 759 ± 25 °C for Garrett residual harzburgite similar to the average of 755 °C for tectonite peridotites from slow-spreading ridges. Results of this study show that mid-ocean ridge peridotites are subject to both fractional melting and metasomatic processes. Evidence for mantle metasomatism is ubiquitous in harzburgite and is likely widespread in the entire Garrett peridotite massif. Magma-harzburgite interactions are very well preserved as pyroxenite lenses, plagioclase dunite pockets or dunitic wall rock to intrusive gabbros. Abundant gabbroic rocks are found as intrusive pockets and dikes in harzburgite and have been injected in the following sequence: olivine-gabbro, gabbro, gabbronorite, and ferrogabbro. The wide variety of magmas that crystallized into gabbros contrast sharply with present-day intratransform basalts, which have a highly primitive composition. Ferrogabbro dikes have been intruded at the ridge-transform intersection and as they represent the last event of a succession of gabbros intrusive into the peridotite, they likely constrain the origin of the entire peridotite massif to the same location. In peridotite massifs from Pacific transform faults (Garrett and Terevaka), primitive to fractionated basaltic magmas have flowed and crystallized variable amounts of dunite (±plagioclase) and minor pyroxenite, followed by a succession of cumulate gabbroic dikes which have extensively intruded and modified the host harzburgitic rocks. The lithosphere and style of magmatic activity within a fast-slipping transform fault (outcrops of ultramafic massif, discontinuous gabbro pockets intrusive in peridotite, magnesian and phyric basalts) are more analogous to slow-spreading Mid-Atlantic Ridge type than the East Pacific Rise. Received: 13 October 1997 / Accepted: 5 February 1999     

Genesis and geological and geochemical characteristics of Qixia gold deposit, Shandong, China

The Qixia gold deposit is one of the important quartz vein-type deposits hosted in metamorphic rocks in the east of Shandong, China. Compositionally the wolframite which is associated with gold mineralization in the deposit is rich in iron, but poor in manganese, showing that this mineral crystallized from hydrothermal solution at low temperature. The temperatures at the main metallogenic stage of the Qixia gold deposit are within the range of 160–270°C. The gaseous phases in fluid inclusions are dominated by H₂O and CO₂, while Na⁺, Ca²⁺ and Cl⁻ are the major species in the fluid phase with K⁺ and F⁻ present in relatively small amounts. The salinities of fluids are 4.2 wt% –8.0 wt% NaCl equiv. Meanwhile, the fluid is characterized by either Ca²⁺ < Na⁺ < K⁺ (in five samples) or Na⁺ < Ca²⁺ < K⁺ (in two samples), quite similar to the composition of ore-forming fluid derived from meteoric water. Primary data on the hydrogen and oxygen isotopic compositions of the ore-forming fluid fall within a wide range: = − 56‱ − 95‱. and = − 3. 6‱ − 4. 5‱ relative to SMOW. These isotopic values fully reflect the distribution features of meteoric water which has exchanged with the metamorphic rocks of the Jiaodong Group at different temperatures and W/ R ratios, and the metallogenic process is characterized by low W/R ratios. The Rb-Sr isochron age of the Qixia gold deposit is 125.8 ± 1.7 Ma, with (⁸⁷Sr/⁸⁶Sr)_i being 0.7168, and the time interval between the gold deposit and its country rocks (granite or metamoprhic rocks) is very large. The formation of the Qiaxia gold deposit is directly related to the evolution of geological history in eastern Shandong, and a genetic model in which the deep convective circulating meteoric water reacts with the country rocks can be used to explain the metallogenic mechanism of the deposit. This project was financially supported by the National Natural Science Foundation of China (No. 49000020).