Experimental study of the system H3BO3–NaF–SiO2-H2O at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions

The phase state of fluid in the system H₃BO₃–NaF–SiO₂–H₂O was studied at 350–800 °C and 1–2 kbar by the method of synthetic fluid inclusions. The increase in the solubility of quartz and the high reciprocal solubility of H₃BO₃ and NaF in water fluid at high temperatures are due to the formation of complexes containing B, F, Si, and Na. At 800 °C and 2 kbar, both liquid and gas immiscible phases (viscous silicate-water-salt liquid and three water fluids with different contents of B and F) are dispersed within each other. The Raman spectra of aqueous solutions and viscous liquid show not only a peak of [B(OH)₃]⁰ but also peaks of complexes [B(OH)₄]^–, polyborates [B₄O₅(OH)₄]^2–, [B₃O₃(OH)₄]^–, and [B₅O₆(OH)₄]^–, and/or fluoroborates [B₃F₆O₃]^3–, [BF₂(OH)₂]^–, [BF₃(OH)]^–, and [BF₄]^–. The high viscosity of nonfreezing fluid is due to the polymerization of complexes of polyborates and fluorine-substituted polyborates containing Si and Na. Solutions in fluid inclusions belong to P–Q type complicated by a metastable or stable immiscibility region. Metastable fluid equilibria transform into stable ones owing to the formation of new complexes at 800 ºC and 2 kbar as a result of the interaction of quartz with B-F-containing fluid. At high concentrations of F and B in natural fluids, complexes containing B, F, Si, and alkaline metals and silicate-water-salt dispersed phases might be produced and concentrate many elements, including ore-forming ones. Their transformation into vitreous masses or viscous liquids (gels, jellies) during cooling and the subsequent crystallization of these products at low temperatures (300–400 °C) should lead to the release of fluid enriched in the above elements.     

Conditions of pocket formation in the Oktyabrskaya tourmaline-rich gem pegmatite (the Malkhan field, Central Transbaikalia, Russia)

Coexisting melt (MI), fluid-melt (FMI) and fluid (FI) inclusions in quartz from the Oktaybrskaya pegmatite, central Transbaikalia, have been studied and the thermodynamic modeling of PVTX-properties of aqueous orthoboric-acid fluids has been carried out to define the conditions of pocket formation. At room temperature, FMI in early pocket quartz and in quartz from the coarse-grained quartz–oligoclase host pegmatite contain crystalline aggregates and an orthoboric-acid fluid. The portion of FMI in inclusion assemblages decreases and the volume of fluid in inclusions increases from the early to the late growth zones in the pocket quartz. No FMI have been found in the late growth zones. Significant variations of solid/fluid ratios in the neighboring FMI result from heterogeneous entrapment of coexisting melts and fluids by a host mineral. Raman spectroscopy, SEM EDS and EMPA indicate that the crystalline aggregates in FMI are dominated by mica minerals of the boron-rich muscovite–nanpingite CsAl₂[AlSi₃O₁₀](OH,F)₂ series as well as lepidolite. Topaz, quartz, potassium feldspar and several unidentified minerals occur in much lower amounts. Fluid isolations in FMI and FI have similar total salinity (4–8 wt.% NaCl eq.) and H₃BO₃ contents (12–16 wt.%). The melt inclusions in host-pegmatite quartz homogenize at 570–600 °C. The silicate crystalline aggregates in large inclusions in pocket quartz completely melt at 615 °C. However, even after those inclusions were significantly overheated at 650±10 °C and 2.5 kbar during 24 h they remained non-homogeneous and displayed two types: (i) glass+unmelted crystals and (ii) fluid+glass. The FMI glasses contain 1.94–2.73 wt.% F, 2.51 wt.% B₂O₃, 3.64–5.20 wt.% Cs₂O, 0.54 wt.% Li₂O, 0.57 wt.% Ta₂O₅, 0.10 wt.% Nb₂O₅, 0.12 wt.% BeO. The H₂O content of the glass could exceed 12 wt.%. Such compositions suggest that the residual melts of the latest magmatic stage were strongly enriched in H₂O, B, F, Cs and contained elevated concentrations of Li, Be, Ta, and Nb. FMI microthermometry showed that those melts could have crystallized at 615–550 °C.

Crystallization of quartz–feldspar pegmatite matrix leads to the formation of H₂O-, B- and F-enriched residual melts and associated fluids (prototypes of pockets). Fluids of different compositions and residual melts of different liquidus–solidus P–T-conditions would form pockets with various internal fluid pressures. During crystallization, those melts release more aqueous fluids resulting in a further increase of the fluid pressure in pockets. A significant overpressure and a possible pressure gradient between the neighboring pockets would induce fracturing of pockets and “fluid explosions”. The fracturing commonly results in the crushing of pocket walls, formation of new fractures connecting adjacent pockets, heterogenization and mixing of pocket fluids. Such newly formed fluids would interact with a primary pegmatite matrix along the fractures and cause autometasomatic alteration, recrystallization, leaching and formation of “primary–secondary” pockets.     

Early Cretaceous trachybasalt-trachyte-trachyrhyolitic volcanism in the Nyalga basin (Central Mongolia): sources and evolution of continental rift magmas

As shown by geological, mineralogical, and isotope geochemical data, trachybasaltic-trachytic-trachyrhyolitic (TTT) rocks from the Nyalga basin in Central Mongolia result from several eruptions of fractionated magmas within a short time span at about 120 Ma. Their parental basaltic melts formed by partial melting of mantle peridotite which was metasomatized and hydrated during previous subduction events. Basaltic trachyandesites have high TiO₂ and K₂O, relatively high P₂O₅, and low MgO contents, medium ⁸⁷Sr/⁸⁶Sr(₀) ratios (0.70526-0.70567), and almost zero or slightly negative ε_Nd(T) values. The isotope geochemical signatures of TTT rocks are typical of Late Mesozoic basaltic rocks from rift zones of Mongolia and Transbaikalia. The sources of basaltic magma at volcanic centers of Northern and Central Asia apparently moved from a shallower and more hydrous region to deeper and less hydrated lithospheric mantle (from spinel to garnet-bearing peridotite) between the Late Paleozoic and the latest Mesozoic. The geochemistry and mineralogy of TTT rocks fit the best models implying fractional crystallization of basaltic trachyandesitic, trachytic, and trachyrhyodacitic magmas. Mass balance calculations indicate that trachytic and trachydacitic magmas formed after crystallization of labradorite-andesine, Ti-augite, Sr-apatite, Ti-magnetite, and ilmenite from basaltic trachyandesitic melts. The melts evolved from trachytic to trachyrhyodacitic and trachyrhyolitic compositions as a result of prevalent crystallization of K-Na feldspar, with zircon, chevkinite-Ce, and LREE-enriched apatite involved in fractionation. Trachytic, trachyrhyodacitic, and trachyrhyolitic residual melts were produced by the evolution of compositionally different parental melts (basaltic trachyandesitic, trachytic, and trachyrhyodacitic, respectively), which moved to shallower continental crust and accumulated in isolated chambers. Judging by their isotopic signatures, the melts assimilated some crustal material, according to the assimilation and fractional crystallization (AFC) model.     

Heterogeneous reduction of Tc(VII) by Fe(II) at the solid-water interface

Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ? structural Fe(II) in phyllosilicates ? Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO₂ monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with ⁵⁶Fe-goethite with adsorbed ⁵⁷Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.     

Fluid and magmatic processes in the formation of the Ary-Bulak ongonite massif (eastern Transbaikalia)

The paper discusses the formation conditions of the Ary-Bulak ongonite massif (eastern Transbaikalia). Studies of melt and fluid inclusions have shown that, along with crystalline phases and a silicate melt, ongonitic magma contained aqueous–saline fluids of different types, fluoride melts compositionally similar to fluorite, sellaite, cryolite, chiolite, and more complex aluminum fluorides as well as silicate melts with abnormal Cs and As contents. An ongonite melt crystallized with the participation of P–Q fluids as vapor solutions, presumably NaF-containing and slightly admixed with chlorides. We studied the properties and composition of brine inclusions from Ca- and F-rich rocks on the margin of the massif. Depending on the thermophysical properties of the host rocks and ongonite melt, the duration of its crystallization has been estimated for a magma chamber of the size and shape of the Ary-Bulak massif. Magma chamber cooling has been modeled, and the density, viscosity, and Rayleigh number of the ongonite melt have been estimated from the composition of silicate glasses in melt inclusions. These data strongly suggest intense convection in the residual magma chamber lasting for centuries. We have calculated possible fluid overpressure during the crystallization and degassing of the ongonite melt in a closed magma chamber.Calcium- and fluorine-rich aphyric and porphyritic rocks on the southwestern margin of the massif might have formed by the following mechanism. Local decompression in the magma chamber quenched an oxygen-containing calcium fluoride melt accumulated at the crystallization front, and then these rocks altered during the interaction with fluids. When penetrating the marginal zone, a P–Q magmatic fluid which coexisted with the melt in the residual chamber cooled and changed its composition and properties. This caused the fluid to boil and segregate into immiscible phases: a vapor solution and a brine extremely rich in Cl, F, K, Cs, Mn, Fe, and Al. The fluoride and silicate liquids were immiscible; the silicate melts had abnormal Cs and As contents; changes in the composition and properties of the magmatic fluids caused them to boil and produce brines. All this is evidence for complex fluid–magma interaction and heterogeneous ongonitic magma during the crystallization of the Ary-Bulak rocks. These processes were favored by the low viscosity and high mobility of the F- and water-rich ongonite melt, intense melt convection in the residual chamber, and rising fluid pressure during its degassing.     

The mineralogic transformation of ferrihydrite induced by heterogeneous reaction with bioreduced anthraquinone disulfonate (AQDS) and the role of phosphate

Bioreduced anthraquinone-2,6-disulfonate (AH₂DS; dihydro-anthraquinone) was reacted with a 2-line, Si-substituted ferrihydrite under anoxic conditions at neutral pH in PIPES buffer. Phosphate (P) and bicarbonate (C); common adsorptive oxyanions and media/buffer components known to effect ferrihydrite mineralization; and Fe(II)_aq (as a catalytic mineralization agent) were used in comparative experiments. Heterogeneous AH₂DS oxidation coupled with Fe(III) reduction occurred within 0.13-1 day, with mineralogic transformation occurring thereafter. The product suite included lepidocrocite, goethite, and/or magnetite, with proportions varing with reductant:oxidant ratio (r:o) and the presence of P or C. Lepidocrocite was the primary product at low r:o in the absence of P or C, with evidence for multiple formation pathways. Phosphate inhibited reductive recrystallization, while C promoted goethite formation. Stoichiometric magnetite was the sole product at higher r:o in the absence and presence of P. Lepidocrocite was the primary mineralization product in the Fe(II)_aq system, with magnetite observed at near equal amounts when Fe(II) was high [Fe(II)/Fe(III)] = 0.5 and P was absent. P had a greater effect on reductive mineralization in the Fe(II)_aq system, while AQDS was more effective than Fe(II)_aq in promoting magnetite formation. The mineral products of the direct AH₂DS-driven reductive reaction are different from those observed in AH₂DS-ferrihydite systems with metal reducing bacteria, particularly in presence of P.     

Inclusions of magmatic fluids: P-V-T-X properties of aqueous salt solutions of various types and petrological implications

The P-V-T-X properties of H₂O-salt systems are compared depending on the solubility coefficient of compounds contained in these systems and the presence or absence of critical phenomena in the saturated solutions. Data on synthetic and natural inclusions captured in minerals at elevated temperatures and pressures and employed to discuss the principal features of phase diagrams of the H₂O-NaCl system (type I) and H₂O-NaF system (type II or P-Q type). It is demonstrated how characteristics of magmatic fluids of various types are manifested during the development of miarolitic pegmatites (Malkhan field in Transbaikalia) and during the crystallization of F-rich ongonitic melts (Ary-Bulak Massif in eastern Transbaikalia). Characteristics of solutions and gas-rich (gaseous) fluid inclusions in quartz phenocrysts from porphyritic ongonites (disappearance of the liquid regardless of its density and the overall salinity near the critical point of water, distinctive features of the dissolution of the crystalline phase, and the ability of the inclusions to withstand heating to 1400°C without decrepitation), and the richness of the fluid-magmatic system as a whole in F suggest that the ongonite melt crystallized in the presence of low-density NaF-bearing fluids of the P-Q type with a minor admixture of chlorides. It is important to identify the type of solutions in the fluid inclusions, because without knowing this type, it is impossible to accurately enough calculate the pressure at the temperatures of inclusion capture. For example, the unwarranted classification of solutions of type II (P-Q) in inclusions with the chloride system results in a significant overestimation of the calculated fluid pressures. A technique is proposed for studying the high-temperature immiscibility region in P-Q systems based on data obtained on gaseous fluid inclusions.     

First <Superscript>40</Superscript>Ar/<Superscript>39</Superscript>Ar age determinations on the Malkhan granite-pegmatite system: Geodynamic implications

The Malkhan granite-pegmatite system located in Central Transbaikalia, in the southwestern portion of the Malkhan-Yablonovy structure-formational zone of the Caledonian folding comprises two granite massifs (Bolsherechensk and Oreshny) and a miarolitic pegmatite field of the same name, which adjoins the Chikoi deep-seated fault and Lower Cretaceous Chikoi rift depression in the north. The first ⁴⁰Ar/³⁹Ar data were obtained on porphyritic biotite granites of the Oreshny massif and on K-feldspar, muscovite, and lepidolite from the Oktyabrskaya pegmatite vein. According to these data, the age of the granitepegmatite system is 123.8–127.6 Ma, which is consistent with the age of Lower Cretaceous rocks from the Chikoi depression. The intimate spatial relationship and isochronism between the Chikoi depression and the Malkhan granite-pegmatite system are strongly suggestive of a rift regime that affected its evolution, thus highlighting the need to regard the evolution of this system as being intimately related to depression development. Such a model can easily be realized within the framework of the concept of a metamorphic core complex, which was used to explain the nature of Transbaikal-type rift depressions and conjugate granite-gneiss swells.