Dissolution of Corundum and Andalusite in H2O-Saturated Haplogranitic Melts at 800{degrees}C and 200 MPa: Constraints on Diffusivities and the Generation of Peraluminous Melts

The mechanisms and kinetics of equilibration between peraluminousminerals and granitic melt were investigated experimentallyby the dissolution of corundum and andalusite into H₂O-saturatedmetaluminous haplogranitic melt at 800°C and 200 MPa. Mineraland haplogranitic glass rods were juxtaposed inside platinumcapsules, and then subjected to experimental conditions fortimes ranging from 12 to 2900 h. Upon melting, the mineral –meltinterface retreats with the square root of time. The compositionof the melt at the interface changes with time, but its ASI[aluminum saturation index = molar Al₂O₃/(CaO + Na₂O + K₂O)]remains constant at     

Contrasting interactions of sodium and potassium with H<Subscript>2</Subscript>O in haplogranitic liquids and glasses at 200 MPa from hydration–diffusion experiments

This study examines hydration–diffusion in the metaluminous haplogranite system at 200 MPa H₂O and 800–300°C. At 800°C hydration is accompanied by melting and uphill diffusion of sodium from anhydrous glass toward the region of hydration and melting, whereas potassium diffuses away from the hydration front and into anhydrous glass. Silicon and aluminum are simply diluted upon hydration. There is no change in molecular Al/(Na + K) throughout the entire hydration-diffusion aureole and, therefore, (1) there is no loss of alkalis to the vapor, and (2) K migrates to replace Na in order to maintain local charge balance required by ^IVAl. Alkali diffusion occurs over a viscosity contrast from 10^4.1 Pa s in hydrous liquid to 10^11.8–10^13.5 Pa s in anhydrous glass. From these results, we interpret that: (1) Na is structurally or energetically favored over K as a charge-balancing cation for ^IVAl in hydrous granitic liquids, whereas the opposite behavior has been observed for anhydrous melts, and (2) the diffusion of alkalis through silicate melts is largely independent of viscosity. Results from 600°C are similar to those at 800°C, but hydration at 300°C involves a loss of Na and concomitant increase in molar Al/(Na + K) in the hydration zone due to hydrogen-alkali exchange between fluid and glass. Hydration behavior at 400°C is transitional between those at 300°C and 600°C, suggesting that the change in hydration mechanism occurs near the glass transition.     

Behavior and effects of phosphorus in the system Na2O−K2O−Al2O3−SiO2−P2O5−H2O at 200 MPa(H2O)

The addition of phosphorus to H₂O-saturated and initially subaluminous haplogranitic (Qz–Ab–Or) compositions at 200 MPa(H₂O) promotes expansion of the liquidus field of quartz, a marked decrease of the solidus temperature, increased solubility limits of H₂O in melt at low phosphorus concentrations, and fractionation of melt out of the haplogranite plane (projected along an Or₂₈ isopleth) toward a peralkaline, silica-poor but quartz-saturated minimum composition. The partition coefficient for P₂O₅ between aqueous vapor and melt with an ASI (aluminum saturation index, mol Al/[mol Na+K])=1 is negligible (0.06), and consequently so are the effects of phosphorus on other melt-vapor relations involving major components. Phosphorus becomes more soluble in vapor, however, as the concentration of a NaPO₃ component increases via the fractionation of melt by crystallization of quartz and feldspar. The experimental results here corroborate existing concepts regarding the interaction of phosphorus with alkali aluminosilicate melt: phosphorus has an affinity for alkalis and Al, but not Si. Phosphorus is incorporated into alkali feldspars by the exchange component AlPSi_-2. For subaluminous compositions (ASI=1), the distribution coefficient of phosphorus between alkali feldspar and melt, D[P]Af/m, is 0.3. This value increases to D[P]Af/m=1.0 at a melt ASI value of 1.3. The increase in D[P]Af/m with ASI is expected from the fact that excess Al promotes the AlPSi_-2 exchange. With this experimental data, the P₂O₅ content of feldspars and whole rocks can reveal important facets of crystallization and phosphorus geochemistry in subaluminous to peraluminous granitic systems.     

Petroleum potential of Baikal deposits

We analyzed oils, gases, and bitumens of bottom sediments from natural shows on the southeastern shore of Lake Baikal, in the mouth of the Stvolovaya River near Capes Tolstyi and Gorevoi Utes. Based on a set of geological data, we have established that: (1) the lake oils underwent biodegradation to a variable degree: “Fresh” nondegraded paraffin oil floats up near Cape Gorevoi Utes; in the mouth of the Stvolovaya River and near Cape Tolstyi, aromatic-naphthene oil lacks n-alkanes, monomethyl alkanes, and acyclic isoprenoids; (2) Cenozoic oil originated from the organic matter of fresh-water basins with significant amounts of higher land plant remains, including angiosperm plants (oleanane), which suggests the lake or delta genesis of oil source formations of Cretaceous and younger ages. Judging from the carbon isotope composition (average δ¹³C = −43.84‰), methane from the bottom sediments near Cape Gorevoi Utes is catagenetic. The initial in-place resources in the Baikal sedimentary basins are estimated by the volumetric-statistical method at 500 mln tons of equivalent hydrocarbons.     

Crystallization of the Little Three layered pegmatite-aplite dike, Ramona District, California

Subhorizontally layered pegmatite-aplite bodies are characterized by fine-grained, sodic to granitic aplite that is usually juxtaposed abruptly above by much coarser-grained, commonly graphic potassic pegmatite. Although well studied, there currently is little concensus as to how such dikes form. The Little Three dike near Ramona, California, is representative of such zoned bodies in this and other regions, and contains discontinuous miarolitic pockets near the base of the graphic pegmatite zone. Tourmaline, garnet, biotite, and muscovite show no changes in major- or minor-element compositions indicative of progressive magmatic fractionation until the immediate vicinity of the main miarolitic zone, where they record abrupt and extreme enrichments in Li, F, and Mn. There is no correlation of chemical changes in the dike with the appearance of small miarolitic vugs well below the main miarolitic zone, nor is there any indication that the aplite, graphic pegmatite, or miarolitic pockets represent separate magma injections. The chemistries of tourmaline, garnet, and micas, however, preclude conventional models of Rayleigh fractionation or traditional zone refining. Textural features and modeled cooling histories indicate that the dike cooled quickly and might have solidified partially or totally to glass before crystallization commenced. Geothermometry based on the compositions of coexisting plagioclase and homogeneous, nonperthitic K-feldspar indicates inward crystallization of the dike, from ∼400–435 °C at the margins to ∼350–390 °C within 20–30 cm of the pocket horizon, then a sharp decrease to 240–275 °C in the pockets where K-feldspar is perthitic. We interpret the feldspar geothermometry (except perhaps in the miarolitic cavities) to reflect the temperatures at crystallization fronts that advanced into the pegmatite, first from the foot wall and eventually joined by a similar front downward from the hanging wall. Crystallization down from the hanging wall may have commenced after ∼70–80% of the foot wall aplite had crystallized. The very abrupt increases of Li, Mn, and F in tourmaline and garnet near the miarolitic zone appear to be explained best by the process of constitutional zone refining, in which a fluxed crystallization front sweeps an incompatible element-enriched boundary layer through a solid or semi-solid. After these two highly fluxed boundary layers merged near the main miarolitic zone, compositional evolution could have proceeded by crystal-melt fractionation. Received: 24 March 1998 / Accepted: 10 March 1999     

Melt-vapor solubilities and elemental partitioning in peraluminous granite-pegmatite systems: experimental results with Macusani glass at 200 MPa

Vapor-saturated experiments at 200 MPa with peraluminous, lithophile-element-rich rhyolite obsidian from Macusani, Peru, reveal high miscibility of H₂O and silicate melt components. The H₂O content of melt at saturation (11.5+-0.5 wt.%) is almost twice that predicted by existing melt speciation models. The corresponding solubility of melt components in vapor decreases from 15 wt.% dissolved solids (750°–775° C) to 9 wt.% at 600° C. With regard to major and most minor components, macusanite melt dissolves congruently in vapor. Among the elements studied (B, P, F, Li, Rb, Cs, Be, Sr, Ba, Nb, Zr, Hf, Y, Pb, Th, U, La, Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, and Tm), only boron has a vapor/melt partition coefficient (D[B]) consistently 1 at superliquidus temperatures (>645° C). Phosphorus and fluorine behave similarly, with D[P] and D[F]<0.5. Little or no significant vapor/melt fractionation is evident among most periodic groups (alkalis, alkaline earths, Zr/Hf, or the REE). The temperature dependence of vapor/melt partition coefficients is generally greatest for cations with charge +3 (except Nb and U); most vapor/melt partition coefficients for trace elements increase with decreasing temperature to the liquidus. Crystallization proceeds by condensation of crystalline phases from vapor; most coexisting melts are aphyric. Changes in the major element content of melt are dominated by the mineral assemblage crystallized from vapor, which includes subequal proportions of white mica, quartz, albite, and orthoclase. The volumetric proportion of (mica + or-thoclase)/albite increases slightly with decreasing T, creating a sodic, alkaline vapor. Vapor deposition of topaz (T500° C), which consumes F from melt, returns K/Na ratios of melt to near unity with the vapor-deposition of albite. The abundances of most trace elements in residual melt change little with the crystallization of major phases, but in some cases are strongly controlled by the deposition of accessory phases including apatite (T550° C), which depletes the melt in P and REE. Below the liquidus, boron increasingly favors the vapor over melt with decreasing temperatures.     

Terpanes and steranes in coals of different genetic types in Siberia

Chloroform extracts of coals from different genetic groups and different ages have been studied by chromato-mass-spectrometry, namely, Devonian liptobioliths from the Barzas region (Kuznetsk Basin) and Lower Cretaceous humites and sapropelites from the Kangalas and Taimylyr deposits, respectively (Lena Coal Basin). It has been established that the most ancient Devonian liptobioliths formed in coastal environments. Lipids of different biotas of marine and continental genesis, including resins of early Conifers, were the source of biomarker molecules. The Mesozoic humic and sapropelic coals differ little in chemofossil biomarkers, which might be related to their significant bacterial transformation and biosynthesis of chemofossils mainly by prokaryotes.     

Re-equilibration of CO2 fluid inclusions at controlled hydrogen fugacities

Abstract Natural, pure CO₂ inclusions in quartz and olivine (c. Fo₉₀) were exposed to controlled f_H2 conditions at T= 718–728°C and P_total= 2 kbar; their compositions were monitored (before and after exposures) by microsampling Raman spectroscopy (MRS) and microthermometry. In both minerals exposed at the graphite–methane buffer (f_H2= 73 bar), fluid speciations record the diffusion of hydrogen into the inclusions. In quartz, room-temperature products in euhedral isolated (EI type) inclusions are carbonic phases with molar compositions of c. CO₂(60) + CH₄(40) plus graphite (Gr) and H₂O, whereas anhedral inclusions along secondary fractures (AS type) are Gr-free and contain H₂O plus carbonic phases with compositions in the range c. CO₂(60) + CH₄(40) to CO₂(10) + CH₄(90). EI type inclusions in olivine evolved to c. CO₂(90–95) + CH₄(5–10) without Gr, whereas AS type inclusions have a range of compositions from CO₂(90) + CH₄(10) ± Gr to CH₄(50) + H₂(50) ± Gr; neither H₂O nor any hydrous species was detected by optical microscopy or MRS in the olivine-hosted products. Differences in composition between and among the texturally distinct populations of inclusions in both minerals probably arise from variations in initial fluid densities, as all inclusions apparently equilibrated with the ambient f_H2. These relations suggest that compositional variability among inclusions in a given natural sample does not require the entrapment of multiple generations of fluids. In addition, the absence of H₂O in the olivine-hosted inclusions would require the extraction of oxygen from the fluids, in which case re-equilibration mechanisms may be dependent on the composition and structure of the host mineral. Many of the same samples were re-exposed to identical P–T conditions using Ar as the pressure medium, yielding ambient f_H2= 0.06 bar. In most inclusions, the carbonic fluids returned to pure CO₂ and graphite persisted in the products. Reversal of the mechanisms from the prior exposure at f_H2= 73 bar did not occur in any inclusions but the AS types in olivine, in which minor CO₂ was produced at the expense of CH₄ and/or graphite. The observed non-reversibility of previous mechanisms may be attributed to: (1) slower fluid–solid reactions compared to reactions in the homogeneous fluid phase; (2) depressed activities of graphite due to poor ordering; and/or (3) low ambient f_O2 at the conditions of the second run.