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1.
The pH-dependence of oxide dissolution rates is controlled by Brønsted acid-base reactions at the mineral surface. These reactions are rapid but depend explicitly on temperature, as do the subsequent slow rates of bond hydrolysis. The net result is that dissolution rates vary in a complicated fashion with temperature and solution pH. The enthalpy changes of acid-base reactions on oxide materials are sufficiently similar, however, that general statements can be made about their contribution. The enthalpy changes from proton adsorption to a hydroxyl functional group (SOH), or to a deprotonated functional group (SO ), are generally exothermic. The enthalpy changes become increasingly endothermic, however, as charge accumulates on the mineral surface and the charged species interact electrostatically. The result is that mineral dissolution rates are least sensitive to temperature, as measured with an Arrhenius-like rate law, at pH conditions near the Point of Zero Net Proton Charge.  相似文献   
2.
Zr-in-rutile thermometry in blueschists from Sifnos, Greece   总被引:1,自引:0,他引:1  
Zr-in-rutile thermometry on samples of blueschist from Sifnos, Greece, yields temperatures that reflect progressive crystallization of rutile from ca. 445 to 505°C with an analytical precision of + 18/−27 and ± 10°C using the electron microprobe and ± 1.5–3.5°C using the ion microprobe. Individual grains are generally homogeneous within analytical uncertainty. Different grains within a single sample record temperature differences as large 55°, although in most samples the range of temperatures is on the order of 25°. In several samples, Zr-in-rutile temperatures from grains within garnet are lower than temperatures from matrix grains, reflecting growth of rutile with increasing temperature of metamorphism. Although the specific rutile-producing reactions have not been identified, it is inferred that rutile grows from either continuous reaction involving the breakdown of lower grade phases (possibly ilmenite), or from pseudomorph reactions involving the breakdown of relic igneous precursors at blueschist-facies conditions. No systematic variation in rutile temperatures was observed across the blueschist belt of northern Sifnos, consistent with the belt having behaved as a coherent block during subduction.  相似文献   
3.
Contaminant migration behaviour in the unsaturated zone of a fractured porous aquifer is discussed in the context of a study site in Cheshire, UK. The site is situated on gently dipping sandstones, adjacent to a linear lagoon historically used to dispose of industrial wastes containing chlorinated solvents. Two cores of more than 100 m length were recovered and measurements of chlorinated hydrocarbons (CHCs), inorganic chemistry, lithology, fracturing and aquifer properties were made. The results show that selecting an appropriate vertical sampling density is crucial both to providing an understanding of contaminant pathways and distinguishing whether CHCs are present in the aqueous or non-aqueous phase. The spacing of such sampling should be on a similar scale to the heterogeneity that controls water and contaminant movement. For some sections of the Permo-Triassic aquifer, significant changes in lithology and permeability occur over vertical distances of less than 1 m and samples need to be collected at this interval, otherwise considerable resolution is lost, potentially leading to erroneous interpretation of data. At this site, although CHC concentrations were high, the consistent ratio of the two main components of the plume (tetrachloroethene and trichloroethene) provided evidence of movement in the aqueous phase rather than in dense non-aqueous phase liquid (DNAPL).  相似文献   
4.
5.
The reaction muscovite+cordierite→biotite+Al2SiO5 +quartz+H2O is of considerable importance in the low pressure metamorphism of pelitic rocks: (1) its operation is implied in the widespread assemblage Ms + Crd +And± Sil + Bt + Qtz, a common mineral assemblage in contact aureoles and low pressure regional terranes; (2) it is potentially an important equilibrium for pressure estimation in low pressure assemblages lacking garnet; and (3) it has been used to distinguish between clockwise and anticlockwise P–T paths in low pressure metamorphic settings. Experiments and thermodynamic databases provide conflicting constraints on the slope and position of the reaction, with most thermodynamic databases predicting a positive slope for the reaction. Evidence from mineral assemblages and microtextures from a large number of natural prograde sequences, in particular contact aureoles, is most consistent with a negative slope (andalusite and/or sillimanite occurs upgrade of, and may show evidence for replacement of, cordierite). Mineral compositional trends as a function of grade are variable but taken as a whole are more consistent with a negative slope than a positive slope. Thermodynamic modelling of reaction 1 and associated equilibria results in a low pressure metapelitic petrogenetic grid in the system K2O–FeO–MgO–Al2O3–SiO2–H2O (KFMASH) which satisfies most of the natural and experimental constraints. Contouring of the Fe–Mg divariant interval represented by reaction 1 allows for pressure estimation in garnet‐absent andalusite+cordierite‐bearing schists and hornfelses. The revised topology of reaction 1 allows for improved analysis of P–T paths from mineral assemblage sequences and microtextures in the same rocks.  相似文献   
6.
We describe for the first time the generation and measurement of capillary waves in a water surface in a wind tunnel running with air at pressures of 15-1000 mbar. These experiments suggest a stronger dependence of wave generation on atmospheric density than the simple proportionality that might be expected from energy transfer arguments. Additionally, airflow over a nonaqueous fluid (kerosene) was found to produce waves of higher amplitude than for water under the same conditions. These preliminary results may indicate different efficiencies of wave generation on other planets, for which empirical terrestrial relations therefore do not apply, and thus may have a bearing on the lack of strong shoreline features on Mars and the possibility of specular glints from hydrocarbon lakes on Titan.  相似文献   
7.
Metapelites containing muscovite, cordierite, staurolite and biotite (Ms+Crd+St+Bt) are relatively rare but have been reported from a number of low-pressure (andalusite–sillimanite) regional metamorphic terranes. Paradoxically, they do not occur in contact aureoles formed at the same low pressures, raising the question as to whether they represent a stable association. A stable Ms+Crd+St+Bt assemblage implies a stable Ms+Bt+Qtz+Crd+St+Al2SiO5+Chl+H2O invariant point (IP1), the latter which has precluded construction of a petrogenetic grid for metapelites that reconciles natural phase relations at high and low pressure. Petrogenetic grids calculated from internally consistent thermodynamic databases do not provide a reliable means to evaluate the problem because the grid topology is sensitive to small changes in the thermodynamic data. Topological analysis of invariant point IP1 places strict limits on possible phase equilibria and mineral compositions for metamorphic field gradients at higher and lower pressure than the invariant point. These constraints are then compared with natural data from contact aureoles and reported Ms+Crd+St+Bt occurrences. We find that there are numerous topological, textural and compositional incongruities in reported natural assemblages that lead us to argue that Ms+Crd+St+Bt is either not a stable association or is restricted to such low pressures and Fe-rich compositions that it is rarely if ever developed in natural rocks. Instead, we argue that reported Ms+Crd+St+Bt assemblages are products of polymetamorphism, and, from their textures, are useful indicators of P–T  paths and tectonothermal processes at low pressure. A number of well-known Ms+Crd+St+Bt occurrences are discussed within this framework, including south-central Maine, the Pyrenees and especially SW Nova Scotia.  相似文献   
8.
A quantitative petrogenetic grid for pelitic schists in the system KFMASH that includes the phases garnet, chlorite, biotite, chloritoid, cordierite, staurolite, talc, kyanite, andalusite, sillimanite, and pyrophyllite (with quartz, H2O and muscovite or K-feldspar in excess) is presented. The grid is based on thermodynamic data of Berman et al. (1985) and Berman (1988) for endmember KFASH and KMASH equilibria and natural Fe-Mg partitioning for the KFMASH system. Calculation of P-T slopes and the change in Fe/(Fe+Mg) along reactions in the KFMASH system were made using the Gibbs method. In addition, the effect on the grid of MnO and CaO is evaluated quantitatively. The resulting grid is consistent with typical Buchan and Barrovian parageneses at medium to high grades. At low grades, the grid predicts an extensive stability field for the paragenesis chloritoid+biotite which arises because of the unusual facing of the reaction chloritoid+biotite + quartz+H2O = garnet+chlorite+muscovite, which proceeds to the right with increasing T in the KFMASH system. However, the reaction proceeds to the left with increasing T in the MnKFASH system so the assemblage chloritoid + biotite is restricted to bulk compositions with high Fe/(Fe+Mg+Mn). Typical metapelites will therefore contain garnet+chlorite at low grades rather than chloritoid + biotite.  相似文献   
9.
The suggestion that Sudbury-type ores may be formed by the introduction of country rock sulfur into still hot intrusions (i.e., sulfurization) suffers from a reputed lack of field evidence. Permissive evidence for sulfurization includes the epigenetic nature of many Sudbury-type ores and that many Sudbury-type ores crystallized from sulfide melts. Visual evidence exists for sulfurization of a gabbro in Zambia. The lead isotopic composition of ore minerals at Sudbury implies that at least some of the metals were derived from the erruptive. Published sulfur isotopic data from several Sudbury-type ores differ from and do not exhibit a common pattern of isotopic enrichment with respect to sulfides within associated intrusions. Evidently the sulfur was derived from the country rocks. Sudbury-type ores exhibiting magmatic textures commonly occur within more siliceous dikes than the host intrusions. Inorganic reduction of sulfate occurs only above 600° C. Reduction of sulfate with resultant sulfurization of ferrous iron and traces of other metals originally present in the still hot parental intrusive rock would make the rock more siliceous. Above 1100° C the silicate-residue and newly formed sulfides would form immiscible magmas. Therefore, ore magmas within and near mafic intrusives can be epigenetic. The processes by which sulfur is introduced into intrusions are still speculative.
Zusammenfassung Für die Annahme, daß Erze vom Sudbury-Typus sich durch Zuführung von Nebengesteinsschwefel in noch heiße Intrusionen bilden können (sulfurization), fehlt es angeblich an Feldunterlagen. Folgende Tatsachen lassen sich mit einer Schwefelung (sulfurization) vereinigen: der epigenetische Charakter vieler Erze vom Sudbury-Typ; auch sind viele Erze von Sudbury-Typus aus sulfidischen Schmelzen kristallisiert. In einem Gabbro in Zambia ist der Beweis für Schwefelung (sulfurization) direkt sichtbar. Die Isotopen-Zusammensetzung von Blei in Erzmineralien in Sudbury zeigt, daß mindestens einige der Metalle aus dem Eruptivgestein stammen. Schwefelisotop-Daten, die für mehrere Lagerstätten von Sudbury-Typen veröffentlicht worden sind, haben hinsichtlich der Isotop-Anreicherung keine gemeinsamen Züge. Offensichtlich stammt der Schwefel aus dem Nebengestein. Erze vom Sudbury-Typ mit magmatischem Gefüge finden sich oft in Gängen, die saurer sind als das Wirtsgestein. Anorganische Reduktion von Sulfat findet nur oberhalb 600°C statt. Reduktion von Sulfat und die entstehende Schwefelung (sulfurization) von zweiwertigem Eisen und Spuren anderer Metalle, die ursprünglich in dem noch heiß eruptiven Gestein anwesend sind, machen das Gestein noch saurer. Oberhalb 1100°C würden der Silicat-Rest und die neugeformten Sulfide nicht mischbare Magmen bilden. Deshalb können sich sulfidische Schmelzen innerhalb und in der Nähe von Mafic-Intrusionen später gebildet haben. Die Prozesse, durch die Schwefel in Intrusionen eingeführt wird, sind noch unbekannt.
  相似文献   
10.
We can presently construct two independent time series of sea level, each at a precision of a few centimeters, from Geosat (1985–1988) and TOPEX/Poseidon (1992–1995) collinear altimetry. Both are based on precise satellite orbits computed using a common geopotential model, JGM-2 (Nerem et al. 1994). We have attempted to connect these series using Geosat-T/P crossover differences in order to assess long-term ocean changes between these missions. Unfortunately, the observed result are large-scale sea level differences which appear to be due to a combination of geodetic and geopotential error sources. The most significant geodetic component seems to be a coordinate system bias for Geosat sea level (relative to T/P) of −7 to −9 cm in the y-axis (towards the Eastern Pacific). The Geosat-T/P sea height differences at crossovers (with JGM-2 orbits) probably also contain stationary geopotential-orbit error of about the same magnitude which also distort any oceanographic interpretation of the observed changes. We also found JGM-3 Geosat orbits have not resolved the datum errors evident from the JGM-2 Geosat -T/P results. We conclude that the direct altimetric approach to accurate determination of sea level change using Geosat and T/P data still depends on further improvement in the Geosat orbits, including definition of the geocenter. Received: 11 March 1996; Accepted: 19 September 1996  相似文献   
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