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1.
Ordering of interfacial water at the hematite and corundum (0 0 1)-water interfaces has been characterized using in situ high resolution specular X-ray reflectivity measurements. The hematite (0 0 1) surface was prepared through an annealing process to produce a surface isostructural with corundum (0 0 1), facilitating direct comparison. Interfacial water was found to display a similar structure on this pair of isostructural surfaces. A single layer of adsorbed water having a large vibrational amplitude was present on each surface and additional ordering of water extended at least 1 nm into the bulk fluid, with the degree of ordering decreasing with increasing distance from the surfaces. Consistent with prior studies of the (0 1 2) and (1 1 0) surfaces of hematite and corundum, the configuration of water above the (0 0 1) surfaces is primarily controlled by the surface structure, specifically the arrangement of surface functional groups. However, interfacial water at the (0 0 1) surfaces displayed significantly larger vibrational amplitudes throughout the interfacial region than at other isostructural sets of hematite and corundum surfaces, indicating weaker ordering. Comparison of the vibrational amplitudes of adsorbed water on a series of oxide, silicate, and phosphate mineral surfaces suggests that the presence or absence of a substantial interfacial electrostatic field is the primary control on water ordering and not the surface structure itself. On surfaces for which charge originates dominantly through protonation-deprotonation reactions the controlling factor appears to be whether conditions exist where most functional groups are uncharged as opposed to the net surface charge. The doubly coordinated functional groups on hematite and corundum (0 0 1) surfaces are largely uncharged under slightly acidic to circumneutral pH conditions, leading to weak ordering, whereas singly coordinated groups on (0 1 2) and (1 1 0) surfaces of these phases are always charged, even when the net surface charge is zero, and induce strong water ordering. Surfaces lacking structural charge can thus be divided into two distinct classes that induce either strong or weak ordering of interfacial water. Surface functional group coordination is the ultimate control on this division as it determines the charge state of such groups under different protonation configurations. Ion adsorption and electron transfer processes may differ between these classes of surfaces because of the effect of water ordering strength on interfacial capacitances and hydrogen bonding.  相似文献   

2.
Jarosite is an important mineral on Earth, and possibly on Mars, where it controls the mobility of iron, sulfate and potentially toxic metals. Atomistic simulations have been used to study the incorporation of Al3+, and the M2+ impurities Cd, Cu and Zn, in the (0 1 2) and (0 0 1) surfaces of jarosite. The calculations show that the incorporation of Al on an Fe site is favorable on all surfaces in which terminal Fe ions are exposed, and especially on the (0 0 1) [Fe3(OH)3]6+ surface. Incorporation of Cd, Cu or Zn on a K site balanced by a K vacancy is predicted to stabilize the surfaces, but calculated endothermic solution energies and the high degree of distortion of the surfaces following incorporation suggest that these substitutions will be limited. The calculations also suggest that incorporation of Cd, Cu and Zn on an Fe site balanced by an OH vacancy, or by coupled substitution on both K and Fe sites, is unfavorable, although this might be compensated for by growth of a new layer of jarosite or goethite, as predicted for bulk jarosite. The results of the simulations show that surface structure will exert an influence on uptake of impurities in the order Cu > Cd > Zn, with the most favorable surfaces for incorporation being (0 1 2) [KFe(OH)4]0 and (0 0 1) [Fe3(OH)3]6+.  相似文献   

3.
Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.  相似文献   

4.
Anatase and its allomorphic mineral rutile have the most prominent economic significance among titanium mineral resources and constitute one of the badly needed mineral resources currently in China. The Yantizishan-Moshishan anatase deposit was formerly referred to as an iron deposit. Based on recent investigation and exploration the authors believe that it is actually a large metamorphosed sedimentary anatase-dominated deposit belonging to a new genetic type. Ore bodies occur in stratoid and lenticular forms in Mesoproterozoic (1751 Ma) schist, metasandstone (metasiltstone), and amphibolite. Rich ores have perthitic structure comprising chiefly interbedded quartz perthite (with disseminated anatase and rutile) and anatase perthite. Ore minerals are mainly anatase and subordinately rutile and ilmenite (±hematite), while nonmetallic minerals are chiefly quartz with a certain amount of anthophyllite and biotite (±garnet). The grain sizes of anatase, rutile and ilmenite are 0.01–0.1 mm. Rich ores contain 3.14% to 15.46% TiO2, averaging 6.91%, while the low-grade ores have TiO2 content about 1.2%to 2.97%, averaging 1.76%. The ores have relatively high TFe and V contents. Trace elements in anatase and rutile such as Nb and Cr were analyzed by the electron microprobe. According to their relatively low Nb and Cr contents, source anatase and rutile must have come from meta-mafic rocks. Trace elements of the associated ilmenite show relatively high MnO and low MgO contents, just in contrast to those of ilmenite in V-Ti-magnetite ores of magmatic origin. The protoliths of amphibolite wall rocks should be basalt and picrite-basalt. Pertochemical data suggest that the tectonic setting of these rocks belongs to an island arc or a transitional belt between the island arc and oceanic ridge. Silicon isotope study shows that δ30Si values of different anatase ores, quartzite, and schist in this deposit are 0.1‰ to –0.9‰, similar to those of marine hydrothermal exhalative sedimentary deposits. All of these geological and geochemical characteristics of the ore deposit suggest that the anatase ores and amphibolite are products of submarine basic volcanism. The ores had chemical precipitation features, but were later subjected to regional intermediate (or somewhat lower) grade metamorphism (1158 Ma). Rutile was formed mainly in the process of this metamorphism. The ore belt locally underwent hydrothermal modification during the emplacement of Late Yanshanian granite (118?Ma).  相似文献   

5.
This paper mainly describes mineralogy and geochemistry of coals from the Weibei coalfield in the southeastern Ordos Basin, North China. A number of Al-hydroxide/oxyhydroxide minerals were detected in the Late Carboniferous coals (Nos. 5, 10 and 11 coals), especially in the No. 10 coal. Aluminum-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite and diaspore) in the No. 10 coal are associated with kaolinite, suggesting that these minerals are derived from the breakdown of kaolinite. A model in which Al-hydroxide/oxyhydroxide minerals form from the incongruent dissolution of kaolinite is presented. Nordstrandite and boehmite mainly occur as massive lenses (<500 μm in length). Diaspore appears as massive aggregates and as single euhedral crystals (<50 μm in length) in a kaolinite matrix. The presence of high temperature quartz, and zircon indicates that there was input of felsic volcanic debris during accumulation of the Late Carboniferous coals. These volcanic materials have also had a significant influence on the enrichment of certain trace elements including Li, Be, Ga, Zr, Nb, Mo, Sn, W and U in the Late Carboniferous coals (Nos. 5, 10, and 11 coals). SEM-EDX results show that Ga in the No. 10 coal (whole coal average 33.4 μg/g; n = 2) mainly occurs within Al-hydroxide/oxyhydroxide minerals (nordstrandite, boehmite, and diaspore), kaolinite and organic matter.  相似文献   

6.
Boron is an important micronutrient for plants but is toxic at high pore solution concentrations. Its mobility and migration in many geochemical environments is often controlled by reactions with mineral surfaces, and thus its speciation on mineral surfaces has been extensively investigated. Most previous studies have used IR spectroscopy to characterize the surface B-environments. We present here the first 11B MAS NMR study of surface sorbed boron on minerals. The results demonstrate the capability of this method to effectively probe the local structure of the sorption sites at total B-concentrations in the samples as small as 0.03 wt% and to provide insight into the mechanisms of sorption. Signal is readily resolved for both trigonal (B(3)) and tetrahedral (B(4)) boron exchanged onto boehmite, silica gel and illite, and the resonances are readily assigned on the basis of chemical shift and quadrupole coupling constant. Boron surface densities on illite are approximately order of magnitude greater than on silica gel or boehmite. For boehmite, both B(3) and B(4) occur dominantly as inner-sphere complexes formed by ligand exchange reaction with surface aluminol sites. The B(3)/[B(3) + B(4)] ratio of approximately 0.87 does not vary significantly with pH from 3 to 11, with solution B-concentration, or with washing. The occurrence of B(3) and B(4) as inner-sphere complexes is in agreement with previous suggestions from IR studies of B-sorption on iron hydroxide, allophone, kaolinite, and hydrous ferric oxide. For silica gel, B(3) and B(4) occur principally as outer-sphere complexes or as residual precipitate from un-removed solution. The B(3)/B(4) ratio decreases with increasing pH paralleling the speciation in solution, but the relative abundance of B(4) is greater than in solution. A small fraction of the B(4) occurs as inner-sphere complexes with B(4)-O-Si linkages formed by ligand exchange reaction with silanol sites. For illite, surface boron occurs as outer-sphere B(3) and B(4), as for silica gel, and as inner-sphere B(3) and B(4), as for boehmite. Outer-sphere B(3) and B(4) are dominant at pH 3 and 5, whereas inner-sphere B(3) and B(4) are dominant at pH 9 and 11. The inner-sphere complexes probably form dominantly by ligand exchange reactions involving sites on the broken edges of illite layers.  相似文献   

7.
This paper discusses the mineralogy and geochemistry of the No. 6 Coal (Pennsylvanian) in the Junger Coalfield, Ordos Basin, China. The results show that the vitrinite reflectance (0.58%) is lowest and the proportions of inertinite and liptinite (37.4% and 7.1%, respectively) in the No. 6 Coal of the Junger Coalfield are highest among all of the Late Paleozoic coals in the Ordos Basin. The No. 6 Coal may be divided vertically into four sections based on their mineral compositions and elemental concentrations. A high boehmite content (mean 6.1%) was identified in the No. 6 Coal. The minerals associated with the boehmite in the coal include goyazite, rutile, zircon, and Pb-bearing minerals (galena, clausthalite, and selenio-galena). The boehmite is derived from weathered and oxidized bauxite in the weathered crust of the underlying Benxi Formation (Pennsylvanian). A high Pb-bearing mineral content of samples ZG6-2 and ZG6-3 is likely of hydrothermal origin. The No. 6 coal is enriched in Ga (44.8 μg/g), Se (8.2 μg/g), Sr (423 μg/g), Zr (234 μg/g), REEs (193.3 μg/g), Hg (0.35 μg/g), Pb (35.7 μg/g), and Th (17.8 μg/g). Gallium and Th in the No. 6 Coal mainly occur in boehmite, and the Pb-bearing selenide and sulfide minerals contribute not only to Se and Pb contents in the coal, but also probably to Hg content. A high Zr content is attributed to the presence of zircon, and Sr is related to goyazite. The REEs in the coal are supplied from the sediment-source region, and the REEs leached from the adjacent partings by groundwater.  相似文献   

8.
Molecular dynamics simulations of water in contact with the (0 0 1) and (0 1 0) surfaces of orthoclase (KAlSi3O8) were carried out to investigate the structure and dynamics of the feldspar-water interface, contrast the intrinsic structural properties of the two surfaces, and provide a basis for future work on the diffusion of ions and molecules in microscopic mineral fractures. Electron density profiles were computed from the molecular dynamics trajectories and compared with those derived experimentally from high-resolution X-ray reflectivity measurements by Fenter and co-workers [Fenter P., Cheng L., Park C., Zhang H. and Sturchio N. C. (2003a) Structure of the orthoclase (0 0 1)- and (0 1 0)-water interfaces by high-resolution X-ray reflectivity. Geochim. Cosmochim. Acta67, 4267-4275]. For each surface, three scenarios were considered whereby the interfacial species is potassium, water, or a hydronium ion. Excellent agreement was obtained for the (0 0 1) surface when potassium is the predominant interfacial species; however, some discrepancies in the position of the interfacial peaks were obtained for the (0 1 0) surface. The two surfaces showed similarities in the extent of water ordering at the interface, the activation energies for water and potassium desorption, and the adsorption localization of interfacial species. However, there are also important differences between the two surfaces in the coordination of a given adsorbed species, adsorption site densities, and the propensity for water molecules in surface cavities and those in the first hydration layer to coordinate to surface bridging oxygen atoms. These differences may have implications for the extent of dissolution in the low-pH regime since hydrolysis of Si(Al)OSi(Al) bonds is a major dissolution mechanism.  相似文献   

9.
Adsorption of Rb+ and Sr2+ at the orthoclase (0 0 1)-solution interface is probed with high-resolution X-ray reflectivity and resonant anomalous X-ray reflectivity. Specular X-ray reflectivity data for orthoclase in contact with 0.01 m RbCl solution at pH 5.5 reveal a systematic increase in electron density adjacent to the mineral surface with respect to that observed in contact with de-ionized water (DIW). Quantitative analysis indicates that Rb+ adsorbs at a height of 0.83 ± 0.03 Å with respect to the bulk K+ site with a nominal coverage of 0.72 ± 0.10 ions per surface unit mesh (55.7 Å2). These results are consistent with an ion-exchange reaction in which Rb+ occupies an inner-sphere adsorption (IS) site. In contrast, X-ray reflectivity data for orthoclase in contact with 0.01 m Sr(NO3)2 solution at pH 5.3 reveal few significant changes with respect to DIW. Resonant anomalous X-ray reflectivity was used to probe Sr2+ adsorption and to image its vertical distribution. This element-specific measurement reveals that Sr2+ adsorbs with a total coverage of 0.37 ± 0.02 ions per surface unit mesh, at a substantially larger height (3.28 ± 0.05 Å) than found for Rb+, and with a relatively broad density distribution (having a root-mean-square width of 1.88 ± 0.08 Å for a single-peak model), implying that Sr2+ adsorbs primarily as a fully-hydrated outer-sphere (OS), species. Comparison to a two-height model suggests that 13 ± 5% of the adsorbed Sr2+ may be present as an IS species. This partitioning implies a ∼5 kJ/mol difference in free energy between the IS and OS Sr2+ on orthoclase. Differences in the partitioning of Sr2+ between IS and OS species for orthoclase (0 0 1) and muscovite (0 0 1) suggest control by the geometry of the IS adsorption site. Results for the OS distribution are compared to predictions of the Poisson-Boltzmann equation in the strong coupling regime, which predicts an intrinsically narrow vertical diffuse ion distribution; the OS distribution might thus be thought of as the diffuse ion profile in the limit of high surface charge.  相似文献   

10.
79Se is a potentially mobile long-lived fission product, which may make a dominant contribution to the long-term radiation exposure resulting from deep geological disposal of radioactive waste. Its mobility is affected by sorption on minerals. Selenium sorption processes have been studied mainly by considering interaction with a single mineral surface. In the case of multi-component systems (e.g. soils), it is difficult to predict the radioelement behaviour only from the mineral constituents. This study contributes to the understanding of multi-component controls of Se concentrations towards predicting Se behaviour in soils after migration from a disposal site. This goal was approached by measuring selenite sorption on mono and multi-phase systems physically separated by dialysis membranes. To the best of the authors’ knowledge, very few studies have used dialysis membranes to study the sorption competition of selenite between several mineral phases. Other workers have used this method to study the sorption of pesticides on montmorillonite in the presence of dissolved organic matter. Indeed, this method allows measurement of individual Kd in a system composed of several mineral phases. Dialysis membranes allowed (i) determination of the competition of two mineral phases for selenite sorption (ii) and determination of the role of humic acids (HAs) on selenite sorption in oxidising conditions. Experimental results at pH 7.0 show an average Se(IV) sorption distribution coefficient (Kd) of approximately 125 and 9410 L kg−1 for bentonite and goethite, respectively. The average Kd for goethite decreases to 613 L kg−1 or 3215 L kg−1 in the presence of bentonite or HA, respectively. For bentonite, the average Kd decreases slightly in the presence of goethite (60 L kg−1) and remains unchanged in the presence of HA. The experimental data were successfully modelled with a surface complexation model using the PHREEQC geochemical code. The drastic decrease in Se(IV) sorption on goethite in a multi-phase system is attributed to competition with dissolved silica released by bentonite. As with Si the HA compete with Se for sorption sites on goethite.  相似文献   

11.
The fossilization of biota and formation of low- and high-temperature hydrothermally altered rocks were studied in solfataric fields, artificial hot lakes, at natural hot springs, and on heated beach within the present-day rift zone at the Reykjanes, Nesjavellir, Geysir, Landmannalaugar, Namafjall, and Oxarfjodur geothermal areas. The hydrothermally altered rocks can be divided into the following mineral types: (1) smectite assemblage with iron oxides and hydroxides; (2) smectite assemblage with sulfides (pyrite); (3) kaolinite-metahalloysite assemblage with sulfates, anatase, and boehmite; and (4) siliceous assemblage. The detailed study of the hydrothermally altered rocks allowed us to elucidate some environmental features of modern fossilization and replacement of organic matter with clay minerals, iron oxyhydroxides, and silica. The fossilized microstructures have been described in rocks of the smectite and siliceous assemblages. It has been shown that the pseudobiomorphic (actually, abiogenic) micro- and nannostructures are formed in the moving water of silica deposition zone.  相似文献   

12.
A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg−1, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, Cp?, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young’s rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, Cp? (‘NaAl(OH)4’(aq)). Slopes of the Young’s rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of Cp? (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C.  相似文献   

13.
The western retroarc of the Southern Andes between 38° and 40° S is formed by a NNW-elongated ridge not associated with stacked thrust sheets. On the contrary, during the last 4–3 Ma this ridge was affected by extensional deformation, regional uplift and related folding on a very broad scale. Receiver function analysis shows that the drainage divide area and adjacent retroarc lie over an attenuated crust. Expected crustal thickness at these latitudes is around 38 km, whereas in this part of the retroarc the thickness is less than 32 km. The causes for such attenuation have been linked to a moderate steepening of the subducted Nazca plate beneath the South American plate, which is suggested by a westward shift and narrowing of the magmatic arc during the last 4 to 5 Ma. Gravimetric studies show that the upper plate did not react homogeneously to slab steepening, but ancient sutures and lithospheric discontinuities deeply buried under Mesozoic to Cenozoic sequences in the retroarc were locally reactivated. These processes resulted in an asthenospheric anomaly that correlates at the surface with the area of Pliocene to Quaternary doming, widespread extension and three radial troughs. Two of the troughs have accommodated substantial amounts of extension, but the third was probably aborted at an early stage. Moreover, the presence of an anomalous concentration of calderas and large volcanic centers over the proposed asthenospheric anomaly, and their age distribution, may indicate minor migration of the asthenospheric anomaly between 4 and 2 Ma through the western South American plate.  相似文献   

14.
Carbon dioxide- and salt-bearing solutions are common in granulite, ore-forming and magmatic environments. The presence of CO2 affects mineral solubilities, fluid miscibility, and viscosity and wetting properties, and is expected to affect salt speciation. EXAFS measurements of RbBr-H2O-CO2 fluids contained in corundum-osed synthetic fluid inclusions (SFLINCs) have been used to investigate the effect of CO2 on salt speciation at temperatures to 579 °C and pressures to around 0.26 GPa.Forward modelling indicates that solute dehydration is difficult to distinguish from up to around 40% of Rb-Br ion-pairing, so results refer to the total number of nearest neighbours, which are likely to be mostly O present in waters of hydration, but may also include Br, if ion pairing is present. Additionally, results relate to the number of well-ordered neighbours in the first shell, because nearest neighbours with a high degree of disorder may be present but contribute minimally to the EXAFS signal. Analysis of the EXAFS results at the Rb edge for the CO2-free solution is consistent with previous work and shows that the number of nearest neighbours for Rb in CO2-free solutions decreases from 6 ± 0.6 to 1.4 ± 0.1 as temperature increases from 20 to 534 °C. The decrease is accompanied by a decrease in Rb-x bondlengths of 0.05 Å, where x is the first shell scatterer. Results for the CO2-bearing solution are different to those for the CO2-free solution. The number of nearest neighbours is 16 and 22% less than for the CO2-bearing solution at 312 and 445 °C respectively. Changes in the numbers of nearest neighbours correlate well with calculated changes in the bulk solution dielectric constant; CO2-bearing and CO2-free solutions lie on the same trend, which suggests that it may be possible to calculate the number of nearest neighbours from dielectric constant. Rb-x bondlengths for the CO2-bearing solution are statistically indistinguishable to those for the CO2-free inclusions. Results for Br are worse quality than for Rb so EXAFS analysis could not be completed, however XANES spectra for CO2-free and CO2-bearing solutions are consistent with solute dehydration similar to that recorded by the Rb spectra. The conclusions of this study provide support for the notion that CO2 has a fundamental effect on the mechanics of solubility, and that these effects should be incorporated into conceptual and quantitative thermodynamic models.  相似文献   

15.
This study used batch reactors to characterize the rates and mechanisms of elemental release during the interaction of a single bacterial species (Burkholderia fungorum) with Columbia River Flood Basalt at T = 28 °C for 36 days. We primarily examined the release of Ca, Mg, P, Si, and Sr under a variety of biotic and abiotic conditions with the aim of evaluating how actively metabolizing bacteria might influence basalt weathering on the continents. Four days after inoculating P-limited reactors (those lacking P in the growth medium), the concentration of viable planktonic cells increased from ∼104 to 108 CFU (Colony Forming Units)/mL, pH decreased from ∼7 to 4, and glucose decreased from ∼1200 to 0 μmol/L. Mass-balance and acid-base equilibria calculations suggest that the lowered pH resulted from either respired CO2, organic acids released during biomass synthesis, or H+ extrusion during uptake. Between days 4 and 36, cell numbers remained constant at ∼108 CFU/mL and pH increased to ∼5. Purely abiotic control reactors as well as control reactors containing inert cells (∼108 CFU/mL) showed constant glucose concentrations, thus confirming the absence of biological activity in these experiments. The pH of all control reactors remained near-neutral, except for one experiment where the pH was initially adjusted to 4 but rapidly rose to 7 within 2 days. Over the entire 36 day period, P-limited reactors containing viable bacteria yielded the highest Ca, Mg, Si, and Sr release rates. Release rates inversely correlate with pH, indicating that proton-promoted dissolution was the dominant reaction mechanism. Both biotic and abiotic P-limited reactors displayed low P concentrations. Chemical analyses of bacteria collected at the end of the experiments, combined with mass-balances between the biological and fluid phases, demonstrate that the absence of dissolved P in the biotic reactors resulted from microbial P uptake. The only P source in the basalt is a small amount of apatite (∼1.2%), which occurs as needles within feldspar grains and glass. We therefore conclude that B. fungorum utilized apatite as a P source for biomass synthesis, which stimulated elemental release from coexisting mineral phases via pH lowering. The results of this study suggest that actively metabolizing bacteria have the potential to influence elemental release from basalt in continental settings.  相似文献   

16.
The bauxites deposits of Kachchh area in Gujarat are investigated to characterize them based on mineralogical and petrographic studies. The major bauxitic mineral in these occurrences is gibbsite, with minor concentration of boehmite and diaspore. Apart from the bauxitic minerals, the other associate minerals are kaolin, calcite, alunite and the iron ore minerals such as hematite and goethite and titanium rich anatase. The iron ore minerals (hematite and goethite) are 10-50microns in size and are disseminated throughout the oolitic and pisolitic bauxitic minerals. At places the goethite exhibits colloform texture. The preservation of basaltic texture in some of the samples indicate that the insitu nature of these bauxites, which are formed by the alteration of calcic plagioclase from the parent basalt. Although, the basalt occurs as the main parent rock for these bauxites, the presence of calcite in some of the samples represent the possibility of having a limestone parent rock at least in some of the bauxite occurrences.  相似文献   

17.
Highly reducing and high-pH vent fluids characterize moderately low temperature ultramafic-hosted hydrothermal systems, such as the recently discovered Lost City hydrothermal field at 30°N Mid-Atlantic Ridge Ridge (MAR). To better understand the role of mineral reaction rates on changes in fluid chemistry and mineralization processes in these and similar systems, we conducted an experimental study involving seawater and peridotite at 200 °C, 500 bar. Time series changes in fluid chemistry were monitored and compared with analogous data predicted using experimental and theoretical data for mineral dissolution rates. Although there was qualitative agreement between predicted and measured changes in the chemical evolution of the fluid for some species, the rate and magnitude of increase in pH, dissolved chloride and H2 did not agree well with predictions based on theoretical modeling results. Experimental data indicate that dissolved H2 abruptly and intermittently increased, reaching a value only approximately 20% of that predicted assuming magnetite as the primary Fe-bearing alteration phase. The distribution and valence of Fe in primary and secondary minerals reveal that the most abundant secondary mineral, serpentine, contained significant amounts of both ferric and ferrous Fe, with the less abundant brucite, also being Fe-rich (XFe = 0.3). Surprisingly, magnetite was present in only trace amounts, indicating that H2 generation was largely accommodated by the formation of Fe-chrysotile. Accordingly, the diversity of Fe-bearing secondary minerals together with rates of serpentinization less than theoretically predicted, account best for the relatively low dissolved H2 concentrations produced. Thus, the experimental data can be used to obtain provisional estimates of thermodynamic data for Fe-bearing minerals, enhancing the application of reaction path models depicting mass transfer processes during serpentinization at mid-ocean ridges. Similarly, the observed differences between theoretically predicted and experimentally measured pH values result from constraints imposed by complex patterns of mass transfer inherent to the experimental system. In particular, the experimental observation of a late stage increase in Na/Cl ratio likely results from the dissolution of a Na2O component of clinopyroxene, which causes pH to increase sufficiently to induce precipitation of a Ca-bearing phase, perhaps portlandite. As with the redox variability observed during the experiment, this event could not be predicted, underscoring the need to use caution when modeling alteration processes in the chemically complex ultramafic-hosted hydrothermal systems at elevated temperatures and pressures.  相似文献   

18.
The aqueous interfacial chemistry of kaolinite and Na-montmorillonite samples was investigated by potentiometric measurements using acid/base continuous titrations and batch experiments at 25 and 60 °C. Using the batch experimental method, a continuous drift of pH was observed reflecting the mineral dissolution. Consequently, the continuous titration method appears to be the best way of studying solid surface reactions. For each clay mineral, the net proton surface excess/consumption was calculated as a function of pH and ionic strength (0.025, 0.1 and 0.5 M). At 25 °C, and according to the literature data, the pH corresponding to zero net proton consumption for montmorillonite appears to depend on ionic strength, whereas the value for kaolinite is constant and close to 5. Similar results are obtained at 60 °C, which suggests that the point of zero net proton consumption for clay minerals does not depend on temperature, at least up to 60 °C. On the other hand, the temperature rise induces a slight increase of the net proton surface excess. Finally, the diffuse double layer formalism (DDLM) is used to model the experimental data. The model involves two processes: the protonation/deprotonation of two types of edge sites (aluminol and silanol) and H+/Na+ exchange reactions on basal surfaces, while a tiny proportion of the negative structural charge remains uncompensated. This last process maintains a negative surface potential whatever the pH of the solution, which is in agreement with electrokinetic data.  相似文献   

19.
The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H2O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H2O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H2O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi3O6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P-T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.  相似文献   

20.
Dissolution of the synthetic hydroxylapatite (HAP) and fluorapatite (FAP) in pure water was studied at 25 °C and 45 °C in a series of batch experiments. The XRD, FT-IR and SEM analyses indicated that the synthetic, microcrystalline HAP and FAP with apatite structure used in the experiments were found to have no obvious variation after dissolution except that the existence of OH groups in FT-IR spectra for FAP after 2880 h dissolution was observed. During the HAP dissolution (0–4320 h), the aqueous calcium and phosphate concentrations reached the maxima after 120 h and then decreased slowly with time. For the FAP dissolution in pure water, after a transient time of 1440 h (< 60 d), element concentrations and pH became constant suggesting attainment of a steady-state between the solution and solid. During early stages of the FAP dissolution reaction (< 72–120 h), mineral components were released in non-stoichiometric ratios with reacted solution ratios of dissolved Ca:P, Ca:F and P:F being lower than mineral stoichiometric ratios of Ca5(PO4)3F, i.e., 1.67, 5.0 and 3.0, respectively. This indicated that F were preferentially released compared to Ca from the mineral structure. The mean Ksp values were calculated by using PHREEQC for HAP of 10− 53.28 (10− 53.02–10− 53.51) and for FAP of 10− 55.71 (10− 55.18–10− 56.13) at 25 °C, the free energies of formation ΔGfo[HAP] and ΔGfo[FAP] were calculated to be − 6282.82 kJ/mol and − 6415.87 kJ/mol, respectively.  相似文献   

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