共查询到20条相似文献，搜索用时 46 毫秒
1.
《Applied Geochemistry》2000,15(9):1399-1416
Dissolution of a simulated British Magnox waste glass is governed by two pH-dependent processes. At low pH, dissolution is governed by reactions occurring predominantly at non-Si sites and residual Si-rich gels develop at the glass surface as B, Al and modifier cations are selectively leached. Here, extensive proton promoted hydrolysis of BO and AlO bonds is coupled with hydration and ion exchange processes. Hydrolysis of siloxane bonds governs the rate of dissolution at high pH and the glass dissolves congruently as the silicate network breaks down extensively. Differences in the surface chemistries and morphologies of glass samples reacted in strongly acidic and highly alkaline media reflect the net effects of these processes. The rate of the congruent dissolution process is influenced by the activity of silicic acid. The results are compared with published data for other glass formulations and are discussed in the context of proposed kinetic dissolution models. 相似文献
2.
The short range distribution of interatomic distances in three feldspar glasses has been determined by X-ray radial distribution analysis. The resulting radial distribution functions (RDF's) are interpreted by comparison with RDF's calculated for various quasi-crystalline models of the glass structure.The experimental RDF's of the alkali feldspar glasses were found to be inconsistent with the four-membered rings of tetrahedra associated with crystalline feldspars; the structures of these glasses are probably based on interconnected six-membered rings of the type found in tridymite, nepheline, or kalsilite. In contrast, the RDF of calcic feldspar glass is consistent with a four-membered ring structure of the type found in crystalline anorthite. T-O bond lengths (T = Si,Al) increase from 1.60 Å in SiO2 glass [J. H. Konnert and J. Karle (1973) Acta Cryst.A29, 702–710] to 1.63 Å in the alkali feldspar glasses to 1.66 Å in the calcic feldspar glass due to the substitution of Al for Si in the tetrahedra] sites. The T-O-T bond angles inferred from the RDF peak positions are 151° in SiO2 glass (see reference above), 146° in the alkali feldspar glasses, and 143° in the calcic feldspar glass. Detail in the RDF at distances greater than 5 Å suggests that the alkali feldspar glasses have a higher degree of long range order than the calcic feldspar glasses.Assuming that the structural details of our feldspar glasses are similar to those of the melts, the observed structural differences between the alkali feldspar and calcic feldspar glasses helps explain the differences in crystallization kinetics of anhydrous feldspar composition melts. Structural interpretations of some thermodynamic and rheologic phenomena associated with feldspar melts are also presented based on these results. 相似文献
3.
Comparison of measured far-from-equilibrium dissolution rates of natural glasses and silicate minerals at 25 °C and pH 4 reveals the systematic effects of crystallinity and elemental composition on these rates. Rates for both minerals and glasses decrease with increasing Si:O ratio, but glass dissolution rates are faster than corresponding mineral rates. The difference between glass and mineral dissolution rates increases with increasing Si:O ratio; ultra-mafic glasses (Si:O ? 0.28) dissolve at similar rates as correspondingly compositioned minerals, but Si-rich glasses such as rhyolite (Si:O ∼ 0.40) dissolve ?1.6 orders of magnitude faster than corresponding minerals. This behaviour is interpreted to stem from the effect of Si-O polymerisation on silicate dissolution rates. The rate controlling step of dissolution for silicate minerals and glasses for which Si:O > 0.28 is the breaking of Si-O bonds. Owing to rapid quenching, natural glasses will exhibit less polymerisation and less ordering of Si-O bonds than minerals, making them less resistant to dissolution. Dissolution rates summarized in this study are used to determine the Ca release rates of natural rocks at far-from-equilibrium conditions, which in turn are used to estimate their CO2 consumption capacity. Results indicate that Ca release rates for glasses are faster than those of corresponding rocks. This difference is, however, significantly less than the corresponding difference between glass and mineral bulk dissolution rates. This is due to the presence of Ca in relatively reactive minerals. In both cases, Ca release rates increase by ∼two orders of magnitude from high to low Si:O ratios (e.g., from granite to gabbro or from rhyolitic to basaltic glass), illustrating the important role of Si-poor silicates in the long-term global CO2 cycle. 相似文献
4.
库车坳陷白垩系深层致密砂岩储层溶蚀作用实验模拟研究 总被引：1，自引：1，他引：0
库车坳陷前陆区白垩系发育特低物性、强非均质性和高稳产砂岩储层,溶蚀作用显著,但成因机制尚不是很明确。利用高温高压热模拟实验还原了目的层在成岩演化过程中1种表生流体和2种埋藏流体环境下溶蚀作用差异,揭示了成岩矿物演化过程及储集空间结构变化特征。结果表明,表生成岩期大气淡水淋滤弱酸性流体环境（CO2饱和溶液,pCO2=1 MPa）溶蚀作用最为显著,长石类矿物发生明显溶蚀,石英和黏土矿物相对难溶,Na+、Ca2+和K+等离子析出明显,Si4+和Al3+析出较少,样品表面沉淀出较多的疑似多边形石英和铝硅酸类矿物;成岩晚期油气充注酸性流体环境（乙酸溶液,2 mL/L）溶蚀作用其次,易于溶解白云石、石膏和长石类矿物,Ca2+、Mg2+、Na+和Si4+等离子析出明显,样品表面无沉淀;成岩早-中期碱性流体环境（NaHCO3溶液,pH=7.46、HCO3-=0.6 mol/L）溶蚀作用相对较弱,石英、长石和部分黏土矿物均发生了不同程度的溶蚀,且随着温度、压力的增加,溶蚀作用程度增加。综合分析表明:表生流体是研究区砂岩储层溶蚀孔隙发育的关键因素,其次为有机酸和碱性埋藏流体。这一认识能够丰富致密砂岩储层孔隙成岩演化理论,为下一步寻找规模储层发育区和气田有效开发提供理论支撑。 相似文献
5.
Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol−1, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.
Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H+ and OH− ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H+ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH− on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pHzpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.
Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H2O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H+- or OH−-promoted dissolution. 相似文献
6.
Mark E. Hodson 《Chemical Geology》2002,190(1-4):91-112
Far-from-equilibrium batch dissolution experiments were carried out on the 2000–500, 500–250, 250–53 and 53–2 μm size fractions of the mineral component of the B horizon of a granitic iron humus podzol after removal of organic matter and secondary precipitates. The different size fractions were mineralogically and chemically similar, the main minerals present being quartz, alkali and plagioclase feldspar, biotite and chlorite. Specific surface area increased with decreasing grain size. The measured element release rates decreased in the order 53–2>>>2000–500>500–250>250–53 μm. Surface area normalised element release rates from the 2000–500, 500–250 and 250–53 μm size fractions (0.6–77×10−14 mol/m2/s) were intermediate between literature reported surface area normalised dissolution rates for monomineralic powders of feldspar (0.1–0.01×10−14 mol/m2/s) and sheet silicates (100×10−14 mol/m2/s) dissolving under similar conditions. Element release rates from the 53–2 μm fraction (400–3000×10−14 mol/m2/s) were a factor of 4–30 larger than literature reported values for sheet silicates. The large element release rate of the 53–2 μm fraction means that, despite the small mass fraction of 53–2 μm sized particles present in the soil, dissolution of this fraction is the most important for element release into the soil. A theoretical model predicted similar (within a factor of <2) bulk element release rates for all the mineral powders if observed thicknesses of sheet silicate grains were used as input parameters. Decreasing element release rates with decreasing grain size were only predicted if the thickness of sheet silicates in the powders was held constant. A significantly larger release rate for the 53–2 μm fraction relative to the other size fractions was only predicted if either surface roughness was set several orders of magnitude higher for sheet silicates and several orders of magnitude lower for quartz and feldspars in the 53–2 μm fraction compared to the other size fractions or if the sheet silicate thickness input in the 53–2 μm fraction was set unrealistically low. It is therefore hypothesised that the reason for the unpredicted large release rate from the 52–3 μm size fraction is due to one or more of the following reasons: (1) the greater reactivity of the smaller particles due to surface free energy effects, (2) the lack of proportionality between the BET surface area used to normalise the release rates and the actual reactive surface area of the grains and, (3) the presence of traces quantities of reactive minerals which were undetected in the 53–2 μm fraction but were entirely absent in the coarser fractions. 相似文献
7.
长石类矿物是地壳中最常见的硅酸盐矿物,其风化作用对地球表面环境有显著影响,因而是风化作用研究的重点矿物之一。文中以长石为例,对硅酸盐矿物的风化作用研究现状从矿物的自然风化、模拟矿物化学风化和矿物的生物风化3个方面进行阐述;对影响矿物风化的各种因素及其在风化过程中所起的作用,以及长石微生物风化作用的机理和过程进行分析;指出目前硅酸盐矿物风化研究中存在的问题,并对未来的发展方向提出建议,指出对微生物-矿物复合体微环境物理化学性质的深入研究可能成为揭示微生物-矿物相互作用机理的一个突破口。 相似文献
8.
The effect of Fe-oxidizing bacteria on Fe-silicate mineral dissolution 总被引：11，自引：0，他引：11
Cara M. Santelli Susan A. Welch Henry R. Westrich Jillian F. Banfield 《Chemical Geology》2001,180(1-4):99-115
Acidithiobacillus ferrooxidans are commonly present in acid mine drainage (AMD). A. ferrooxidans derive metabolic energy from oxidation of Fe2+ present in natural acid solutions and also may be able to utilize Fe2+ released by dissolution of silicate minerals during acid neutralization reactions. Natural and synthetic fayalites were reacted in solutions with initial pH values of 2.0, 3.0 and 4.0 in the presence of A. ferrooxidans and in abiotic solutions in order to determine whether these chemolithotrophic bacteria can be sustained by acid-promoted fayalite dissolution and to measure the impact of their metabolism on acid neutralization rates. The production of almost the maximum Fe3+ from the available Fe in solution in microbial experiments (compared to no production of Fe3+ in abiotic controls) confirms A. ferrooxidans metabolism. Furthermore, cell division was detected and the total cell numbers increased over the duration of experiments. Thus, over the pH range 2–4, fayalite dissolution can sustain growth of A. ferrooxidans. However, ferric iron released by A. ferrooxidans metabolism dramatically inhibited dissolution rates by 50–98% compared to the abiotic controls.
Two sets of abiotic experiments were conducted to determine why microbial iron oxidation suppressed fayalite dissolution. Firstly, fayalite was dissolved at pH 2 in fully oxygenated and anoxic solutions. No significant difference was observed between rates in these experiments, as expected, due to extremely slow inorganic ferrous iron oxidation rates at pH 2. Experiments were also carried out to determine the effects of the concentrations of Fe2+, Mg2+ and Fe3+ on fayalite dissolution. Neither Fe2+ nor Mg2+ had an effect on the dissolution reaction. However, Fe3+, in the solution, inhibited both silica and iron release in the control, very similar to the biologically mediated fayalite dissolution reaction. Because ferric iron produced in microbial experiments was partitioned into nanocrystalline goethite (with very low Si) that was loosely associated with fayalite surfaces or coated the A. ferrooxidans cells, the decreased rates of accumulation of Fe and Si in solution cannot be attributed to diffusion inhibition by goethite or to precipitation of Fe–Si-rich minerals. The magnitude of the effect of Fe3+ addition (or enzymatic iron oxidation) on fayalite dissolution rates, especially at low extents of fayalite reaction, is most consistent with suppression of dissolution by interaction between Fe3+ and surface sites. These results suggest that microorganisms can significantly reduce the rate at which silicate hydrolysis reactions can neutralize acidic solutions in the environment. 相似文献
9.
Harold C. Helgeson William M. Murphy Per Aagaard 《Geochimica et cosmochimica acta》1984,48(12):2405-2432
Analysis of experimental data reported by Lagache (1965, 1976), Evans (1965), Busenberg (1975), Busenberg and Clemency (1976), Holdren and Berner (1979), Siegel and Pfannkuch (1984), and Chou and Wollast (1984) with the aid of irreversible thermodynamics and transition state theory (Aagaard and Helgeson, 1977, 1982) suggests that at temperatures at least up to 650°C, the rate of both congruent and incongruent feldspar hydrolysis in aqueous solutions far from equilibrium at pH ? 10.6 ? (2300/T), where T stands for temperature in kelvins, is a function solely of effective surface area and pH at constant pressure and temperature. At higher pH, the rate is apparently pH-independent up to ~pH 8 at 25°C, where it again becomes pH-dependent at higher pH. Observations of scanning electron micrographs indicate that the cross-sectional area of etch pits on hydrolyzed feldspar grains is of the order of 10?9 to 10?8 cm2 and that the ratio of the effective to total surface area (which may or may not change with reaction progress) ranges from <0.01 to 1, depending on the grain size, dislocation density, and the extent of comminution damage on the surfaces of the grains. Apparent rate constants retrieved from experimental data reported in the literature for feldspar hydrolysis in the lower pH-dependent range extend from ~10?13 to ~10?7 moles cm?2 sec?1 at temperatures from 25° to 200°C, which is consistent with activation enthalpies for albite and adularia of the order of 20 kcal mole?1. In contrast, the apparent rate constants for the pH-independent rate law range from ~10?16 to ~10?11 moles cm?2 sec?1 at temperatures from 25° to 650°C, which requires an activation enthalpy for adularia of ~ 9 kcal mole?1. These observations are consistent with surface control of reaction rates among minerals and aqueous solutions. The rate-limiting step in the pH-dependent case apparently corresponds at the lower end of the pH scale to breakdown of a protonated configuration of atoms on the surface of the reactant feldspar, but at higher pH the rate is limited by decomposition of an activated surface complex corresponding in stoichiometry to hydrous feldspar. In highly alkaline solutions, an activated complex containing hydroxyl ions apparently controls the rate of feldspar hydrolysis. Nevertheless, near equilibrium, regardless of pH the rate is proportional to the chemical affinity of the overall hydrolysis reaction. 相似文献
10.
《Applied Geochemistry》1997,12(1):83-95
In a column experiment, acidic groundwater from Pinal Creek Arizona, a Cu mining area, was eluted through a composited alluvial sample obtained from a core that had been removed from a well downgradient of the acidic groundwater. The minerals present in typical grains and flakes in the alluvium before and after the elution were determined by X-ray diffraction (XRD), scanning electron microscopy, and energy dispersive multichannel analyses (EDX). The concentrations of Fe, Ti, Mn, Si, Al, Na, Ca, K, Mg and S in these grains and flakes and in their microcrystalline surface coatings were measured by EDX.In addition to magnetite, hematite, and Fe-Ti oxides, Fe was most concentrated in micas (especially biotite-like flakes) and in the microcrystalline coatings. The measured elements in these microcrystalline coatings were primarily K, Fe, Al, and Si. The microcrystalline coatings on the mica flakes also contained Mg. The approximate l:3 Mg:Si atomic ratios (ARs)_of the biotite-life flake both before and after the elution would suggest that the Fe deposited during the elution had not substituted for Mg in these flakes. As a result of the elution, assuming no loss of Si, the averaged recorded Fe:Si AR of the microcrystalline coatings increased from (0.46 to 0.58):3.00.Iron deposition on the typical grains and flakes may relate to the presence of Fe in the particle on which it is deposited or to the presence of Fe in the microcrystalline surface coatings before elution. The data here are not sufficient for a statistical evaluation, but elution caused the following trends: (l) The Fe:Si AR increased in the (K,Fe,Al,Si)-microcrystalline surface coatings; (2) For the mica flakes, there was more than a 2-fold increase in the Fe:Si AR for the microcrystalline surface coatings of the Fe-rich biotite-like flakes but no measurable increase of the Fe:Si AR for the microcrystalline surface coatings of the muscovite-like flakes that contained 3–5 times less Fe; (3) Also for the biotite-like flakes, the increase in Fe:Si AR was greater in the flakes that had a higher Fe:Si AR; (4) The Fe deposition on the Fe-rich microcrystalline surface coatings of the feldspar was much greater than on the Fe-poor, beige quartz and feldspar grains that, prior to elution, had only CaS04 microcrystalline coatings; and (5) No Fe was deposited on Fe-poor grains with no microcrystalline surface coating. 相似文献
11.
利用扫描电镜和能谱分析研究天池火山天文峰剖面全新世喷发物中长石表面硅膜的结构状态和化学组成,结果显示:天文峰剖面从顶部黑色浮岩向下到暗灰色浮岩中,长石表面发育有不同结构状态的硅膜.硅膜的结构特征有随火山喷发时代越早,长石颗粒表面硅膜越厚,结构越复杂;喷发时代越晚,长石颗粒表面硅膜越薄,其结构越简单的变化趋势,即长石表面... 相似文献
12.
At Mt. Vulture volcano (Basilicata, Italy) calcite globules (5–150 μm) are hosted by silicate glass pools or veins cross-cutting amphibole-bearing, or more common spinel-bearing mantle xenoliths and xenocrysts. The carbonate globules are rounded or elongated and are composed of a mosaic of 2–20 μm crystals, with varying optical orientation. These features are consistent with formation from a quenched calciocarbonatite melt. Where in contact with carbonate amphibole has reacted to form fassaitic pyroxene. Some of these globules contain liquid/gaseous CO2 bubbles and sulphide inclusions, and are pierced by quench microphenocrysts of silicate phases. The carbonate composition varies from calcite to Mg-calcite (3.8–5.0 wt.% MgO) both within the carbonate globules and from globule to globule. Trace element contents of the carbonate, determined by LAICPMS, are similar to those of carbonatites worldwide including ΣREE up to 123 ppm. The Sr–Nd isotope ratios of the xenolith carbonate are similar to the extrusive carbonatite and silicate rocks of Mt. Vulture testifying to derivation from the same mantle source. Formation of immiscibile silicate–carbonatite liquids within mantle xenoliths occurred via disequilibrium immiscibility during their exhumation. 相似文献
13.
水热法分解钾长石制备雪硅钙石的实验研究 总被引：10，自引：3，他引：7
采用CaO作为助剂,在低温、中压的水热条件下分解钾长石,继而合成一种水合硅酸钙--雪硅钙石,同时得到KOH稀溶液,可用于制备高纯碳酸钾。影响晶化反应的主要因素有n(Ca)/n(Al+Si)、晶化温度、晶化时间、水固比（质量比）、搅拌速度等。讨论了各因素对钾长石分解及雪硅钙石形成的影响,通过X射线粉末衍射、热重-差热分析、扫描电镜等手段对合成产物进行结构性能表征。实验结果表明,以CaO为助剂分解钾长石,同时合成雪硅钙石的工艺方法可行,资源利用率接近100%。实验得到的优化工艺条件为：晶化温度为220～250 ℃,n(Ca)/n(Al+Si)在0.8～1.0之间,晶化时间5～8 h,水固比为20～25,搅拌速度400 r/min。在此条件下,钾长石中K2O的溶出率达80%以上,同时得到结晶良好的针状雪硅钙石晶体。 相似文献
14.
《Geochimica et cosmochimica acta》1999,63(19-20):3247-3259
The rate of Si release from dissolving bytownite feldspar in abiotic batch reactors increased as temperatures increased from 5° to 35°C. Metabolically inert subsurface bacteria (bacteria in solution with no organic substrate) had no apparent effect on dissolution rates over this temperature range. When glucose was added to the microbial cultures, the bacteria responded by producing gluconic acid, which catalyzed the dissolution reaction by both proton- and ligand-promoted mechanisms. The metabolic production, excretion, and consumption of gluconic acid in the course of glucose oxidation, and therefore, the degree of microbial enhancement of mineral dissolution, depend on temperature. There was little accumulation of gluconic acid and therefore, no significant enhancement of mineral dissolution rates at 35°C compared to the abiotic controls. At 20°C, gluconate accumulated in the experimental solutions only at the beginning of the experiment and led to a twofold increase in dissolved Si release compared to the controls, primarily by the ligand-promoted dissolution mechanism. There was significant accumulation of gluconic acid in the 5°C experiment, which is reflected in a significant reduction in pH, leading to 20-fold increase in Si release, primarily attributable to the proton-promoted dissolution mechanism. These results indicate that bacteria and microbial metabolism can affect mineral dissolution rates in organic-rich, nutrient-poor environments; the impact of microbial metabolism on aluminum silicate dissolution rates may be greater at lower rather than at higher temperatures due to the metabolic accumulation of dissolution-enhancing protons and ligands in solution. 相似文献
15.
Li Zhang 《Geochimica et cosmochimica acta》2009,73(10):2832-4139
The more rapid dissolution of Ca-rich feldspars relative to Na, K-rich feldspars has been attributed to the preferential leaching of Al deep within the feldspar structure. Evidence from surface microanalysis (e.g., Hellmann et al., 2003), however, shows that preferential dissolution of Al is confined to the top layers of the feldspar lattice and that the amorphous surface layer most likely results from precipitation versus dissolution. It is thus critical to examine the extent of preferential Al removal. Here we present a theoretical study of plagioclase dissolution behavior using parameterized Monte Carlo simulations. Two different dissolution mechanisms, a mechanism involving preferential leaching of Al and an interfacial dissolution-reprecipitation mechanism, are tested using compositions representing the entire plagioclase solid solution series. Our modeling results indicate that under the control of the preferential Al leaching mechanism, the influence of (Al, Si) disorder on the dissolution rate is significant. At a fixed composition, an increase in the degree of (Al, Si) disorder yields an increased dissolution rate, with an 8-fold increase in dissolution rate observed for highly disordered albite (An0) compared to low albite. Increasing anorthite content tends to decrease the variation in the dissolution rate due to disorder. The difference in the dissolution rate of 293 tested oligoclase configurations with a composition of An20 is 3-fold, and the difference is reduced to 2-fold among 107 andesine configurations of An30. Furthermore, feldspar configurations with completely disordered (Al, Si) distributions yield a consistent log-linear dependence of dissolution rate on the anorthite content (An), while other feldspar configurations with modest degrees of (Al, Si) disorder exhibit rates less than this trend. In contrast, when Al removal is confined to the top surface layers, a variety of feldspar configurations with different (Al, Si) disorder but a single fixed composition have similar dissolution rates; and the dissolution rate of Ca-rich feldspars departs positively from its log-linear relationship with anorthite content. This departure occurs around An80 and is in good agreement with previous experimental studies. Subsequent modeling results of aluminum inhibition, ΔG dependence, and formation of altered surface layers in the framework of the interfacial dissolution-reprecipitation mechanism are all comparable with experimental investigations, and these results suggest that an interfacial dissolution-reprecipitation mechanism governs the dissolution of plagioclase feldspars. 相似文献
16.
We compare the petrogenetic and chemical signatures of two alkali silicate suites from the Cretaceous Damaraland igneous province (Namibia), one with and one without associated carbonatite, in order to explore their differences in terms of magma source and evolution. The Etaneno complex occurs in close spatial proximity to the Kalkfeld bimodal carbonatite–alkali silicate complex, and is dominated by nepheline (ne)-monzosyenites and ne-bearing alkali feldspar syenites. The Etaneno samples have isotopic compositions of 87Sr/86Sr(i)=0.70462–0.70508 and Nd=−0.5 to −1.5, with the highest 87Sr/86Sr(i) and lowest Nd values observed in evolved samples. The magma differentiated via olivine, feldspar, clinopyroxene, and nepheline (ne) fractionation in a F-rich system, which fractionated Zr from Hf, and Y from Ho. Partly glassy, recrystallized inclusions in some samples are less evolved than their host rocks and contain a cumulate component (nepheline, plagioclase). The Kalkfeld ne-foidites (ijolites) and ne-syenites have 87Sr/86Sr(i)=0.70285–0.70592 and Nd=0.5 to 1.1. The isotope ratios show no consistent variation with rock composition, and they are in the same range as the associated carbonatites. The Kalkfeld silicate magma fractionated nepheline and alkali-feldspar in a CO2-dominated, F- and Ca-poor system. As a result, the rocks display some major and trace element trends distinctly different from those of the Etaneno samples.
We suggest that the Etaneno and the Kalkfeld magmas represent different melt fractions of a heterogeneous mantle source, resulting in different compositions especially with respect to CO2 contents of the primitive, parental magmas. In this scenario, the carbonated alkali silicate Kalkfeld parental melt contained a critical CO2 concentration and underwent liquid separation of carbonate and silicate melt fractions at crustal depths. The resulting silicate melt fraction experienced a very different mode of differentiation than the carbonate-poor Etaneno parental magma. Thus, the Kalkfeld rocks are depleted in Ca and other divalent cations, as well as F, rare-earth elements (REE), Ba, and P relative to the Etaneno syenites. We interpret these differences to reflect the partitioning of these elements into the carbonate melt fraction during immiscible separation. 相似文献
17.
《Chemical Geology》2002,182(2-4):265-273
Si adsorption onto Bacillus subtilis and Fe and Al oxide coated cells of B. subtilis was measured both as a function of pH and of bacterial concentration in suspension in order to gain insight into the mechanism of association between silica and silicate precipitates and bacterial cell walls. All experiments were conducted in undersaturated solutions with respect to silicate mineral phases in order to isolate the important adsorption reactions from precipitation kinetics effects of bacterial surfaces. The experimental results indicate that there is little association between aqueous Si and the bacterial surface, even under low pH conditions where most of the organic acid functional groups that are present on the bacterial surface are fully protonated and neutrally charged. Conversely, Fe and Al oxide coated bacteria, and Fe oxide precipitates only, all bind significant concentrations of aqueous Si over a wide range of pH conditions. Our results are consistent with those of Konhauser et al. [Geology 21 (1993) 1103; Environ. Microbiol. 60 (1994) 49] and Konhauser and Urrutia [Chem. Geol. 161 (1999) 399] in that they suggest that the association between silicate minerals and bacterial surfaces is not caused by direct Si–bacteria interactions. Rather, the association is most likely caused by the adsorption of Si onto Fe and Al oxides which are electrostatically bound to the bacterial surface. Therefore, the role of bacteria in silica and silicate mineralization is to concentrate Fe and Al through adsorption and/or precipitation reactions. Bacteria serve as bases, or perhaps templates, for Fe and Al oxide precipitation, and it is these oxide mineral surfaces (and perhaps other metal oxide surfaces as well) that are reactive with aqueous Si, forming surface complexes that are the precursors to the formation of silica and silicate minerals. 相似文献
18.
Radomir Petrović Robert A. Berner Martin B. Goldhaber 《Geochimica et cosmochimica acta》1976,40(5):537-548
Sanidine grains (100–600 μm in diameter) were subjected to dissolution at 82°C in aqueous electrolyte solutions of pH ranging from 4 to 8 for 293 or 377 hr. Dissolution equivalent to the removal of silica from the outer 300–900 A of these grains was accomplished. The shallow subsurfaces of feldspar grains were then analyzed for K, Al, and Si by X-ray photoelectron spectroscopy. The results rule out any continuous precipitate layer; if an alkali-depleted subsurface zone (leached layer) was present in the feldspar, the thickness of such a zone approximated by linear increase of alkali concentration with depth was not more than about 17 Å.It is concluded that in the absence of a compact precipitate layer, dissolution of feldspars in the temperature range corresponding to deep diagenesis is controlled by the processes at the feldspar-solution interface and a leached layer more than one feldspar unit cell thick does not form. Whether the same applies at the temperatures of shallow diagenesis and weathering cannot be judged with certainty, but parallels with leached layers on alkali silicate glasses suggest that it does. 相似文献
19.
The dissolution kinetics of a simulated lunar glass were examined at pH 3, 5, and 7. Additionally, the pH 7 experiments were conducted in the presence of citric and oxalic acid at concentrations of 2 and 20 mM. The organic acids were buffered at pH 7 to examine the effect of each molecule in their dissociated form. At pH 3, 5, and 7, the dissolution of the synthetic lunar glass was observed to proceed via a two-stage process. The first stage involved the parabolic release of Ca, Mg, Al, and Fe, and the linear release of Si. Dissolution was incongruent, creating a leached layer rich in Si and Ti which was verified by transmission electron microscopy (TEM). During the second stage the release of Ca, Mg, Al, and Fe was linear. A coupled diffusion/surface dissolution model was proposed for dissolution of the simulated lunar glass at pH 3, 5, and 7. During the first stage the initial release of mobile cations (i.e., Ca, Mg, Al, Fe) was limited by diffusion through the surface leached layer of the glass (parabolic release), while Si release was controlled by the hydrolysis of the Si-O-Al bonds at the glass surface (linear release). As dissolution continued, the mobile cations diffused from greater depths within the glass surface. A steady-state was then reached where the diffusion rate across the increased path lengths equalled the Si release rate from the surface. In the presence of the organic acids, the dissolution of the synthetic lunar glass proceeded by a one stage process. The release of Ca, Mg, Al, and Fe followed a parabolic relationship, while the release of Si was linear. The relative reactivity of the organic acids used in the experiments was citrate > oxalate. A thinner leached layer rich in Si/Ti, as compared to the pH experiments, was observed using TEM. Rate data suggest that the chemisorption of the organic anion to the surface silanol groups was responsible for enhanced dissolution in the presence of the organic acids. It is proposed that the increased rate of Si release is responsible for the one stage parabolic release of mobile cations and the relatively thin leached layer compared to experiments at pH 3 and 5. 相似文献
20.
《Geochimica et cosmochimica acta》1999,63(13-14):2043-2059
Effects of the organic acid (OA) anions, oxalate and citrate, on the solubility and dissolution kinetics of feldspars (labradorite, orthoclase, and albite) at 80°C and of quartz at 70°C were investigated at pH 6 in separate batch experiments and in media with different ionic strength (0.02–2.2 M NaCl). Although it has been shown that OAs can increase rates of feldspar dissolution, prior experiments have focused primarily on dilute, highly undersaturated and acidic conditions where feldspar dissolution kinetics are dominated by H+ adsorption and exchange reactions. Many natural waters, however, are only weakly acidic and have variable ionic strength and composition which would be expected to influence mineral surface properties and mechanisms of organic ligand-promoted reactions.Oxalate and citrate (2–20 mM) increased the rate of quartz dissolution by up to a factor of 2.5. Quartz solubility, however, was not increased appreciably by these OAs, suggesting that Si–OA complexation is not significant under these conditions. The lack of significant OA–SiO2 interaction is important to understanding the effects of OAs on the release of both Si and Al from feldspars. In contrast to quartz, both the rates of dissolution and amounts of Si and Al released from the three feldspars studied increased regularly with increasing OA concentration. Feldspar dissolution was congruent at all but the lowest OA concentrations. Total dissolved Al concentrations increased by 1–2 orders of magnitude in the presence of oxalate and citrate, and reached values as high as 43 mg/l (1.6 mM). Si concentrations reached values up to 65 mg/l (2.3 mM) in feldspar–OA experiments. Precipitation of authigenic clays was observed only in experiments without or at very low concentrations of OAs. The high concentrations of dissolved Si attained during dissolution of feldspars in OA solutions, relative to Si concentrations in quartz–OA experiments, is attributed to concomitant release of Si driven by strong Al–OA interactions.Modeling of the dependence of feldspar dissolution rates on OA concentration in natural diagenetic environments is complicated by the competing effects of overall solution chemistry and ionic strength on the dissolution mechanism. Results of experiments using labradorite (An70) indicate that in OA-free solutions, dissolution is progressively slower at increasing NaCl concentrations (up to 2.2 M), in agreement with prior experiments on the effects of alkali metals on feldspar dissolution. The combined effects of oxalate and NaCl on labradorite dissolution rates are such that the rate increase due to oxalate is suppressed by the addition of NaCl. Thus, feldspar dissolution kinetics should be most significantly affected by a given concentration of OAs in low ionic strength solutions. 相似文献