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1.
2.
《Applied Geochemistry》1998,13(7):905-916
Experiments measuring kaolinite and smectite dissolution rates were carried out using batch reactors at 35° and 80°C. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of clay of the ≤2 μm fraction and 80, 160 or 240 ml of 0.1–4 M KOH solution. An untreated but sized kaolinite from St. Austell and two treated industrial smectites were used in the experiments. One smectite is a nearly pure montmorillonite, while the second has a significant component of beidellitic charge (35%). The change in solution composition and mineralogy was monitored as a function of time. Initially, the 3 clays dissolved congruently. No new formed phases were observed by XRD and SEM during the pure dissolution stage. The kaolinite dissolution is characterized by a linear release of silica and Al as a function of the log of time. This relationship can be explained by a reaction affinity effect which is controlled by the octahedral layer dissolution. Far from equilibrium, dissolution rates are proportional to a0.56±0.12OH− at 35°C and to a0.81±0.12OH− at 80°C. The activation energy of kaolinite dissolution increases from 33±8 kJ/mol in 0.1 M KOH solutions to 51±8 kJ/mol in 3 M KOH solutions. In contrast to kaolinite, the smectites dissolve at much lower rates and independently of the aqueous silica or Al concentrations. The proportionality of the smectite dissolution rate constant at 35 and 80°C was a0.15±0.06OH−. The activation energy of dissolution appears to be independent of pH for smectite and is found to be 52±4 kJ/mol. The differences in behavior between the two kinds of minerals can be explained by structural differences. The hydrolysis of the tetrahedral and the octahedral layer appears as parallel reactions for kaolinite dissolution and as serial reactions for smectite dissolution. The rate limiting step is the dissolution of the octahedral layer in the case of kaolinite, and the tetrahedral layer in the case of smectite. 相似文献
3.
Cobalt, like Mg, may cause the precipitation of aragonite rather than calcite in aqueous solutions due to the adsorption and crystal poisoning of calcite by a hydrated ion. Solutions containing NaCl and CaCl2, having the ionic strength and Ca content of seawater (35‰ salinity), were spiked with known amounts of CoCl2. Calcium carbonate was precipitated by the addition of 0.7 ml of 1 M Na2CO3. All experimental runs were made at 25°C, and all products were examined by X-ray diffraction. At low concentrations of Co (< 5·?4M) calcite and vaterite formed. At concentrations from 5·10?4 M to 2·10?3M, the products consisted of combinations of calcite and vaterite; aragonite and calcite; aragonite and vaterite; calcite, vaterite and aragonite. In solutions of 3·10?3M CoCl2, most precipitates were aragonite with only one sample containing a small amount of calcite. All precipitates from 5·10?3M CoCl2 solutions either contained aragonite or were amorphous. Solutions with concentrations of 1 · 10?2M CoCl2 produced only amorphous precipitates. All precipitates contained an amorphous violet phase, assumed to be basic cobaltous carbonate (2CoCO3·Co(OH)2·H2O). 相似文献
4.
The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H2SO4 solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites. 相似文献
5.
《Geochimica et cosmochimica acta》1999,63(19-20):3261-3275
Studies on the dissolution kinetics of kaolinite were performed using batch reactors at 25°C and in the pH range from 1 to 13. A rapid initial dissolution step was first observed, followed by a linear kinetic stage reached after approximately 600 hr of reaction during which the kaolinite dissolves congruently at pH < 4 and pH > 11. The apparent incongruency between pH 5 and 10 was due to the precipitation of an Al–hydroxide phase. The true dissolution rates were computed from the amount of Si released into solution. The rate dependence on pH can be described by: r = 10−12.19aH+0.55 + 10−14.36 + 10−10.71aOH−0.75Between pH 5 and 10, the rate is approximately constant, although a smooth minimum was observed at pH close to 9. mAn attempt was made to obtain a general rate law based on the coordination theory, which was first applied to the mineral dissolution studies by Stumm and co-workers. The kinetic data were combined with the results obtained for the surface speciation by Huertas et al. (1998). It is possible to express the linear dissolution rate as a simple power function of the concentration of the surface sites active in various pH ranges: r = 10−8.25 [>Al2OH2+] + 10−10.82 [>AlOH2+]0.5 + 10−9.1 [>Al2OH + >AlOH + >SiOH] + 103.78 [>Al2O− + >AlO−]3This equation assumes that the dissolution mechanism is mainly controlled by the two Al surface sites (external and internal structural hydroxyls, and aluminol at the crystal edges) under both acidic and alkaline conditions. The model reflects well the important contribution of the crystal basal planes to the dissolution of kaolinite. 相似文献
6.
In order to evaluate the extent of CO2–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO2–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔGr relationship can overestimate the extent of feldspar dissolution during CO2 storage. Finally, the literature on feldspar dissolution in CO2-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral information at CO2 storage conditions. 相似文献
7.
Summary The hydrothermal synthesis of kaolinite from various alumina and silica starting materials reacted at 200°C in aqueous solutions of oxalic acid and H2SO4 with the corresponding saturated water vapour pressure, in periods of time from 10 to 25 days, has been followed by X-ray diffraction measurements, scanning electron microscopy, and energy dispersive analysis of the products. The temperature and time periods of reactions were chosen on the basis of previously collected data on the effects of H4EDTA, a complex-forming agent, and of H2SO4, an inorganic acid, on the rate of formation of kaolinite. Aluminium-complexing acids increase the rate of formation or decrease the temperature of formation of kaolinite as shown by evidence from X-ray diffraction patterns. The influence of the starting materials as sources of aluminum, amorphous aluminum hydroxides, pseudoboehmite, allophane or gibbsite, has also been examined by X-ray diffraction, scanning electron microscopy, and by energy dispersive analysis. Scanning electron micrographs indicated that silica is a more mobile phase than alumina, based on the progressive formation of a thin coating on gibbsite during early reaction, then by growth of clusters of platy crystals of kaolin, and finally by production of pellets of stacked crystal flakes. Where gibbsite was used in the reaction mixture, boehmite was commonly observed as an intermediate phase.With 16 Figures 相似文献
8.
《Applied Geochemistry》1998,13(5):619-629
Experiments measuring kaolinite dissolution and recrystallisation rates in KOH solutions were carried out using a batch reactor at 35° and 80°C. An untreated, sized kaolinite from St. Austell was used. No potential catalysts or inhibitors were present in solution. Each reactor was charged with 1 g of kaolinite of the ≤2 μm fraction and 80, 160, 240 ml of 0.1–4 m KOH solution. In these experiments the solution composition and mineralogy were monitored as a function of time for up to one year. A dissolution dominant stage was followed by a precipitation dominant period. The dissolution is not linear as a function of time but linear as a function of (log) time. This apparent relationship is explained by an affinity effect (approach to equilibrium).Under these high pH conditions, the sequence of reaction products observed is: illite, followed by KI-zeolite, phillipsite and finally by the stable product K-feldspar precipitation. The point in time at which crystallisation controls the concentration of Al and Si in solution and the persistence of the various metastable phases is temperature dependent.Concerning the stability of clay barriers in an alkaline solution context, low temperatures allow more material to enter solution before the crystallisation of metastable phases controls the solution composition. Also at low temperatures the dissolution phase continues for longer periods of time. Hence, low temperatures favour an actively aggressive solution (dissolving clays). 相似文献
9.
The reaction between plagioclase (labradorite and oligoclase) and Mg-rich aqueous solutions was studied experimentally at hydrothermal conditions (600–700 °C, 2 kbar). During the experiments, plagioclase grains were readily converted to cordierite and quartz within 4 days. The cordierite crystals had well-developed polyhedral shapes, but showed skeletal internal morphologies suggesting that the initial growth occurred fast under high-driving-force conditions. In pure MgCl2 solutions (0.5–5 M), plagioclase dissolution and cordierite precipitation were spatially uncoupled indicating that Al was to some extent mobile in the fluid. Cordierite crystals formed at 700 °C showed orthorhombic symmetry, whereas those formed at 600 °C dominantly persisted in the metastable hexagonal form suggesting a strong increase in Al, Si ordering speed between 600 and 700 °C. The thermodynamic evolution of the fluid–solid system ultimately resulted in stabilization of Ca-rich plagioclase as demonstrated by partial anorthitization of unreacted plagioclase grains. Cordierite was also observed to form when Mg was added to a potentially albitizing Na-silicate-bearing solution. In that case, cordierite precipitation appeared to be more closely coupled to plagioclase dissolution, and secondary alteration of remnant plagioclase grains did not occur most likely due to armoring of the plagioclase by the cordierite overgrowth. The fast reaction rates observed in our experimental study have potential implications for Mg-metasomatism as a rock-forming process. 相似文献
10.
Natural and constructed clay liners are routinely used to contain waste and wastewater. The impact of acidic solutions on the geochemistry and mineralogy of clays has been widely investigated in relation to acid mine drainage systems at pH > 1.0. The impact of H2SO4 leachate characterized by pH < 1.0 and potentially negative pH values on the geochemistry and mineralogy of clays is, however, not clear. Thus, laboratory batch experiments were conducted on three natural clay samples with different mass ratios of smectite, illite and kaolinite to investigate the impact of H2SO4 on the geochemistry and mineralogy of aluminosilicates from pH 5.0 to −3.0. Batch testing was conducted at seven pH treatments (5.0, 3.0, 1.0, 0.0, −1.0, −2.0 and −3.0) using standardized H2SO4 solutions for four exposure periods (14, 90, 180, and 365 d). Aqueous geochemical and XRD analyses showed: increased dissolution of aluminosilicates with decreasing pH and increasing exposure period, that smectite was more susceptible to dissolution than illite and kaolinite, precipitation of an amorphous silica phase occurred at pH ? 0.0, and anhydrite precipitated in Ca-rich clays at pH ? −1.0. In addition, global dissolution rates were calculated for the clays and showed good agreement to literature smectite, illite and kaolinite dissolution rates, which suggests global dissolution rates for complex clays could be determined from monomineralic studies. A stepwise conceptual model of the impact of H2SO4 on aluminosilicate geochemistry and mineralogy between pH 5.0 and −3.0 is proposed. 相似文献
11.
《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
12.
Nishi Rani J. P. Shrivastava R. K. Bajpai 《Journal of the Geological Society of India》2012,79(4):376-382
Obsidian glass alteration experiments under near hydrothermal conditions were performed to study mechanism and conditions of formation of altered minerals. X-ray diffraction patterns and cell dimensions of the specimens treated at 150, 200 and 300°C (pH = 8.03) revealed appearance of three main minerals — illite (9.5–10 Å), chlorite (7.04 Å) and halloysite (10.25Å). Further increase in the pH favours matrix dissolution with the formation of secondary altered layers. SEM-EDS study show that the alteration causes smoothing of the grain surfaces. These surfaces exhibits etch pits and series of depressions, formed by the process of dissolution. SEM — Back Scattered Electron images of obsidian specimens show thin laminae of smectite, with foliated bulky rims and cellular honeycomb texture, formed by precipitation from the solution as well as by direct transformation of glass during alteration. This mechanism is resulting from the alteration of alkalis by ionic inter-diffusion with H3O+ and H+ and inward diffusion of H2O, leading to free diffusion of silica into solution and then to a local rearrangement of the glass framework. Thus, a direct transformation of glass into clay minerals is the major reaction mechanism as evidenced by the mechanism of glass dissolution and subsequent mineral precipitation. 相似文献
13.
Speciation of aqueous calcium chloride and the solubility of wollastonite represented by the reaction wollastonite + 2HCl° → CaCl2° + quartz + H2O were experimentally investigated at 1 and 2 kbar in the range 425–600°C using rapid-quench hydrothermal techniques and a modified Ag + AgCl buffer technique (Frantz and Popp, 1979). Variation in the measured concentration in HCl° as a function of total dissolved calcium was used to identify associated aqueous CaCl2° as the predominant calcium species in the fluid at temperatures above 500°C at 2 kbar. The data were used to calculate the equilibrium constant for the above reaction as a function of temperature and pressure, from which the difference in Gibbs free energy of formation between CaCl2° and HCl° at 1 and 2 kbar, 450°–600°C was calculated. Solubility constants for minerals in the system MgO-CaO-SiO2-H2O-HCl-CO2 were calculated using the data from this study and from Frantz and Popp (1979). Calculated mineral solubilities were used to calculate the solution compositions and solid alteration products resulting from interactions of a Ca-Mg silicate mineral (diopside) with hydrothermal solutions containing a range of different total chloride concentrations. High total chloride (2.0 m) in the solution results in Si-Mg enrichment in the solids and Ca enrichment in the fluid, whereas low total chloride (0.008 m) results in Mg enrichment in the solids and Ca-Si enrichment in the fluid. 相似文献
14.
The effects of organic acids on the dissolution of silicate minerals: A case study of oxalate catalysis of kaolinite dissolution 总被引：1，自引：0，他引：1
Jordi Cama 《Geochimica et cosmochimica acta》2006,70(9):2191-2209
Most studies agree that the dissolution rate of aluminosilicates in the presence of oxalic and other simple carboxylic acids is faster than the rate with non-organic acid under the same pH. However, the mechanisms by which organic ligands enhance the dissolution of minerals are in debate. The main goal of this paper was to study the mechanism that controls the dissolution rate of kaolinite in the presence of oxalate under far from equilibrium conditions (−29 < ΔGr < −18 kcal mol−1). Two types of experiments were performed: non-stirred flow-through dissolution experiments and batch type adsorption isotherms. All the experiments were conducted at pH 2.5-3.5 in a thermostatic water-bath held at a constant temperature of 25.0, 50.0 or 70.0 ± 0.1 °C. Kaolinite dissolution rates were obtained based on the release of silicon and aluminum at steady state. The results show good agreement between these two estimates of kaolinite dissolution rate. At constant temperature, there is a general trend of increase in the overall dissolution rate as a function of the total concentration of oxalate in solution. The overall kaolinite dissolution rates in the presence of oxalate was up to 30 times faster than the dissolution rate of kaolinite at the same temperature and pH without oxalate as was observed in our previous study. Therefore, these rate differences are related to differences in oxalate and aluminum concentrations. Within the experimental variability, the oxalate adsorption at 25, 50, and 70 °C showed the same dependence on the sum of the activities of oxalate and bioxalate in solution. The change of oxalate concentration on the kaolinite surface (Cs,ox) as a function of the sum of the activities of the oxalate and bioxalate in solution may be described by the general adsorption isotherm:
15.
Dolomite (CaMg(CO3)2) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis. 相似文献
16.
《Applied Geochemistry》2000,15(3):265-279
The conditions for mineral alteration and formation damage during CO2 treatment of Tensleep sandstone reservoirs in northern Wyoming, USA, were examined through core-flooding laboratory experiments carried out under simulated reservoir conditions (80°C and 166 bars). Subsurface cores from the Tensleep sandstone, which were cemented by dolomite and anhydrite, and synthetic brines were used. The brines used were (Ca, Mg, Na)SO4–NaCl solution (9.69 g/l total dissolved solids) for Run 1 and a 0.25 mol/l NaCl solution for Run 2. The solution used in Run 1 was saturated with respect to anhydrite at run conditions, which is characteristic of Tensleep Formation waters.Three major reactions took place during flooding, including (1) dissolution of dolomite, (2) alteration of K-feldspar to form kaolinite, and (3) precipitation (in Run 1) or dissolution (in Run 2) of anhydrite. All sample solutions remained undersaturated with respect to carbonates. The permeability of all the cores (except one used in Run 2) decreased during the experiments despite the dissolution of authigenic cement. Kaolinite crystal growth occurring in pore throats likely reduced the permeability.Application of the experimental results to reservoirs in the Tensleep Formation indicates that an injection solution will obtain saturation with respect to dolomite (and anhydrite) in the immediate vicinity of the injection well. The injection of NaCl-type water, which can be obtained from other formations, causes a greater increase in porosity than the injection of Tensleep Formation waters because of the dissolution of both dolomite and anhydrite cements. 相似文献
17.
Jacques Schott Robert A Berner E.Lennart Sjöberg 《Geochimica et cosmochimica acta》1981,45(11):2123-2135
The short term (2–40 days) dissolution of enstatite, diopside, and tremolite in aqueous solution at low temperatures (20–60°C) and pH 1–6 has been studied in the laboratory by means of chemical analyses of reacting solutions for Ca2+, Mg2+, and Si(OH)4 and by the use of X-ray photoelectron spectroscopy (XPS) for detecting changes in surface chemistry of the minerals. All three minerals were found to release silica at a constant rate (linear kinetics) providing that ultrafine particles, produced by grinding, were removed initially by HF treatment. All three also underwent incongruent dissolution with preferential release of Ca and/or Mg relative to Si from their outermost surfaces. The preferential release of Ca, but not Mg for diopside at pH 6 was found by both XPS and solution chemistry verifying the theoretical prediction of greater mobility of cations located in M2 structural sites. Loss mainly from M2 sites also explains the degree of preferential loss of Mg from enstatite at pH 6; similar structural arguments apply to the loss of Ca and Mg from the surface of tremolite. In the case of diopside and tremolite initial incongruency was followed by essentially congruent cation-plus-silica dissolution indicating rapid formation of a constant-thickness, cation-depleted surface layer. Cation depletion at elevated temperature and low pH (~ 1) for enstatite and diopside was much greater than at low temperature and neutral pH, and continued reaction resulted in the formation of a surface precipitate of pure silica as indicated by solubility calculations, XPS analyses, and scanning electron microscopy.From XPS results at pH 6, model calculations indicate a cation-depleted altered surface layer of only a few atoms thickness in all three minerals. Also, lack of shifts in XPS peak energies for Si, Ca, and Mg, along with undersaturation of solutions with respect to all known Mg and Ca silicate minerals, suggest that cation depletion results from the substitution of hydrogen ion for Ca2+ and/or Mg2+ in a modified silicate structure and not from the precipitation of a new, radically different surface phase. These results, combined with findings of high activation energies for dissolution, a non-linear dependence on aH+ for silica release from enstatite and diopside, and the occurrence of etch pitting, all point to surface chemical reaction and not bulk diffusion (either in solution or through altered surface layers) as the rate controlling mechanism of iron-free pyroxene and amphibole dissolution at earth surface temperatures. 相似文献
18.
A study of the pattern of dissolution of synthetic and natural Fe oxides in 6 M HCl indicates that the rate of element release from synthetic Fe oxides is strongly influenced by mineralogy and the level of element incorporation. Synthetic maghemite (γ-Fe2O3) samples are subject to much more rapid dissolution than goethite (FeOOH) and hematite (α-Fe2O3). In samples dominated by hematite and maghemite, Cu, Zn and particularly Pb, in comparison to Fe, are preferentially released during the early stages of dissolution. Similar patterns are apparent from the dissolution of hematite- and maghemite-dominated samples derived from natural gossan. Comparison of XRD scans with data from the dissolution of natural gossan samples transformed by incremental heating to hematite- and maghemite-dominated assemblages suggests that the degree of crystallinity may also be a significant factor in the release of elements incorporated in the Fe oxides. Ferruginous materials made up of varying proportions of goethite, hematite, maghemite, kaolinite and quartz are important sampling materials in a range of regolith environments. These are products of complex chemical and mechanical mobilization over long periods of geological time. If the patterns of Fe oxide dissolution in 6 M HCl and the release of incorporated metals reflect stability in such weathering regimes, knowledge of the retention characteristics of incorporated metals in different Fe oxide phases, as indicated by this study, will be useful in the planning and interpretation of geochemical surveys in such regions. 相似文献
19.
The surface of arsenopyrite was characterized after acidic, oxidative leaching in the presence of the bacterial species Thiobacillus ferrooxidans. Polished single-crystal grains of arsenopyrite were reacted for 1, 2, and 3 weeks with T. ferrooxidans suspended in a solution (pH 2.3) of essential salts (MgSO4·7H2O, [NH4]2SO4, KH2PO4, and KCl). Abiotic control experiments were conducted in identical solutions. Reaction between arsenopyrite and T. ferrooxidans in the essential salts solution produced a uniform solid FePO4 overlayer (∼0.2 μm thick) on the arsenopyrite surface within 1 week. The overlayer was detected visually by scanning electron microscopy (SEM) and chemically by X-ray photoelectron spectroscopy (XPS). It could not be distinguished by energy-dispersive X-ray analyses. No overlayer formed in the abiotic control. The uniform thickness and lateral continuity of the overlayer suggest an inorganic origin promoted by bacterial production of Fe3+. Iron released from arsenopyrite was oxidized by bacteria and subsequently precipitated with PO43− (from the essential salts), forming ferric phosphate. After 2 and 3 weeks, SEM images revealed a roughened arsenopyrite surface, and XPS depth profiles indicated a progressively thicker phosphate overlayer and continued oxidation, diffusion, and dissolution of arsenopyrite beneath the overlayer. After only 1 week, the cells were isolated from the arsenopyrite surface by the uniform overlayer. Therefore, bacteria need not be attached to arsenopyrite to promote rapid reaction, and the mechanism of alteration at the arsenopyrite surface must have been inorganic. Because the delicate overlayer did not prevent continued alteration of arsenopyrite, FePO4 may not be an effective barrier to oxidation in the tailings environment. The FePO4 coating has likely formed in other experiments using these bacteria but was not detected because analytical techniques were not sufficiently surface sensitive to identify a separate, compositionally distinct overlayer. Some previous experimental results thus may be misleading or inapplicable to the tailings environment. 相似文献
20.
N. I. Kovalenko B. N. Ryzhenko N. I. Prisyagina Ya. V. Bychkova 《Geochemistry International》2011,49(3):262-273
Uraninite solubility in 0.001–2.0 m HCl solutions was experimentally studied at 500°C, 1000 bar, and hydrogen fugacity corresponding to the Ni/NiO buffer. It
was shown that the following U(IV) species dominate in the aqueous solution: U(OH)40, U(OH)2Cl20, and UOH Cl30 Using the results of uraninite solubility measurement, the Gibbs free energies of U(IV) species at 500°C and 1000 bar were
calculated (kJ/mol): −9865.55 for UO2(aq), −1374.57 for U(OH)2 Cl20, and −1265.49 for UOH Cl30, and the equilibrium constants of uraninite dissolution in water and aqueous HCl solutions were estimated: UO2(cr) = UO2(aq), pK
0 = 6.64; UO2(cr) + 2HCl0 = U(OH)2 Cl20, pK
2 = 3.56; and UO2(cr) + 3HCl0 = UOHcl30 + H2O, pK
3 = 3.05. The value pK
1 ≈ 5.0 was obtained as a first approximation for the equilibrium UO2(cr) + H2O + HCl0 = U(OH)3Cl0. The constant of the reaction UO2(cr) + 4HCl0 = UCl40 + 2H2O (pK
4 = 7.02) was calculated taking into account the ionization constants of U Cl40 and U(OH)40, obtained by extrapolation from 25 to 500°C at 1000 bar using the BR model. Intense dissolution and redeposition of gold
(material of experimental capsules) was observed in our experiments. The analysis and modeling of this phenomenon suggested
that the UO2 + x
/UO2 redox pair oxidized Au(cr) to Au+(aq), which was then reduced under the influence of stronger reducers. 相似文献