The dissolution rates of gibbsite in the presence of chloride, nitrate, silica, sulfate, and citrate in open and closed systems at 20°C     

M. Dietzel  G. Böhme 《Geochimica et cosmochimica acta》2005,69(5):1199-1211

The dissolution of well crystallized gibbsite far at from equilibrium was studied in batch and mixed flow through reactors. The dissolution experiments were carried out between pH 2 and 6 in the presence of 10 mmol L⁻¹ citrate, at pH 2 and 3 in the presence of 10 mmol L⁻¹ chloride, nitrate, and sulfate, and at pH 2 and 3 in the presence of 1.5 mmol L⁻¹ silica at 20°C. The dissolution rate of gibbsite, R_Al (mol m⁻² s⁻¹), increases in the order of chloride ≈ nitrate < silica < sulfate ≈ citrate. In presence of silica, sulphate, and citrate dissolution is catalysed by the formation of aluminium complexes at the gibbsite surface (pH 2 and 3). From pH 2 to 3 no effect of R_Al on hydrogen activity is predicted as singly coordinated surface sites at the edges of the platy gibbsite crystals, [≡AlOH₂^+0.5] ≈ [≡AlOH], are almost saturated with protons. However at pH >3 dissolution is slowed by a decrease of [≡AlOH₂^+0.5].Gibbsite dissolution rates measured in closed and open systems were identical within the experimental and analytical uncertainty. This observation indicates that gibbsite dissolution is a surface controlled process. If dissolution of gibbsite occurs close to equilibrium R_Al values may be predicted by an approximately linear function of ΔG_r.  相似文献   

Role of molecular oxygen in the dissolution of siderite and rhodochrosite     

Owen W Duckworth 《Geochimica et cosmochimica acta》2004,68(3):607-621

The dissolution of siderite (FeCO₃) and rhodochrosite (MnCO₃) under oxic and anoxic conditions is investigated at 298 K. The anoxic dissolution rate of siderite is 10^−8.65 mol m⁻² s⁻¹ for 5.5 < pH < 12 and increases as [H⁺]^0.75 for pH < 5.5. The pH dependence is consistent with parallel proton-promoted and water hydrolysis dissolution pathways. Atomic force microscopy (AFM) reveals a change in pit morphology from rhombohedral pits for pH > 4 to pits elongated at one vertex for pH < 4. Under oxic conditions the dissolution rate decreases to below the detection limit of 10⁻¹⁰ mol m⁻² s⁻¹ for 6.0 < pH < 10.3, and hillock precipitation preferential to steps is observed in concurrent AFM micrographs. X-ray photoelectron spectroscopy (XPS) and thermodynamic analysis identify the precipitate as ferrihydrite. At pH > 10.3, the oxic dissolution rate is as high as 10^−7.5 mol m⁻² s⁻¹, which is greater than under the corresponding anoxic conditions. A fast electron transfer reaction between solution O₂ or [Fe³⁺(OH)₄]⁻ species and surficial >Fe^II hydroxyl groups is hypothesized to explain the dissolution kinetics. AFM micrographs do not show precipitation under these conditions. Anoxic dissolution of rhodochrosite is physically observed as rhombohedral pit expansion for 3.7 < pH < 10.3 and is chemically explained by parallel proton- and water-promoted pathways. The dissolution rate law is 10^−4.93[H⁺] + 10^−8.45 mol m⁻² s⁻¹. For 5.8 < pH < 7.7 under oxic conditions, the AFM micrographs show a tabular precipitate growing by preferential expansion along the a-axis, though the macroscopic dissolution rate is apparently unaffected. For pH > 7.7 under oxic conditions, the dissolution rate decreases from 10^−8.45 to 10^−9.0 mol m⁻² s⁻¹. Flattened hillock precipitates grow across the entire surface without apparent morphological influence by the underlying rhodochrosite surface. XPS spectra and thermodynamic calculations implicate the precipitate as bixbyite for 5.8 < pH < 7.7 and MnOOH (possibly feitnkechtite) for pH >7.7.  相似文献   

Kaolinite and smectite dissolution rate in high molar KOH solutions at 35° and 80°C     

《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 a^0.56±0.12_OH⁻ at 35°C and to a^0.81±0.12_OH⁻ 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 a^0.15±0.06_OH⁻. 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   

Theoretical reaction pathways for the formation of [Si(OH)5]1− and the deprotonation of orthosilicic acid in basic solution     

《Geochimica et cosmochimica acta》1993,57(16):3847-3853

Ab initio, molecular orbital calculations at the 6-31G¹ level including second-order Møller-Plesset electron correlation predict that the species [Si(OH)₅]¹⁻ is dynamically stable in a distorted trigonal bipyramid configuration. Reaction pathways for Si(OH)₄ + (OH)⁻ → [Si(OH)₅]¹⁻ → [(OH)₃SiO]¹⁻—H₂O are also calculated. The first reaction represents the formation of pentacoordinate Si from orthosilicic acid and hydroxide. The activation energy for adding a fifth Si-(OH)⁻ bond to the Si(OH)₄ molecule is ≈0.1 eV /molec (≈10kJ/mol). The second reaction is the deprotonation of the Si(OH)₄ which forms as a hydroxyl group leaves the [Si(OH)₅]¹⁻ molecule. Removal of a bond from this complex requires 0.9 eV/molecule (≈85 kJ/mol). Lengthening the Si—OH₂ distance results in the isolated molecules [(OH)₃SiO]¹⁻ + H₂O. This represents dehydration of the deprotonated orthosilicic acid.[Si(OH)₅]¹⁻ and [(OH)₃SiO]¹⁻- H₂O have the same energetic stability within the accuracy of these calculations. The potential energies of the isolated molecular systems [(OH)₃SiO]¹⁻+ H₂O and Si(OH)₄ + (OH)⁻ are considerably higher. These results suggest that [Si(OH)₅]¹⁻ may be a stable species or reaction intermediate in dissolution of silicate minerals in basic aqueous solutions.  相似文献   

Dissolution of illite in saline-acidic solutions at 25 °C     

Irshad Bibi  Ewen Silvester 《Geochimica et cosmochimica acta》2011,75(11):3237-3249

The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K_1.38Na_0.05)(Al_2.87Mg_0.46Fe³⁺_0.39Fe²⁺_0.28Ti_0.07)[Si_7.02Al_0.98]O₂₀(OH)₄ was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H₂SO₄) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K⁺ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na⁺ from the solution and K⁺ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower R_Al (dissolution rate calculated from steady state Al release) than R_Si (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

Connections between surface complexation and geometric models of mineral dissolution investigated for rhodochrosite     

Owen W Duckworth 《Geochimica et cosmochimica acta》2003,67(10):1787-1801

Mineral dissolution rates have been rationalized in the literature by surface complexation models (SCM) and morphological and geometric models (GM), and reconciliation of these conceptually different yet separately highly successful models is an important goal. In the current work, morphological alterations of the surface are observed in real time at the microscopic level by atomic force microscopy (AFM) while dissolution rates are simultaneously measured at the macroscopic level by utilizing the AFM fluid cell as a classic flow-through reactor. Rhodochrosite dissolution is studied from pH = 2 to 11 at 298 K, and quantitative agreement is found between the dissolution rates determined from microscopic and macroscopic observations. Application of a SCM model for the interpretation of the kinetic data indicates that the surface concentration of >CO₃H regulates dissolution for pH < 7 while the surface concentration of >MnOH₂⁺ regulates dissolution for pH > 7. A GM model explains well the microscopic observations, from which it is apparent that dissolution occurs at steps associated with anisotropic pit expansion. On the basis of the observations, we combine the SCM and GM models to propose a step-site surface complexation model (SSCM), in which the dissolution rates are quantitatively related to the surface chemical speciation of steps. The governing SSCM equation is as follows: R = χ_1/2(k_co + k_ca)[>CO₃H] + χ_1/2(k_mo + k_ma)[>MnOH₂⁺ ], where R is the dissolution rate (mol m⁻² s⁻¹), 2χ_1/2 is the fraction of surface sites located at steps, [>CO₃H] and [>MnOH₂⁺ ] are surface concentrations (mol m⁻²), and k_co, k_ca, k_mo, and k_ma are the respective dissolution rate coefficients (s⁻¹) for the >CO₃H and the >MnOH₂⁺ surface species on obtuse and acute steps. We find k_co = 2.7 s⁻¹, k_ca = 2.1 × 10⁻¹ s⁻¹, k_mo = 4.1 × 10⁻² s⁻¹, k_ma = 3.7 × 10⁻² s⁻¹, and χ_1/2 = 0.015 ± 0.005. The rate coefficients quantify the net result of complex surface step processes, including double-kink initiation and single-kink propagation. We propose that the SSCM model may have general applicability for dissolution far from equilibrium of flat mineral surfaces of ionic crystals, at least those that dissolve by step retreat.  相似文献   

Dissolution kinetics of galena in acid NaCl solutions at 25—75 °C     

《Applied Geochemistry》2004,19(6):835-841

Experiments on dissolution kinetics of galena were performed in 1 mol l⁻¹ NaCl solutions at pH 0.43–2.45 and 25–75 °C. When the dissolution reaction is far from equilibrium, a linear relation exits between the dissolution rate, r, and the H⁺ ion activity, [H⁺]. The rate law for galena dissolution is given by the following equation: r=k[H⁺]. With respect to H⁺, the dissolution reaction is in the first order. The apparent rate constant, k, has values of 2.34×10⁻⁷ mol m⁻² s⁻¹ at 25 °C, 1.38×10⁻⁶ mol m⁻² s⁻¹ at 50 °C, and 7.08×10⁻⁶ mol m⁻² s⁻¹ at 75 °C. The activation energy of dissolution reaction is 43.54 kJ mol⁻¹. The mechanism of dissolution is suggested to be surface chemical reaction, and the rate determining step is the dissociation of the Pb–S bond of the surface complex, which releases Pb²⁺ into the solution.  相似文献   

On the Stability of the <Emphasis Type="Italic">AlOSi</Emphasis>(<Emphasis Type="Italic">OH</Emphasis>)<Stack><Subscript>3</Subscript><Superscript>2+</Superscript></Stack> Complex in Aqueous Solution     

Lorenzo?SpadiniEmail author  Paul?W.?Schindler  Staffan?Sj?berg 《Aquatic Geochemistry》2005,11(1):21-31

Summary The complexation of aluminium(III) and silicon(IV) was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25 °C. The measurements were performed as potentiometric titrations using a hydrogen electrode with OH ⁻ ions being generated coulometrically. The total concentrations of Si(IV) and Al(III) respectively [Si _tot ] and [Al _t ot], and −log[H ⁺] were varied within the limits 0.3 < [Si _tot ] < 2.5 mM, 0.5 < [Al _tot ] < 2.6 mM, and 2 ≤ -log[H ⁺] ≤ 4.2. Within these ranges of concentration, evidence is given for the formation of an AlSiO(OH) ₃ ²⁺ complex with a formation constant log β_1,1-1 = −2.75 ± 0.1 defined by the reaction Al ³⁺+Si (OH)₄ ↔ AlOSi(OH) ₃ ²⁺ +H ⁺ An extrapolation of this value to I=0 gives log β_1,1-1 = −2.30. The calculated value of log K (Al ³⁺+SiO(OH) ₃ ⁻ ↔ AlOSi(OH) ₃ ²⁺ ) = 6.72 (I=0.6 M) can be compared with corresponding constants for the formation of AlF ²⁺ and AlOH ²⁺ , which are equal to 6.16 and 8.20. Obviously, the stability of these Al(III) complexes decreases within the series OH ⁻>SiO(OH) ₃ ⁻  > F ⁻  相似文献   

Dolomite surface speciation and reactivity in aquatic systems     

《Geochimica et cosmochimica acta》1999,63(19-20):3133-3143

  相似文献   

Solubility of Ca6[Al(OH)6]2(CrO4)3·26H2O,the chromate analog of ettringite; 5–75°C     

《Applied Geochemistry》2000,15(8):1203-1218

Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O, the chromate analog of the sulfate mineral ettringite, was synthesized and characterized by X-ray diffraction, Fourier transform infra-red spectroscopy, thermogravimetric analyses, energy dispersive X-ray spectrometry, and bulk chemical analyses. The solubility of the synthesized solid was measured in a series of dissolution and precipitation experiments conducted at 5–75°C and at initial pH values between 10.5 and 12.5. The ion activity product (IAP) for the reaction Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O⇌6Ca²⁺+2Al(OH)⁻₄+3CrO²⁻₄+4OH⁻+26H₂O varies with pH unless a CaCrO_4(aq) complex is included in the speciation model. The log K for the formation of this complex by the reaction Ca²⁺+CrO²⁻₄=CaCrO_4(aq) was obtained by minimizing the variance in the IAP for Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O. There is no significant trend in the formation constant with temperature and the average log K is 2.77±0.16 over the temperature range 5–75°C. The log solubility product (log K_SP) of Ca₆[Al(OH)₆]₂(CrO₄)₃·26H₂O at 25°C is −41.46±0.30. The temperature dependence of the log K_SP is log K_SP=A−B/T+D log(T) where A=498.94±48.99, B=27,499±2257, and D=−181.11±16.74. The values of ΔG⁰_r,298 and ΔH⁰_r,298 for the dissolution reaction are 236.6±3.9 and 77.5±2.4 kJ mol⁻¹. the values of ΔC⁰_P,r,298 and ΔS⁰_r,298 are −1506±140 and −534±83 J mol⁻¹ K⁻¹. Using these values and published standard state partial molal quantities for constituent ions, ΔG⁰_f,298=−15,131±19 kJ mol⁻¹, ΔH⁰_f,298=−17,330±8.6 kJ mol⁻¹, ΔS⁰₂₉₈=2.19±0.10 kJ mol⁻¹ K⁻¹, and ΔC⁰_Pf,298=2.12±0.53 kJ mol⁻¹ K⁻¹, were calculated.  相似文献   

Quantification of drying induced acidity at the mineral-water interface using ATR-FTIR spectroscopy     

C.E. Clarke  J. Aguilar-Carrillo  A.N. Roychoudhury 《Geochimica et cosmochimica acta》2011,75(17):4846-4856

Drying induced pH changes were quantified on the surface of Na⁺, Ca²⁺, Mg²⁺ and Al³⁺ saturated smectite and kaolinite clays. This was achieved using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to measure real time changes to a pH indicator, sorbed to the clay mineral surface, during wetting and drying events. Using this technique it was possible to measure how low the pH of the surface drops during dehydration, the critical water content at which acidification of the surface begins and lastly how reversible the pH decrease is. The results show that only Al³⁺-smectite shows acidification below pH 4.8 with drying. The pH starts to decrease on the Al³⁺-smectite surface even when significantly hydrated (gravimetric water content ∼ 125 mg/m²), and falls to between 1.2 and 1.4 when completely air dry. The drying induced pH decrease is completely reversible on rewetting, suggesting large pH oscillations may occur on smectite surfaces with appreciable exchangeable Al³⁺. Aluminium saturated kaolinite did not show significant acidification in response to drying (pH > 3.5), however, a 0.1 M AlCl₃ solution evaporated to a final pH of 2.8. The enhanced acidification observed on an Al-smectite clay compared to a solution containing free Al³⁺ ions highlights the role of highly charged surfaces in the hydrolysis reaction that occurs within the hydration shell of exchangeable Al³⁺ ions.  相似文献   

Water soluble components of PM10 Chongqing, China   总被引：1，自引：0，他引：1  

Luo Qingquan  Xian Xuefu  Chen Gangcai  Yang Qinglin 《中国地球化学学报》2005,24(2):155-157

The concentrations of water soluble ions (Na⁺, NH₄ ⁺, K⁺, Mg²⁺, Ca²⁺, NO₃ ^-, Cl^-, and SO ₄ ^2- ) in PM₁₀ samples collected on cellulose filters by a medium-volume cascade impactor were determined, which were obtained from three kinds of areas in Chongqing: industrial area (Jiulongpo district), commercial and residential area (Jiangbei district) and background area (Jinyun Mountain in the Beibei district). The results showed that except for the background site, the annual average values of PM₁₀ are 23% – 61% higher than the national air quality standard (GradeII) (0.1 mg/m³), even that the value of the control site is still 20% higher than American standard (0.05 mg/m³). This implied that serious pollution of fine particles occurred in Chongqing. Nine kinds of soluble ions in water of PM₁₀ were analyzed by ion chromatography (IC) and the annual average concentrations follow the order of [SO ₄ ^2- ] > [NO³ _-] > [Cl^-] > [F^-], and [Ca²⁺] > [NH₄ ⁺] > [K⁺] > [Na⁺] > [Mg²⁺]. Their values were different in these areas: the industrial area > the commercial and living area > the control area. As for NH_{4 +}, K⁺, Ca²⁺, NO₃ ^- and SO ₄ ^2- , their seasonal average concentrations show a similar variation trend: the values in spring and fall were higher than those in summer and winter. The seasonal average concentrations of [Cl^-], [F^-], [Na⁺] and [Mg²⁺] are much lower than those of other ions. However, the concentrations of [Na⁺] changed more greatly in different seasons than those of the other three ions. Correlation coefficients showed that the three areas have been polluted by coal smoke and dust to different extents, while some local resources of pollution should be taken into consideration as well.  相似文献   

Limestone drains to increase pH and remove dissolved metals from acidic mine drainage     

《Applied Geochemistry》1999,14(5):581-606

Despite encrustation by Fe and Al hydroxides, limestone can be effective for remediation of acidic mine drainage (AMD). Samples of water and limestone (CaCO₃) were collected periodically for 1 a at 3 identical limestone-filled drains in Pennsylvania to evaluate the attenuation of dissolved metals and the effects of pH and Fe- and Al-hydrolysis products on the rate of CaCO₃ dissolution. The influent was acidic and relatively dilute (pH<4; acidity <90 mg) but contained 1–4 mg·L⁻¹ of O₂, Fe³⁺, Al³⁺ and Mn²⁺. The total retention time in the oxic limestone drains (OLDs) ranged from 1.0 to 3.1 hr. Effluent remained oxic (O₂>1 mg·L⁻¹) but was near neutral (pH=6.2–7.0); Fe and Al decreased to less than 5% of influent concentrations. As pH increased near the inflow, hydrous Fe and Al oxides precipitated in the OLDs. The hydrous oxides, nominally Fe(OH)₃ and Al(OH)₃, were visible as loosely bound, orange-yellow coatings on limestone near the inflow. As time elapsed, Fe(OH)₃ and Al(OH)₃ particles were transported downflow. The accumulation of hydrous oxides and elevated pH (>5) in the downflow part of the OLDs promoted sorption and coprecipitation of dissolved Mn, Cu, Co, Ni and Zn as indicated by decreased UK concentrations of the metals in effluent and their enrichment relative to Fe in hydrous-oxide particles and coatings on limestone. Despite thick (∼1 mm) hydrous-oxide coatings on limestone near the inflow, CaCO₃ dissolution was more rapid near the inflow than at downflow points within and the OLD where the limestone was not coated. The high rates of CaCO₃ dissolution and Fe(OH₃) precipitation were associated with the relatively low pH and high Fe³⁺ concentration near the inflow. The rate of CaCO₃ dissolution decreased with increased pH and concentrations of Ca²⁺ and HCO₃⁻ and decreased Pco₂. Because overall efficiency is increased by combining neutralization and hydrolysis reactions, an OLD followed by a settling pond requires less land area than needed for a two-stage treatment system consisting of an anoxic limestone drain an oxidation-settling pond or wetland. To facilitate removal of hydrous-oxide sludge, a perforated-pipe subdrain can be installed within an OLD.  相似文献   

Dissolution Kinetics of Calcite in 0.1 M NaCl Solution at Room Temperature: An Atomic Force Microscopic (AFM) Study   总被引：1，自引：0，他引：1  

Ryoji Shiraki  Peter A. Rock  William H. Casey 《Aquatic Geochemistry》2000,6(1):87-108

Atomic force microscopy (AFM) was used to study the rates of migration of the (10¯1 4) plane of a single-crystal of calcite dissolving in 0.1 M NaCl aqueous solutions at room temperature. The solution pH and P_{CO 2} controlled in the ranges 4.4 < pH < 12.2 and 0 < P_{CO 2} < 10^-3.5 atm (ambient), respectively. Measured step velocities were compared with the mineral dissolution rates determined from the calcium fluxes. The step velocity is defined as the average of the velocities of the obtuse and acute steps. Rates of step motion increased gradually from 1.4(±0.2) at pH 5.3 to 2.4(±0.3) nm s^-1 at pH 8.2, whereas the rates inverted and decreased to the minimum value of 0.69(±0.18) nm s^-1 at pH 10.8. For pH > 10.8, only the velocity of the obtuse steps increased as pH increased, whereas that of acute steps gradually decreased.The dissolution rate of the mineral can be calculated from the measured step velocities and average slope, which is proportional to the concentration of exposed monomolecular steps on the surface. The average slope of the dissolving mineral, measured at pH 5.6 and 9.7, was 0.026 (±0.015). Using this slope, we calculate bulk dissolution rates for 5.3 < pH < 12.2 of 4.9(±3.0) × 10^-11 to 1.8(±1.0) × 10^-10 mol cm^-2 s^-1. The obtained dissolution rate can be expressed by the following empirical equation:R_dss = 10^{-4.66(±0.13)}[H⁺] + 10^{-3.87(±0.06)}[HCO₃ ^-] + 10^{-7.99(plusmn; 0.08)}[OH^-]We propose that calcite dissolution in these solutions is controlled by elementary reactions that are similar to those that control the dissolution of other amphoteric solids, such as oxides. The mechanisms include the proton-enhanced hydration and detachment of calcium-carbonate ion pairs. The detachments are enhanced by the presence of adsorbed nucleophiles, such as hydroxyl and bicarbonate ions, and by protons adsorbed to key oxygens. A molecular model is proposed that illustrates these processes.  相似文献   

Steady-state kinetics and equilibrium between ground water and granitic rock     

Tomas Paces 《Geochimica et cosmochimica acta》1973,37(12):2641-2663

A hypothesis is presented that the dissolution of albite includes the exchange of sodium for hydrogen ion in a surface layer of the mineral and the structural collapse of the residual anionic lattice of the layer. The ion exchange is described by the first law of diffusion (D_25°C = 3 × 10^?22 and 1.5 × 10^?20 cm²sec^?1 at P_CO2 = 0 and 26.2 atm, respectively). The surface residual layer reaches a steady-state thickness ranging from n × 10^?8 to n × 10^?5 cm according to the temperature and P_CO2. The increase in aqueous sodium with time in a continuous ground-water system is described by a simple exponential equation. The equation is used to estimate the percolation time of ground water from the data on the chemical composition of a water sample. The probable times range from 14 to 3840 days for various ground-water systems and are compared to the times of percolation calculated from the geothermal and hydraulic data. Both estimates are found to be in general agreement. The concentrations of Al and Si in cold water from granitic rocks are shown to be controlled by the chemical equilibrium with respect to an aged aluminosilicate. The aluminosilicate precipitates from ground water as an amorphous isoelectric solid. Its chemical composition is represented by a simplified stoichiometric formula [Al(OH)₃](_1?x)[SiO₂]_x and varies linearly with pH of the solution. The atoms of Al, O and H tend to occupy a fixed position in the solid given by the gibbsite structure upon aging in the field. The solubility product of the solid is estimated from the published data on experimental and field research into the dissolution of feldspars: logK = (1 ? x) × log [Al³⁺] + xlog [H₄SiO₄] ? (3 ? 3x) log [H⁺] = 8.56 ? 11.26x, where x is the molar fraction of silica in the aluminosilicate.  相似文献   

The adsorption characteristics of δ-manganese dioxide: a collection of diffuse double layer constants for the adsorption of H+, Cu2+, Ni2+, Zn2+, Cd2+ and Pb2+     

《Applied Geochemistry》2001,16(9-10):1067-1082

Thermodynamic data for all fate-determining processes are needed in order to predict the fate and transport of metals in natural systems. The surface complexation properties of a synthetic MnO₂, δ-MnO₂, have accordingly been investigated using glass electrode potentiometry. Experimental data were interpreted according to the surface complexation model in conjunction with the diffuse double layer model of the solid/solution interface. Adsorption constants were determined using the non-linear optimisation program FITEQL. Surface complexation parameters determined in this way were validated against results obtained from the literature. Best fits of alkalimetric titration data were obtained with a 2-site, 3 surface-species model of the δ-MnO₂ surface. Site concentrations of 2.23×10⁻³ mol g⁻¹ and 7.66×10⁻⁴ mol g⁻¹ were obtained. Corresponding logarithms of formation constants for the postulated surface species are −1.27 (≡XO⁻), −5.99 (≡YO⁻) and 3.52 (≡YOH₂⁺) at I=0.1 M. The surface speciation of δ-MnO₂ is dominated by ≡XO⁻ over the pH range investigated. Metal adsorption was modelled with surface species of the type ≡XOM⁺, ≡XOMOH, ≡YOM⁺, ≡YOMOH (M=Cu, Ni, Zn, Cd and Pb) and ≡XOM₂OH²⁺ (M=Pb). For Cu, Ni and Zn, titration data could be modelled with ≡XOM⁺, ≡XOMOH, ≡YOM⁺ and ≡YOMOH, whereas for Cd, ≡XOM⁺ and ≡YOM⁺ were sufficient. Lead data were best modelled by assuming the dinuclear species ≡XOM₂OH²⁺ to be the only surface species to form. Adsorption constants determined for Ni, Cu and Zn follow the Irving-Williams sequence. The model suggests an adsorption order of (Pb, Cu) > (Ni, Zn) > Cd. The discrepancy between model predictions and published adsorption results is similar to the variability observed in experimental results from different laboratories.  相似文献   

Field determination of Fe2+ oxidation rates in acid mine drainage using a continuously-stirred tank reactor     

《Applied Geochemistry》1998,13(4):509-520

A gravity-fed, battery-powered, portable continuously-stirred tank reactor has been developed to directly measure aqueous reaction rates in the field. Dye and tracer experiments indicate the reactor is well-mixed. Rates of Fe²⁺ oxidation at untreated and passively treated coal mine drainage sites in Pennsylvania were measured under ambient conditions and with the addition of either O₂ gas or NaOH solutions. Rates at 5 sites ranged from below the detection limit for this technique (approximately 10⁻⁹ mol L⁻¹ s⁻¹) to 3.27±0.01×10⁻⁶ mol L⁻¹ s⁻¹. Uncertainties in rates ranged from 70% near the lower limit of measurement to as little as 1% at higher rates of reaction. Multiple linear regressions showed no universal correlations of rates to Fe²⁺, dissolved O₂, and pH (Thiobacillus populations were not measured), although data for two more acidic sites were found to fit well for the model log rate=log K+a log [Fe²⁺]+b log [OH⁻]+c log [O₂]. Field rates of Fe oxidation from this and other studies vary by 4 orders of magnitude. A model using the ambient field rate of Fe oxidation from this study successfully reproduced independently-measured Fe²⁺ concentrations observed in a passive wetland treatment facility.  相似文献   

On the chemistry of the keggin Al13 polymer: kinetics of proton-promoted decomposition     

《Geochimica et cosmochimica acta》1999,63(19-20):3069-3076

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Iron control by equilibria between hydroxy-Green Rusts and solutions in hydromorphic soils     

《Geochimica et cosmochimica acta》1999,63(19-20):3417-3427

In order to verify Fe control by solution - mineral equilibria, soil solutions were sampled in hydromorphic soils on granites and shales, where the occurrence of Green Rusts had been demonstrated by Mössbauer and Raman spectroscopies. Eh and pH were measured in situ, and Fe(II) analyzed by colorimetry. Ionic Activity Products were computed from aqueous Fe(II) rather than total Fe in an attempt to avoid overestimation by including colloidal particles. Solid phases considered are Fe(II) and Fe(III) hydroxides and oxides, and the Green Rusts whose general formula is [Fe^II_1−xFe^III_x(OH)₂]^+x· [x/z A^−z]^−x, where compensating interlayer anions, A⁻, can be Cl⁻, SO₄²⁻, CO₃²⁻ or OH⁻, and where x ranges a priori from 0 to 1. In large ranges of variation of pH, pe and Fe(II) concentration, soil solutions are (i) oversaturated with respect to Fe(III) oxides; (ii) undersaturated with respect to Fe(II) oxides, chloride-, sulphate- and carbonate-Green Rusts; (iii) in equilibrium with hydroxy-Green Rusts, i.e., Fe(II)-Fe(III) mixed hydroxides. The ratios, x = Fe(III)/Fe_t, derived from the best fits for equilibrium between minerals and soil solutions are 1/3, 1/2 and 2/3, depending on the sampling site, and are in every case identical to the same ratios directly measured by Mössbauer spectroscopy. This implies reversible equilibrium between Green Rust and solution. Solubility products are proposed for the various hydroxy-Green Rusts as follows: log K_sp = 28.2 ± 0.8 for the reaction Fe₃(OH)₇ + e⁻ + 7 H⁺ = 3 Fe²⁺ + 7 H₂O; log K_sp = 25.4 ± 0.7 for the reaction Fe₂(OH)₅ + e⁻ + 5 H⁺ = 2 Fe²⁺ + 5 H₂O; log K_sp = 45.8 ± 0.9 for the reaction Fe₃(OH)₈ + 2e⁻ + 8 H⁺ = 3 Fe²⁺ + 8 H₂O at an average temperature of 9 ± 1°C, and 1 atm. pressure. Tentative values for the Gibbs free energies of formation of hydroxy-Green Rusts obtained are: Δ_fG° (Fe₃(OH)₇, cr, 282.15 K) = −1799.7 ± 6 kJ mol⁻¹, Δ_fG° (Fe₂(OH)₅, cr, 282.15 K) = −1244.1 ± 6 kJ mol⁻¹ and Δ_fG° (Fe₃(OH)₈, cr, 282.15 K) = −1944.3 ± 6 kJ mol⁻¹.  相似文献   

Reaction pathways for quartz dissolution determined by statistical and graphical analysis of macroscopic experimental data     

Barry R. Bickmore  Justin C. Wheeler  Kathryn L. Nagy 《Geochimica et cosmochimica acta》2008,72(18):4521-4536

In light of recent work on the reactivity of specific sites on large (hydr)oxo-molecules and the evolution of surface topography during dissolution, we examined the ability to extract molecular-scale reaction pathways from macroscopic dissolution and surface charge measurements of powdered minerals using an approach that involved regression of multiple datasets and statistical graphical analysis of model fits. The test case (far-from-equilibrium quartz dissolution from 25 to 300 °C, pH 1-12, in solutions with [Na⁺] ? 0.5 M) avoids the objections to this goal raised in these recent studies. The strategy was used to assess several mechanistic rate laws, and was more powerful in distinguishing between models than the statistical approaches employed previously. The best-fit model included three mechanisms—two involving hydrolysis of Si centers by H₂O next to neutral (>Si-OH⁰) and deprotonated (>Si-O⁻) silanol groups, and one involving hydrolysis of Si centers by OH⁻. The model rate law is