Surface chemistry and dissolution kinetics of glassy rocks at 25°C

The weathering rates and mechanisms of three types of glassy rocks were investigated experimentally at 25 °C, pH 1.0 to 6.2, and reaction times as much as to 3 months. Changes in major element chemistry were monitored concurrently as a function of time in the aqueous solution and within the near surface region of the glass. Leach profiles, obtained by a HF leaching technique, displayed near-surface zones depleted in major cations. These zones increased in depth with increasing time and decreasing pH of reactions. Release rates into the aqueous solution were parabolic for Na and K and linear for Si and Al. A coupled weathering model, involving surface dissolution with concurrent diffusion of Na, K, and Al, produced a mass balance between the aqueous and glass phases. Steady state conditions are reached at pH 1.0 after approximately 3 weeks of reaction. Steady-state is not reached even after 3 months at pH 6.2.An interdiffusion model describes observed changes in Na diffusion profiles for perlite at pH 1.0. The calculated Na self-diffusion coefficient of 5 × 10^?19 cm²·s^?1 at 25°C approximates coefficients extrapolated from previously reported high temperature data for obsidian. The self-diffusion coefficient for H₃O⁺, 1.2 × 10^?20 cm²·s^?1, is similar to measured rates of water diffusion during hydration of obsidian to form perlite.     

Monazite solubility and dissolution kinetics: implications for the thorium and light rare earth chemistry of felsic magmas

A series of monazite dissolution experiments was conducted in a hydrous (1–6 wt.%) granitic melt at 8 kbar over the temperature range 1,000–1,400° C. A polished cube of monazite was immersed in a natural obsidian melt and allowed to partially dissolve. Electron microprobe traverses perpendicular to the crystal-melt interface revealed concentration gradients in the LREEs and P. Diffusivities of the LREEs and P were calculated from these profiles, yielding the following Arrhenius relations for the LREEs: D=0.23 exp(–60.1 kcal mol^–1/RT) at 6% water D=2.30×10⁷ exp(–122.1 kcal mol^–1/RT) at 1% water These results demonstrate the importance of dissolved water on REE diffusion. Phosphorus diffusivities are nearly identical to those of the rare-earths, suggesting that P diffusion charge-compensates REE diffusion. The concentration of LREEs required for monazite saturation in these melts is given by the level of dissolved LREEs at the crystal-melt interface. These values also show a dependence on dissolved water, with LREE_sat=60 ppm at 6% H₂O when extrapolated down to 700° C, and LREE_sat=30 ppm at 1% H₂O. Calculated dissolution rates based on the above parameters indicate that minute (<30 m diameter) monazite crystals will be readily digested by an enclosing anatectic magma under reasonable geologic conditions (i.e., T=700–800° C and >2% H₂O), whereas larger (> 50 m) crystals will likely be residual over the duration of an anatectic event. The low solubility of monazite in this melt suggests that the LREE depletion observed in some felsic differentiation suites may be the result of monazite crystallization. Limited experimental and geochemical/petrologic evidence indicates that compositional changes in the melt accompanying differentiation decrease the solubility of monazite drastically. Kinetic and chemical constraints may also lead to localized monazite saturation and inclusion in major phases or even other accessories. Variations in the REE composition of monazite from different parageneses probably reflects the REE pattern of the parent melt, and may be due to gradational differences in the stability of individual or subgroup REE-complexes as a function of melt composition. Particularly important in this regard seems to be the lime+alkali/alumina balance of the melt and its volatile content.     

Surface chemistry and reactivity of plant phytoliths in aqueous solutions

In order to better understand the reactivity of plant phytoliths in soil solutions, we determined the solubility, surface properties (electrophoretic mobilities and surface charge) and dissolution kinetics of phytoliths extracted from fresh biomass of representative plant species (larch tree and elm, horsetail, fern, and four grasses) containing significant amount of biogenic silica. The solubility product of larch, horsetail, elm and fern phytoliths is close to that of amorphous silica and soil bamboo phytoliths. Electrophoretic measurements yield isoelectric point pH_IEP = 0.9, 1.1, 2.0 and 2.2 for four grasses, elm, larch and horsetail phytoliths respectively, which is very close to that of quartz or amorphous silica. Surface acid–base titrations allowed generation of a 2-pK surface complexation model (SCM) for larch, elm and horsetail phytoliths. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 1 ≤ pH ≤ 8, were found to be very similar among the species, and close to those of soil bamboo phytoliths. Mechanistic treatment of all plant phytoliths dissolution rates provided three-parameters equation sufficient to describe phytoliths reactivity in aqueous solutions:$R(\text{mol}/{\text{cm}}^2/\text{s})=6?{10}^{?16}?a_{\text{H+}}+5.0?{10}^{?18}+3.5?{10}^{?13}?a_{\text{OH}?}^{0.33}$Alternatively, the dissolution rate dependence on pH can be modeled within the concept of surface coordination theory assuming the rate proportional to concentration of > SiOH₂⁺, > SiOH⁰ and > SiO^? species. In the range of Al concentration from 20 to 5000 ppm in the phytoliths, we have not observed any correlation between their Al content and solubility, surface acid–base properties and dissolution kinetics.It follows from the results of this study that phytoliths dissolution rates exhibit a minimum at pH ～ 3. Mass-normalized dissolution rates are similar among all four types of plant species studied and these rates are an order of magnitude higher than those of typical soil clay minerals. The minimal half life time of larch and horsetail phytoliths in the interstitial soil solution ranges from 10–12 years at pH = 2–3 to < 1 year at pH above 6, comparable with mean residence time of phytoliths in soil from natural observations.     

The kinetics of chlorite dissolution

A model for the dissolution of chlorite has been developed based on fast ligand assisted proton attack of the alumina tetrahedra within the alumina-silica lattice followed by slower dissolution of the remnant silica lattice. While the rate determining step is within the silica dissolution regime, the rate is a function of the H⁺ and Al³⁺ concentrations and the dominant aqueous Al species. Individual rates may be described by a generic rate equation applicable across the spectrum of Al species:

     

Magnesium inhibition of calcite dissolution kinetics

We present evidence of inhibition of calcite dissolution by dissolved magnesium through direct observations of the (104) surface using atomic force microscopy (AFM) and vertical scanning interferometry (VSI). Far from equilibrium, the pattern of magnesium inhibition is dependent on solution composition and specific to surface step geometry. In CO₂-free solutions (pH 8.8), dissolved magnesium brings about little inhibition even at concentrations of 0.8 × 10⁻³ molal. At the same pH, magnesium concentrations of less than 0.05 × 10⁻³ molal in carbonate-buffered solutions generate significant inhibition, although no changes in surface and etch pit morphology are observed. As concentrations exceed magnesite saturation, the dissolution rate shows little additional decrease; however, selective pinning of step edges results in unique etch pit profiles, seen in both AFM and VSI datasets. Despite the decreases in step velocity, magnesium addition in carbonated solutions also appears to activate the surface by increasing the nucleation rate of new defects. These relationships suggest that the modest depression of the bulk rate measured by VSI reflects a balance between competing reaction mechanisms that simultaneously depress the rate through selective inhibition of step movement, but also enhance reactivity on terraces by lowering the energy barrier to new etch pit formation.     

Some kinetics of bronzite orthopyroxene dissolution

The kinetics of bronzite orthopyroxene dissolution were investigated in HClKCl solutions having a total concentration of 0.1 M, over the pH range 1–4.5, at temperatures between 42 and 1°C. Dissolution of the pyroxene was incongruent and followed a parabolic rate law. The activation energy of the reaction is 10.5 ± 0.6 kcal mole^?1. The rate dependence on hydrogen ion activity is one-half order. The rate of dissolution is unaffected by substitution of sodium for potassium, or sulfate or nitrate for chloride anion, or by addition of citrate or acetate ions. However, traces of fluoride increase the dissolution rate. The rates observed are one to two orders of magnitude slower than those previously reported by Luceet al. (1972) for dissolution of enstatite.     

The mechanism and kinetics of DTPA-promoted dissolution of barite

The dissolution rate of natural barite, BaSO₄, was measured in solutions of DTPA (diethylene triamine penta-acetic acid) to investigate the mechanism of ligand-promoted dissolution using a strong chelating agent. Experiments were carried out over a range of DTPA concentrations 0.5–0.0001 M solutions, at room temperature (22 °C), as well as a range of temperatures, 22–80 °C at 1 atm. The dissolution rate is inversely related to the DTPA concentration in solution. A more dilute DTPA solution is shown to be more efficient as a solvent in terms of the approach to the equilibrium saturation value for the dissolution of Ba²⁺. An analysis of the temperature dependence of the dissolution rate at high pH by the determination of activation energies indicates that the reaction is probably controlled by the pre-exponential term in the rate constant. This indicates that reaction frequency mostly controls differences in reactivity and suggests an explanation for the results in terms of stearic hindrance due to adsorbed DTPA molecules at the barite surface. The effect of DTPA on the solvation of the Ba²⁺ ion may also influence the dissolution rate.     

Synthesis,solubility, electrokinetic properties and refined crystallographic data of sabugalite

Sabugalite has been synthesized directly from pure chemicals. From chemical, differential thermal and thermogravimetric analyses, its formula is calculated as HA1(UO₂/PO₄)₂·16H₂O. The natural relationship between hydrogen autunite, autunite and sabugalite was investigated by means of ion exchange experiments, and its infrared spectrum, electrokinetic properties and solubility studied. An increase in solubility results in a more positive zeta-potential. The cell dimensions have been determined from Guinier-Hägg diffraction data. Synthetic sabugalite crystallizes in the monoclinic system with space group C2/m and cell parameters: a=19.426 Å; b=9.843 Å; c=9.850 Å; α=γ=90°; β=96.161°; V=1,872.54 ų and Z=2.     

应力作用下岩石的化学动力学溶解机制研究

通过结合化学热力学及动力学、过渡态理论和岩石力学等方面的知识,建立了应力作用下岩石的溶解动力学模型,分析了应力作用对岩石固相物质活度及矿物溶解动力学速率的影响,探讨了应力作用下水岩相互作用机制。研究结果表明：岩石所承受应力与周围流体压力之间存在的应力差所产生的化学势差是应力作用下溶解反应的驱动力;应力的施加显著提高了岩石中固相物质的活度,由此加快了矿物溶解反应的动力学速率;应力作用下的岩石细观溶解机制可根据固液界面应力分配及优先溶解部位上的差别分别用水膜扩散模型或岛渠模型进行描述;应力作用下水岩相互作用存在着应力、化学与渗流的3场耦合问题：应力推动化学反应的发生,化学作用使得岩石表面的细观形貌发生改变,局部的应力分布及大小也随着形貌的变化而改变,进而影响化学反应发生的位置及进程,同时也改变渗流通道的演化规律     

Synthesis,crystallographic data,solubility and electrokinetic properties of meta-zeunerite,meta-kirchheimerite and nickel-uranylarsenate

{M[UO₂¦AsO₄]₂ · nH₂O} with M=Cu²⁺, Co²⁺, Ni²⁺ has been synthesized from reagent grade chemicals and by ion exchange of trögerite {HUO₂AsO₄ · 4 H₂O}. Synthetic meta-zeunerite (M=Cu²⁺), meta-kirchheimerite (M=Co²⁺) and nickel-uranylarsenate are all tetragonal. The cell parameters determined from Guinier-Hägg diffraction data for {Cu[UO₂¦AsO₄]₂ · 8 H₂O} are a=b=7.10 Å and c=17.42 Å, with Z=2 and the measured density 3.70 g cm^?3. The cell parameters for {Co[UO₂¦AsO₄]₂ · 7 H₂O} and {Ni[UO²¦AsO⁴]² · 7 H₂O} are a=b=20.25 Å and c=17.20 Å, with Z=16 and the measured density 3.82 and 3.74 g cm^?3, respectively. The solubility products for synthetic Cu-, Co- and Ni-uranylarsenate at 25° C are 10^?49.20, 10^?45.34 and 10^?45.10, respectively. The zeta-potential remains negative between pH=2 and pH=9 and is strongly affected by the presence of different cations.     

The dissolution kinetics of biogenic calcium carbonates in seawater

Dissolution rate as a function of degree of undersaturation was measured on shells of individual species of coccoliths and foraminifera, various size fractions of sediment from the Ontong-Java Plateau and the Rio Grande Rise, a collection of large pteropods, and on synthetic calcite and aragonite powder.Results of the study indicate that all biogenic and synthetic calcium carbonate follows the rate law $\text{R\% = k\%(1 ? Ω)}{}^{\mathrm{n}}$ where $\text{Ω  [Ca}{}^{\mathrm{2+}}\text{][CO}{}_3{}^{\mathrm{2?}}\text{]/K'}{}_{\mathrm{sp}}$ and K'_sp is the apparent solubility product of calcite or aragonitic seawater. In the case of all calcite samples, n_c = 4.5, while for aragonitic samples n_a = 4.2. The ‘rate constant’, k%, varies widely between samples and in many cases is inversely correlated with grain size. However, the individual species of coccoliths, E. huxleyi and C. neohelis, which were cultured in the laboratory appear not to follow this rule, with dissolution rates an order to magnitude lower than expected.     

The mechanism of surface chemical kinetics of dissolution of minerals

This paper deals with the mechanism of dissolution reaction kinetics of minerals in aqueous solution based on the theory of surface chemistry.Surface chemical catalysis would lead to an obvous decrease in active energy of dissolution reaction of minerals.The dissolution rate of minerals is controlled by suface adsorption,surface exchange reaction and desorption,depending on pH of the solution and is directly proportional to δH^n0 ,When controlled by surface adsorption,i.e.,nθ=1,the dissolution rate will decrease with increasing pH;when controlled by surface exchane reaction,i.e.,nθ=0,the dissolution rate is independent of pH;when controlled by desorption,nθis a positive decimal between 0 and 1 in acidic solution and a negative decimal between-1 and 0 in alkaline solution.Dissolution of many minerals is controlled by surface adsorption and/or surface exchange reactions under acid conditions and by desorption under alkaline conditions.     

The influence of grinding on the dissolution kinetics of calcite

This study of the dissolution of calcite in an acid environment demonstrates a significant dissolution anomaly for small particles. This cannot be attributed to very small, finely ground particles “stuck” to the grains, as there were too few to explain the magnitude of the observed anomaly. It is linked to the disruption resulting from the grinding. When observed in the electron microscope, the grains appear to be constructed of an aggregate of small crystals oriented in several principal directions. Their size increases progressively from the surface to the interior of the grain. An exothermic reaction is produced when the calcite is heated to 350° C. This causes a change in the microcrystalline structure leading to a nearly monocrystalline state. This recrystallisation retards the dissolution speed.     

The dissolution kinetics of a granite and its minerals—Implications for comparison between laboratory and field dissolution rates

The present study compares the dissolution rates of plagioclase, microcline and biotite/chlorite from a bulk granite to the dissolution rates of the same minerals in mineral-rich fractions that were separated from the granite sample. The dissolution rate of plagioclase is enhanced with time as a result of exposure of its surface sites due to the removal of an iron oxide coating. Removal of the iron coating was slower in the experiment with the bulk granite than in the mineral-rich fractions due to a higher Fe concentration from biotite dissolution. As a result, the increase in plagioclase dissolution rate was initially slower in the experiment with the bulk granite. The measured steady state dissolution rates of both plagioclase (6.2 ± 1.2 × 10⁻¹¹ mol g⁻¹ s⁻¹) and microcline (1.6 ± 0.3 × 10⁻¹¹ mol g⁻¹ s⁻¹) were the same in experiments conducted with the plagioclase-rich fraction, the alkali feldspar-rich fraction and the bulk granite.Based on the observed release rates of the major elements, we suggest that the biotite/chlorite-rich fraction dissolved non-congruently under near-equilibrium conditions. In contrast, the biotite and chlorite within the bulk granite sample dissolved congruently under far from equilibrium conditions. These differences result from variations in the degree of saturation of the solutions with respect to both the dissolving biotite/chlorite and to nontronite, which probably was precipitating during dissolution of the biotite and chlorite-rich fraction. Following drying of the bulk granite, the dissolution rate of biotite was significantly enhanced, whereas the dissolution rate of plagioclase decreased.The presence of coatings, wetting and drying cycles and near equilibrium conditions all significantly affect mineral dissolution rates in the field in comparison to the dissolution rate of fully wetted clean minerals under far from equilibrium laboratory conditions. To bridge the gap between the field and the laboratory mineral dissolution rates, these effects on dissolution rate should be further studied.     

Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals

The influence of pH on the rate of dissolution of various carbonates (calcite, aragonite, witherite, magnesite and dolomite) has been investigated at 25°C using a continuous fluidized bed reactor. The general rate dependence on pH observed for the simple carbonates is very similar and is in agreement with the results observed for calcite and aragonite by L.N. Plummer and coworkers. However, the rate of dissolution of magnesite is approximately four orders of magnitude lower than calcite.

For simple carbonates, the elementary steps involved in the dissolution reaction are:

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where M represents the metal ion which can be Ca, Mg and Ba. According to the stoichiometry of the three reaction steps and the thermodynamic constraints, the total forward and backward rates can be expressed as:

R_f=k₁a_H+k₂a_H2CO3^*+K₃

r_b=k_-1^aM²+^aHCO₃^-+k_-2^aHCO3^-+k_{-3^aM²+^aCO3^2-}

The rate constants (k₁, k₂, k₃ and k₋₃) determined with our experimental results for calcite, aragonite and witherite show that the dissolution rates are similar for these three minerals and that the nature of the cations does not play a significant role. The good agreement between the K_sp calculated from the measured k₃/k₋₃ ratio and the theromodynamic value suggests that our dissolution mechanism is coherent.

The rate dependence on pH of the dissolution of dolomite obeys a fractional order at low pH's and confirms previously published observations therein. However, the two-step reaction mechanism proposed does not explain the fractional reaction order observed, which is likely due to a more complex surface reaction.     

Geochemistry,dissolved elemental flux rates,and dissolution kinetics of lithologies of Alaknanda and Bhagirathi rivers in Himalayas,India

Alaknanda and Bhagirathi (AB) river basins in the Himalayan region in India expose lithologies comprising mainly of granites, low–high-grade metamorphics, shales and carbonates which, in conjunction with the monsoon rains and glacial melt, control water chemistry and dissolved elemental flux rates. In the present study, we monitored two locations: (a) Srinagar on the Alaknanda river and (b) Maneri on the Bhagirathi river for daily variations in total suspended sediments, major ions and dissolved silica over one complete year (July 2004–June 2005). Based on long-term discharge data, discharge-weighted composition and dissolved elemental flux rates (with respect to Ca, Mg, HCO₃, Si) of the river were estimated. The information thus obtained has substantially added up to the existing chemical data of these rivers and has refined the flux rates. Our high-frequency samples provide informations such as (a) water chemical compositions that show a large temporal and spatial variation and (b) carbonate lithology that controls water chemistry predominantly. The dissolution kinetics of various lithologies namely leucogranite, gneiss, quartzite, phyllite and shale of the AB river basins were studied through batch experiments at controlled temperature (25 and 5°C) and pH (8.4) condition. In laboratory, these lithologies undergo slow rates of dissolution (10⁻¹³ to 10⁻¹⁵ mol/m² s), while field weathering rates based on dissolved elemental flux rates in the AB rivers are much higher (10⁻⁸ to 10⁻⁹ mol/m² s). Extremely high physical weathering rates in AB rivers, which enhance chemical weathering significantly, mainly attribute this wide discrepancy in laboratory-derived rates of representative basin rocks and dissolved elemental fluxes in the field. However, laboratory-simulated experiments facilitate to quantify elemental release rates, understand the kinetics of the dissolution reactions, and compare their roles at individual level.     

Orthoclase dissolution kinetics probed by in situ X-ray reflectivity: effects of temperature, pH, and crystal orientation

Initial dissolution kinetics at orthoclase (001) and (010) cleavage surfaces were measured for ∼2 to 7 monolayers as a function of temperature using in situ X-ray reflectivity. The sensitivity of X-ray reflectivity to probe mineral dissolution is discussed, including the applicability of this approach for different dissolution processes and the range of dissolution rates (∼10⁻¹² to 10⁻⁶ mol/m²/sec) that can be measured. Measurements were performed at pH 12.9 for the (001) surface and at pH 1.1 for the (001) and (010) surfaces at temperatures between 46 and 83°C. Dissolution at pH 12.9 showed a temperature-invariant process with an apparent activation energy of 65 ± 7 kJ/mol for the (001) cleavage surface consistent with previous powder dissolution results. Dissolution at pH 1.1 of the (001) and (010) surfaces revealed a similar process for both surfaces, with apparent activation energies of 87 ± 7 and 41 ± 7 kJ/mol, respectively, but with systematic differences in the dissolution process as a function of temperature. Longer-term measurements (five monolayers) show that the initial rates reported here at acidic pH are greater than steady-state rates by a factor of 2. Apparent activation energies at acidic pH differ substantially from powder dissolution results for K-feldspar; the present results bracket the value derived from powder dissolution measurements. The difference in apparent activation energies for the (001) and (010) faces at pH 1.1 reveals an anisotropy in dissolution kinetics that depends strongly on temperature. Our results imply a projected ∼25-fold change in the ratio of dissolution rates for the (001) and (010) surfaces between 25 and 90°C. The dissolution rate of the (001) surface is higher than that of the (010) surface above 51°C and is projected to be lower below this temperature. These results indicate clearly that the kinetics and energetics of orthoclase dissolution at acidic pH depend on crystal orientation. This dependence may reflect the different manifestation of the Al-Si ordering between the T1 and T2 tetrahedral sites at these two crystal faces and can be rationalized in terms of recent theoretical models of mineral dissolution.     

Factors affecting the dissolution kinetics of volcanic ash soils: dependencies on pH,CO2, and oxalate

Laboratory experiments were conducted with volcanic ash soils from Mammoth Mountain, California to examine the dependence of soil dissolution rates on pH and CO₂ (in batch experiments) and on oxalate (in flow-through experiments). In all experiments, an initial period of rapid dissolution was observed followed by steady-state dissolution. A decrease in the specific surface area of the soil samples, ranging from 50% to 80%, was observed; this decrease occurred during the period of rapid, initial dissolution. Steady-state dissolution rates, normalized to specific surface areas determined at the conclusion of the batch experiments, ranged from 0.03 μmol Si m⁻² h⁻¹ at pH 2.78 in the batch experiments to 0.009 μmol Si m⁻² h⁻¹ at pH 4 in the flow-through experiments. Over the pH range of 2.78–4.0, the dissolution rates exhibited a fractional order dependence on pH of 0.47 for rates determined from H⁺ consumption data and 0.27 for rates determined from Si release data. Experiments at ambient and 1 atm CO₂ demonstrated that dissolution rates were independent of CO₂ within experimental error at both pH 2.78 and 4.0. Dissolution at pH 4.0 was enhanced by addition of 1 mM oxalate. These observations provide insight into how the rates of soil weathering may be changing in areas on the flanks of Mammoth Mountain where concentrations of soil CO₂ have been elevated over the last decade. This release of magmatic CO₂ has depressed the soil pH and killed all vegetation (thus possibly changing the organic acid composition). These indirect effects of CO₂ may be enhancing the weathering of these volcanic ash soils but a strong direct effect of CO₂ can be excluded.