Experimental study of the effect of pH and temperature on the kinetics of montmorillonite dissolution

The effect of pH on the kinetics of smectite (K-montmorillonite) dissolution was investigated at 50 and 70 °C in stirred flow-through reactors over the pH range of 1-13.5. Experiments done at very acidic and very basic pH were far from equilibrium. Near neutral pH experiments were closer to equilibrium. The Al/Si release ratio, while initially being incongruent, ultimately approached the stoichiometric value in most of the experiments. Temperature, extreme pH, and time favor congruency. Rates can be described by:

     

Fluorite dissolution at acidic pH: In situ AFM and ex situ VSI experiments and Monte Carlo simulations

Dissolution of the fluorite (1 1 1) cleavage surface was investigated by means of in situ atomic force microscopy (AFM) and ex situ vertical scanning interferometry (VSI) experiments at pH range 1-3 in HCl solutions. Surface retreat was quantified at different pH values, yielding dissolution rates that were used to derive an empirical rate law for fluorite dissolution:

     

Quartz dissolution experiments at various pH, temperature and stress conditions: CLSM and ICP-AES investigations

To understand the effects of temperature, pH and mechanical stress on the pressure dissolution of quartz, two experiments using monocrystalline quartz samples were conducted. The first was a closed-fluid experiment to investigate the effect of pH, and the second was a flow-through experiment to investigate stress and temperature effects. To initiate the pressure dissolution, a pair of samples was immersed in a solution with a prescribed pH. The samples were stressed mechanically by pressing one sample against the other. In the closed-fluid experiments, the pH of the solution was fixed to 7, 9, 11 and 13, the applied stress was approximately 200 MPa and temperature 25°C. The flow-through experiments were conducted at three different temperatures (35, 50 and 75°C) at the same pH 11.7. The value of the applied stress was 7.32, 13.72, 21.42 or 25.27 MPa. During each of these dissolution tests, the solution was regularly sampled and analyzed by an Inductively Coupled Plasma-Atomic Emission Spectrometry technique to measure Si-concentration. With the measured Si-concentration, a dissolution rate constant was computed the different pH, stress and temperature conditions. The rate constant is proportional to pH, stress and temperature, as indicated in the literature. It should be noted that the rate constant for the highest stress (200 MPa) was considerably greater than for the other cases. In addition, island-channel patterns characterized by micro-cracks a few nanometers in length were seen on the dissolved parts of the samples. The findings and the measured data in this paper may be useful for the future development of theoretical models for pressure dissolution and its validation.     

Structure and growth of stearate monolayers on calcite: first results of an in situ X-ray reflectivity study

The adsorption of organic molecules at mineral–fluid interfaces has a profound influence upon geochemical reaction and transport processes, yet little is known about the in situ structures or properties of organic layers at mineral–fluid interfaces. We describe an X-ray reflectivity study of stearate monolayers adsorbed at the calcite surface from methanolic solutions. Using these measurements we are able to determine important aspects of the in situ structure, bonding, adsorption, and growth mechanisms of stearate monolayers. The experimental approach demonstrated here can be applied widely in studying the interaction of organic molecules with mineral surfaces in aqueous systems.     

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.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

In situ X-ray observations of the coesite-stishovite transition: reversed phase boundary and kinetics

Using a DIA-type, cubic-anvil, high-pressure apparatus (SAM-85) in conjunction with in situ X-ray diffraction, we have investigated phase relations between coesite and stishovite up to 12 GPa and 1530 °C using synthetic powders of the two phases as the starting materials. The phase transition between coesite and stishovite was identified by observing the first appearance of a phase that did not already exist or by a change in the relative intensity of the two patterns. In most experiments, the diffraction patterns on samples were collected within 10 minutes after reaching a pressure and temperature condition. On this time scale, two phase boundaries associated with the coesite-stishovite transition have been determined: (1) for the stishovite-to-coesite transition, observations were made in the temperature range of 950–1530 °C, and (2) for the coesite-to-stishovite transition from 500 to 1300 °C. These observations reveal that there exists a critical temperature of about 1000 °C to constrain the coesite-stishovite equilibrium phase boundary. Above this temperature, both boundaries are linear, have positive dP/dT slopes, and lie within a pressure interval of 0.4 GPa. Below this temperature, the dP/dT slope for the stishovite-to-coesite phase boundary becomes significantly larger and that for the coesite-tostishovite phase boundary changes from positive to negative. As a result, an equilibrium phase boundary can only be determined from the results above 1000 °C and is described by a linear equation P (GPa)=6.1 (4)+ 0.0026 (2) T (°C). This dP/dT slope is in good agreement with that of Zhang et al. (1993) but more than twice that of Yagi and Akimoto (1976). For the kinetics of the phase transition, preliminary rate data were obtained for the stishovite-to-coesite transition at 1160 and 1430 °C and are in agreement with the simple geometric transformation model of Avrami and Cahn.     

The kinetics and mechanisms of simulated British Magnox waste glass dissolution as a function of pH,silicic acid activity and time in low temperature aqueous systems

Dissolution of a simulated British Magnox waste glass is governed by two pH-dependent processes. At low pH, dissolution is governed by reactions occurring predominantly at non-Si sites and residual Si-rich gels develop at the glass surface as B, Al and modifier cations are selectively leached. Here, extensive proton promoted hydrolysis of BO and AlO bonds is coupled with hydration and ion exchange processes. Hydrolysis of siloxane bonds governs the rate of dissolution at high pH and the glass dissolves congruently as the silicate network breaks down extensively. Differences in the surface chemistries and morphologies of glass samples reacted in strongly acidic and highly alkaline media reflect the net effects of these processes. The rate of the congruent dissolution process is influenced by the activity of silicic acid. The results are compared with published data for other glass formulations and are discussed in the context of proposed kinetic dissolution models.     

A Study on the Dissolution Kinetics of Basalt—Water Interaction under Different pH Conditions I：Release of Elements and pH Neutralization Effect

Experimental research on the chemical weathering of alkaline-olivine basalt from Huangyi Mountain,Kuandain County,Liaoning.Province and olivine basalt from Dayangke,Mingxi County,Fujian Province has shown that the acidity of the solution tends to become neutral regardless of what the acidity of the starting solution would be during basalt0-water interaction.We call this phenome-non“pH neutralized Effect”.The dissolved species in the solution were determined and unreacted and reacted sample-surface chemical components involved or uninvolved in reaction were analyzed using X-ray photoelectron spectroscopy(XPS).The results revealed two different mechanisms of dissolution of basalt in acidic and basic solutions.     

The combined effect of pH and temperature on smectite dissolution rate under acidic conditions

The main goal of this paper is to propose a new rate law describing the combined effect of pH (1 to 4.5) and temperature (25 to 70 °C) on smectite dissolution rate, under far from equilibrium conditions, as a step towards establishing the full rate law of smectite dissolution under acidic conditions. Dissolution experiments were carried out using non-stirred flow-through reactors fully immersed in a thermostatic water bath held at a constant temperature of 25.0°C, 50.0°C or 70.0°C ± 0.1°C. Smectite 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 smectite dissolution rate. Low Al/Si ratios were obtained in experiments that were conducted at pH ≥4. These low Al/Si ratios are explained by precipitation of gibbsite and/or diaspore.Dissolution rate increases with temperature and decreases with increasing pH. Dissolution rates of experiments in which ΔG_r ≤ −21 kcal mol ⁻¹, are not affected by deviation from equilibrium. Dissolution rates in most experiments are not affected by the addition of up to 0.3 M NaNO₃ to the input solution.A simple model is used to describe the combined effect of pH and temperature on smectite dissolution rate. According to this model, dissolution rate is linearly proportional to the concentration of adsorbed protons on the mineral surface, and proton adsorption is described using a Langmuir adsorption isotherm. All experimental results at pH <4 were fitted to the model using a multiple non-linear regression. The resulting rate law is:

(A1)     

Surface properties, solubility and dissolution kinetics of bamboo phytoliths

Although phytoliths, constituted mainly by micrometric opal, exhibit an important control on silicon cycle in superficial continental environments, their thermodynamic properties and reactivity in aqueous solution are still poorly known. In this work, we determined the solubility and dissolution rates of bamboo phytoliths collected in the Réunion Island and characterized their surface properties via electrophoretic measurements and potentiometric titrations in a wide range of pH. The solubility product of “soil” phytoliths ( at 25 °C) is equal to that of vitreous silica and is 17 times higher than that of quartz. Similarly, the enthalpy of phytoliths dissolution reaction is close to that of amorphous silica but is significantly lower than the enthalpy of quartz dissolution. Electrophoretic measurements yield isoelectric point pH_IEP = 1.2 ± 0.1 and 2.5 ± 0.2 for “soil” (native) and “heated” (450 °C heating to remove organic matter) phytoliths, respectively. Surface acid-base titrations allowed generation of a 2-pK surface complexation model. Phytoliths dissolution rates, measured in mixed-flow reactors at far from equilibrium conditions at 2 ? pH ? 12, were found to be intermediate between those of quartz and vitreous silica. The dissolution rate dependence on pH was modeled within the concept of surface coordination theory using the equation:

     

Probing interfacial reactions with X-ray reflectivity and X-ray reflection interface microscopy: Influence of NaCl on the dissolution of orthoclase at pOH 2 and 85 °C

The role of electrolyte ions in the dissolution of orthoclase (0 0 1) in 0.01 m NaOH (pOH ∼ 2) at 84 ± 1 °C is studied using a combination of in-situ X-ray reflectivity (XR) and ex-situ X-ray reflection interface microscopy (XRIM). The real-time XR measurements show characteristic intensity oscillations as a function of time indicative of the successive removal of individual layers. The dissolution rate in 0.01 m NaOH increases approximately linearly with increasing NaCl concentration up to 2 m NaCl. XRIM measurements of the lateral interfacial topography/structure were made for unreacted surfaces and those reacted in 0.01 m NaOH/1.0 m NaCl solution for 15, 30 and 58 min. The XRIM images reveal that the dissolution reaction leads to the formation of micron-scale regions that are characterized by intrinsically lower reflectivity than the unreacted regions, and appears to be nucleated at steps and defect sites. The reflectivity signal from these reacted regions in the presence of NaCl in solution is significantly lower than that calculated from an idealized layer-by-layer dissolution process, as observed previously in 0.1 m NaOH in the absence of added electrolyte. This difference suggests that dissolved NaCl results in a higher terrace reactivity leading to a more three-dimensional process, consistent with the real-time XR measurements. These observations demonstrate the feasibility of XRIM to gain new insights into processes that control interfacial reactivity, specifically the role of electrolytes in feldspar dissolution at alkaline conditions.     

同步辐射软X射线吸收谱与发射谱测定天然针铁矿能带结构

天然半导体矿物由于成分、缺陷复杂,传统测试方法如紫外可见漫反射等难以准确测定其禁带宽度.本文以针铁矿为例,通过第一性原理计算得到纯针铁矿及掺Al针铁矿的电子结构.计算结果显示,纯针铁矿导带底与价带顶均由Fe3d与O2p轨道组成,而当含杂质Al时,Al2p与O2p发生杂化参与了价带组成.在此基础上,利用同步辐射X射线氧的K边吸收谱与发射谱对纯针铁矿及天然针铁矿的能带结构进行了测定.结果表明,天然含Al的针铁矿禁带宽度为2.30eV,小于纯针铁矿(2.57eV).本研究提供了一种测定天然氧化物矿物禁带宽度的新方法,为深入研究天然半导体可见光催化活性产生机制提供了理论依据.     

The kinetics of the dissolution of chlorite as a function of pH and at 25°C

Far from equilibrium, quasi-steady state dissolution rates of an iron rich chlorite (Mg_2.76Fe²⁺_1.90Fe³⁺_0.07Al_0.97)[Si_2.48Al_1.52O₁₀](OH)₈, have been measured as a function of H⁺ concentration for the pH range 3 to 10.5 and at 25°C. The rates were determined using a single pass flow through cell and with a time frame for observing the steady state condition of between 10 to 50 days. Rates are independent of the buffers used to control the pH, sample preparation, experimental methodology and chlorite composition. The results were collated with literature values allowing the rate to be expressed as a function of H⁺ as;

     

Dehydration kinetics of muscovite by in situ infrared microspectroscopy

Dehydration behavior of muscovite flake was investigated at 760–860°C by using in situ high-temperature IR microspectroscopy for the OH absorption band around 3,620 cm⁻¹. Isothermal kinetic heating experiments at each temperature gave detailed decrease curves of the OH band area with time. These curves have been simulated by the first and second order reactions or mono- and two-dimensional diffusion processes. The mono-dimensional diffusion was found to give the best fit to the experimental data and apparent diffusion coefficients D were determined at 760–860°C with the activation energy of 290 ± 20 kJ/mol. The apparent diffusion coefficients D varied with the sample thickness L. This variation can be explained by an m layers model with a unit length of L′ with a constant diffusion coefficient D′. Therefore, the dehydration process might be rate-limited by mono-dimensional diffusion through tetrahedral silicate sheet perpendicular to (001) planes of muscovite with a unit length of L′.     

Dissolution kinetics of soil clays in sulfuric acid solutions: Ionic strength and temperature effects

Significant amounts of sulfuric acid (H₂SO₄) rich saline water can be produced by the oxidation of sulfide minerals contained in inland acid sulfate soils (IASS). In the absence of carbonate minerals, the dissolution of phyllosilicate minerals is one of very few processes that can provide long-term acid neutralisation. It is therefore important to understand the acid dissolution behavior of naturally occurring clay minerals from IASS under saline–acidic solutions. The objective of this study was to investigate the dissolution of a natural clay-rich sample under saline–acidic conditions (pH 1–4; ionic strengths = 0.01 and 0.25 M; 25 °C) and over a range of temperatures (25–45 °C; pH 1 and pH 4). The clay-rich sample referred to as Bottle Bend clay (BB clay) used was from an IASS (Bottle Bend lagoon) in south-western New South Wales (Australia) and contained smectite (40%), illite (27%), kaolinite (26%) and quartz (6%). Acid dissolution of the BB clay was initially rapid, as indicated by the fast release of cations (Si, Al, K, Fe, Mg). Relatively higher Al (pH 4) and K (pH 2–4) release was obtained from BB clay dissolution in higher ionic strength solutions compared to the lower ionic strength solutions. The steady state dissolution rate (as determined from Si, Al and Fe release rates; R_Si, R_Al, R_Fe) increased with decreasing solution pH and increasing temperature. For example, the highest log R_Si value was obtained at pH 1 and 45 °C (−9.07 mol g⁻¹ s⁻¹), while the lowest log R_Si value was obtained at pH 4 and 25 °C (−11.20 mol g⁻¹ s⁻¹). A comparison of these results with pure mineral dissolution rates from the literature suggests that the BB clay dissolved at a much faster rate compared to the pure mineral samples. Apparent activation energies calculated for the clay sample varied over the range 76.6 kJ mol⁻¹ (pH 1) to 37.7 kJ mol⁻¹ (pH 4) which compare very well with the activation energy values for acidic dissolution of monomineralic samples e.g. montmorillonite from previous studies. The acid neutralisation capacity (ANC) of the clay sample was calculated from the release of all structural cations except Si (i.e. Al, Fe, K, Mg). According to these calculations an ANC of 1.11 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 (I = 0.25 M, 25 °C) compared to an ANC of 0.21 kg H₂SO₄/tonne clay/day at pH 4 (I = 0.25 M, 25 °C). The highest ANC of 6.91 kg H₂SO₄/tonne clay/day was provided by clay dissolution at pH 1 and at 45 °C (I = 0.25 M), which is more than three times higher than the ANC provided under the similar solution conditions at 25 °C. In wetlands with little solid phase buffering available apart from clay minerals, it is imperative to consider the potential ANC provided by the dissolution of abundantly occurring phyllosilicate minerals in devising rehabilitation schemes.     

Temperature dependence of calcite dissolution kinetics between 1 and 62°C at pH 2.7 to 8.4 in aqueous solutions

The kinetics of calcite dissolution in aqueous KCl-solutions far from equilibrium, between 1 and 62°C in the pH-range 2.7 to 8.4 have been investigated using a rotating disc apparatus. At neutral and alkaline pH in the mixed kinetic regime the empirical apparent activation energy (EAAE) for the surface chemical reaction rate constant is 54 ± 4 kJ mole^?1 for Carrara marble and 46 ± 4 kJ mole^?1 for Iceland spar. Under similar conditions the EAAE of the transport rate constant increases with decreasing temperature, but has a mean value of 27 ± 2 kJ mole^?1. The corresponding diffusion coefficient has a mean EAAE of 37 ± 3 kJ mole^?1 and this high EAAE is consistent with transport dependence on product diffusion in this H⁺-independent regime.In contrast, in acid solutions, where the rate approaches end-member transport control, the EAAE of the diffusion coefficient is 16 kJ mole^?1, also decreasing with increasing temperature. This is compatible with H⁺-diffusion to the surface being rate-controlling.In inhibitor-free natural systems, calcite dissolution kinetics far from equilibrium can be described in terms of three regimes: an H⁺-dependent regime (pH < 4 at 25°C), a transition regime (4 < pH < 5.5 at 25°C) and an H⁺-independent regime (pH > 5.5 at 25°C). At lower temperatures these boundaries move to higher pH values. The presence of inhibitors in natural systems may enhance surface controlled kinetics.