The dissolution of biotite and chlorite at 25°C in the near-neutral pH region
ABSTRACT We studied the dissolution of biotite and chlorite in laboratory systems with flow-through and batch reactors. The initial dissolution of biotite in the near-neutral pH region, under N2(g) atmosphere is highly non-stoichiometric. A slow linear release of iron during a period of weeks indicates a surface-chemical-reaction-controlled mechanism of release for iron. The release of potassium is much faster than that of iron. A parabolic dependence of accumulated release with time suggests a diffusion-controlled mechanism of potassium release. The rates of magnesium, aluminium and silicon release are between those for potassium and iron and approach that of iron with time. There is no significant influence of (bi)carbonate or pH on biotite dissolution rate or stoichiometry in the pH region 7 < pH < 8.5. The release rates of elements from chlorite are close to stoichiometric and similar to the iron release rate from biotite. In closed batch reactors at near-basic pH the composition of test solutions in contact with biotite is apparently controlled by gibbsite (Al), kaolinite (Si) and Fe(III)-(hydr)oxide. We estimated a turn-over time (101−102 yr) for molecular oxygen and a time scale (10 months) to develop characteristic Fe(II) concentrations for a granitic groundwater.
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ABSTRACT: The effects of simulant groundwater composition, pH and temperature on the dissolution and alteration of Na- and Ca-montmorillonite have been studied. Prior to the experiments, Wyoming type Na-montmorillonite, Swy-2, was purified to decrease the amount of accessory minerals. For Ca-montmorillonite experiments, the interlayer cation Na+ of purified Swy-2 was exchanged with Ca2+. The batch experiments were conducted with the purified montmorillonites in simulated fresh and saline waters at 25°C and 60°C under anaerobic conditions in an Ar atmosphere. The concentrations of Si, Al, Fe and Mg were analysed from ultra-filtered solution samples with High Resolution Inductively Coupled Plasma Mass Spectrometry (HR-ICP-MS) as a function of dissolution time. The pH evolution was also measured. The solid smectite phases were analysed with X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM). XRD analyses indicated that the nature of the smectite mineral did not change over 140 days. However, the experimental conditions, more or less, modified the structure (e.g. the layer stacking of montmorilllonite; the partial dissolution of the smectite), which cannot be detected by XRD but was evidenced by chemical data, and can be considered as a possible contributor to the stacking faults of the montmorillonite. The log rates (mol g–1 s–1), based on the dissolved amount of Si, varied between –10.64 and –12.13 depending on the experimental conditions.Clay Minerals 05/2013; 48(2). · 0.76 Impact Factor
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ABSTRACT: The chemical composition and charge of the biotite near-surface, in contact with NaCl bearing aqueous solutions at 25 °C from pH 1 to 12, have been derived via zeta potential measurements and potentiometric titrations performed for 20 and 60 min in batch reactors. Zeta potential measurements yielded an isoelectric point of pH 3.0 (±0.2) and batch potentiometric titrations yielded a pH of immersion of 9.66 (S.D. 0.24). From batch potentiometric titrations we determined both the proton consumption and the metal release from the biotite surface as a function of pH. Potassium removal from the near-surface of biotite is only slightly dependent on pH with a minimum of ∼6 atoms nm−2 removed at the immersion pH, corresponding to an average depletion depth of ∼1.5 nm. In contrast, the release of Mg, Al and Fe is strongly pH-dependent as those metals are preferentially removed from the biotite surface at pH less than 9 (Mg) and 4 (Al, Fe). The average depletion depth of Mg, Al, and Fe increases with decreasing pH, reaching on average ∼2 nm at pH ∼1. The removal of K, Mg, Al, and Fe is not charge conservative, resulting in a relative negative charge in the biotite near-surface. Taken together, our results indicate that the composition of the biotite surface varies dramatically as a function of pH. At basic conditions, the biotite near-surface is K depleted and likely hydrogen enriched. At near-neutral conditions, the biotite near-surface is comprised of only the Si and Al tetrahedral, and the Fe(II) octahedral framework, following the removal of both alkali metals and Mg. Finally, at acidic conditions, the biotite near-surface is comprised exclusively of a remnant Si, O and H framework. The results of these experiments give an indication of the composition and charge of the biotite surface in the natural environment, following contact with water, for example in the vadose zone, and can help us understand weathering reactions in these systems.Geochimica et Cosmochimica Acta 03/2014; 128:58–70. · 4.25 Impact Factor
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ABSTRACT: Chlorite dissolution rates were measured in a series of batch reactor experiments testing the effect of pCO2, pH, chloride and bicarbonate concentrations and temperature. Chlorite is an important diagenetic mineral in sedimentary basins, often found cementing mineral grains and filling pore space in formations that may serve as reservoirs for storing carbon dioxide. Conflicting reports of whether chlorite acts as a barrier to reservoir rock reactivity or leads to enhanced porosity due to dissolution, after the injection of supercritical CO2 into a reservoir, makes studying the reactivity of chlorite in contact with CO2 saturated waters pertinent. Measured dissolution rates were initially rapid and decreased over time as the saturation state of solution relative to chlorite increased. Temperature had the strongest effect on dissolution rate, with an apparent activation energy of 16 ± 0.5 kJ mol−1 and rate constant of log k0 = −9.56 ± 0.07 mol m−2 s−1 assuming a rate law of the form: rate = k0exp(−EA/RT). The apparent activation energy is lower than previously accepted values, but is consistent with a study of chlorite dissolution using flow through techniques (Smith et al., 2013). Mineral dissolution rates are typically proton enhanced, but the lack of a significant pH effect or pCO2 effect on chlorite dissolution rate in this study suggests that the use of NaHCO3 to buffer the pH of CO2 saturated solutions led to an inhibition of mineral dissolution in competition with the expected pH effect. This is supported by the observed dissolution rate increasing dramatically (half a log unit) with the use of an organic acid buffer (KHpthalate) under CO2 free conditions. The effect of chloride (NaCl ∼5 to 50 g/L) was found not to affect the dissolution rate of chlorite. Various empirical rate laws are proposed and fit to the data and lead to the development of a surface complex model describing proton promoted dissolution and bicarbonate inhibition of chlorite dissolution rates. The model can be applied to predict the rate of chlorite dissolution under elevated pCO2 conditions relevant to the storage of CO2 in reservoirs from 50 to 275 °C in contact with fluids ranging in pH from 3.4 to 5.4.Geochimica et Cosmochimica Acta 01/2014; 125:225–240. · 4.25 Impact Factor