Dissolution study of tremolite and anthophyllite: pH effect on the reaction kinetics

The effect of pH on the kinetics of tremolite and anthophyllite dissolution was investigated at 25 °C in batch reactors over the pH range of 1–13.5, in inorganic buffered solutions. Dissolution rates were obtained based on the release of Si and Mg. Results obtained in this study show different behaviors for both minerals. For tremolite, dissolution rates show a noticeable dependence on pH between 1 and 8, decreasing as pH increases and reaching a minimum around neutral conditions. At basic pH this dependence becomes even stronger, but dissolution takes place together with collateral effects of saturation and carbonation. A preferential release of Ca and Mg is observed in acid media, lowering the Mg/Si ratio to the extent that Mg solubility decreases with pH. For anthophyllite, dissolution rates also show a strong dependence on pH, between 1 and 9.5. At the same pH, anthophyllite dissolves up to 8 times faster than tremolite. For pH > 9.5 this dependence is smooth, and it is probably associated with effects of saturation and carbonation. Dissolution is also non-stoichiometric with a faster release of Mg with respect to Si in acid media. SEM observations show differences in the breakage mechanism of the fibers. The anthophyllite particle breakage during dissolution consists of the splitting of bundle fibers parallel to the fiber longitudinal direction. However, for tremolite, other than fiber splitting, particles shorten induced by coalescence of etch pits developed perpendicular to c axe.     

Albite dissolution kinetics as a function of distance from equilibrium: Implications for natural feldspar weathering

Determining the kinetics of many geologic and engineering processes involving solid/fluid interactions requires a fundamental understanding of the Gibbs free energy dependency of the system. Currently, significant discrepancies seem to exist between kinetic datasets measured to determine the relationship between dissolution rate and Gibbs free energy. To identify the causes of these discrepancies, we have combined vertical scanning interferometry, atomic force microscopy, and scanning electron microscopy techniques to identify dissolution mechanisms and quantify dissolution rates of albite single crystals over a range of Gibbs free energy (−61.1 < ΔG < −10.2 kJ/mol). During our experiments, both a previously dissolved albite surface exhibiting etch pits and a pristine surface lacking dissolution features were dissolved simultaneously within a hydrothermal, flow-through reactor. Experimental results document an up to 2 orders of magnitude difference in dissolution rate between the differently pretreated surfaces, which are dominated by different dissolution mechanisms. The rate difference, which persists over a range of solution saturation state, indicates that the dissolution mechanisms obey different Gibbs free energy dependencies. We propose that this difference in rates is the direct consequence of a kinetic change in dissolution mechanism with deviation from equilibrium conditions. The existence of this kinetic “switch” indicates that a single, continuous function describing the relationship between dissolution rate and Gibbs free energy may be insufficient. Finally, we discuss some of the potential consequences of our findings on albite’s weathering rates with a particular focus on the sample’s history.     

Dissolution kinetics of synthetic Na-smectite. An integrated experimental approach

The effect of pH and Gibbs energy on the dissolution rate of a synthetic Na-montmorillonite was investigated by means of flow-through experiments at 25 and 80 °C at pH of 7 and 9. The dissolution reaction took place stoichiometrically at 80 °C, whereas at 25 °C preferential release of Mg over Si and Al was observed. The TEM-EDX analyses (transmission electronic microscopy with quantitative chemical analysis) of the dissolved synthetic phase at 25 °C showed the presence of newly formed Si-rich phases, which accounts for the Si deficit. At low temperature, depletion of Si concentration was attributed to incongruent clay dissolution with the formation of detached Si tetrahedral sheets (i.e., alteration product) whereas the Al behaviour remains uncertain (e.g., possible incorporation into Al-rich phases). Hence, steady-state rates were based on the release of Mg. Ex situ AFM measurements were used to investigate the variations in reactive surface area. Accordingly, steady-state rates were normalized to the initial edge surface area (11.2 m² g⁻¹) and used to propose the dissolution rate law for the dissolution reactions as a function of ΔG_r at 25 °C and pH∼9:

     

The dependence of albite feldspar dissolution kinetics on fluid saturation state at acid and basic pH: Progress towards a universal relation

Here we report on two separate ongoing, multi-year investigations on the dependence of the dissolution rate (R) of albite feldspar on fluid saturation state, as defined by the Gibbs free energy of reaction (ΔG_r) for dissolution. The investigations are based on dissolution at pH 9.2, 150 °C and pH 3.3, 100 °C. Both studies reveal that the R–ΔG_r relation is highly non-linear and sigmoidal. The kinetic data from the first study, being the most complete, can be fitted with a sigmoidal rate curve that is composed of two separate, parallel rate laws that represent distinct mechanisms of dissolution. The switch between one dominant mechanism and the other may be controlled by a critical free energy. The fact that in both studies the same type of sigmoidal R–ΔG_r relation exists for dissolution at different pH and temperature condition suggests that this behavior may be universal for albite and other feldspars. Moreover, the experimental data contradict the commonly used R–ΔG_r relation that is loosely based on transition state theory (TST). This has important implications with respect to the accuracy of geochemical codes that model water–rock interactions at near-equilibrium conditions.     

利用钾长石粉体合成雪硅钙石的实验研究

以氧化钙为反应物料,在200～250℃的水热反应条件下分解钾长石。实验研究了在不同的Ca/(Si Al)摩尔比、水固比、反应温度和反应时间条件下,钾长石中K2O的溶出率和固相的物相变化。结果表明,液相中K2O的溶出率为40%～87%,固相反应产物为结晶良好雪硅钙石晶体。采用化学分析、XRD、SEM、DSC_TG和BET等方法对合成的雪硅钙石粉体进行了表征,结果表明,合成的雪硅钙石粉体是由长5～10μm、宽100～200nm、厚度为49～50nm的薄片纤维晶体交织成的直径为30～40μm的空心球形团聚体,耐火温度高于650℃,是制备硅酸钙保温材料的良好原料。     

An experimental study of the diffusion of oxygen in quartz and albite using an overgrowth technique

Diffusion rates of¹⁸O tracer in quartz ( c, 1 Kb H₂O) and Amelia albite ( 001, 2 Kb H₂O) have been measured, using Secondary Ion Mass Spectrometry (SIMS). A new technique involving hydrothermal deposition of labelled materials has removed the possibility of pressure solution-reprecipitation processes adversely affecting the experiments. Reported diffusion constants are:-quartz ( c), ,Q=98±7 KJ mol^–1 (600–825° C, 1 Kb); Amelia albite ( 001), ,Q=85±7 KJ mol^–1, (400–600° C, 2 Kb). Measured quartz¹⁸O diffusivities decrease discontinuously at the- transition, reflecting strong structural influences. The reported albite data agree with previously recorded studies, but-quartz data indicate significantly lower activation energies. Possible causes of this discrepancy, and some geological consequences, are noted.     

The entropy and Gibbs free energy of formation of the aluminum ion

A reevaluation of the entropy and Gibbs free energy of formation of Al³⁺_(aq) yields ?308 ± 15 J/K·mol and 489.4 ± 1.4kj/mol for S⁰₂₉₈ and $\text{ΔG}{}^0{}_{\mathrm{?,298}}$ respectively. The standard electrode potential for aluminum is 1.691 ± 0.005 volts.     

Oxygen regime of granulite metamorphism: Modeling by the method of Gibbs free energy minimization

Using a new version of the Selektor-C program package for the minimization of Gibbs free energy, physicochemical modeling was conducted for real mineral assemblages from the rocks of the Okhotsk and Chogar complexes and the Larba block, which crystallized under granulite-facies conditions. Considering a two-reservoir fluid-rock system, model assemblages of metapelites and metabasites adequate to natural assemblages were reconstructed by the method of Gibbs potential minimization. The P-T parameters of crystallization, oxygen potential, and the composition of the deep fluid that produced the assemblages were estimated. It was shown that the character of oxygen behavior can be dual under granulite-facies metamorphic conditions: inert behavior in rocks enriched in magnetite and (or) hemoilmenite and perfectly mobile behavior (after D.S. Korzhinskii) in rocks devoid of these minerals. It was shown that the oxygen regime is controlled by the degree of complete or partial leveling of oxygen potential between the deep reduced fluid and the rock in agreement with their oxygen capacities.     

针铁矿/水界面反应性的实验研究

选择针铁矿对Pb2+、Cu2+、Cd2+等3种重金属离子的吸附实验,开展矿物/水界面反应性研究.金属离子(M2+)在矿物-水溶液间分配有多种表面反应机制,这些表面反应发生作用的条件主要取决于吸附质水化学性质和矿物表面荷电性,因此,溶液pH值是影响矿物/水界面反应性的关键因素.在不同pH值条件下, 表面羟基可通过发生质子化或去质子化反应而使得矿物表面产生荷电性并发生改变,而金属离子的水解则可显著加快金属羟基配合物的形成,从而进一步增强了矿物/水界面反应.本实验条件下针铁矿表面对重金属离子的吸着量随pH值升高而升高,在一个较窄的pH值范围内吸附率急剧升高,呈S形分布.针铁矿对3种不同的重金属离子的吸附能力的强弱顺序是Cu2+＞Pb2+＞Cd2+.无论是Langmuir方程还是Freundlich方程,都能较好拟合针铁矿对重金属离子的等温吸附过程.Freundlich方程的n值均在0.1～0.5之间,说明重金属离子在针铁矿表面的吸附并不能简单地归结为单配位或双配位模式,可能存在着多种吸附结合形态.表观吸附常数KM值的变化规律,说明重金属离子与针铁矿表面反应模式及其表面吸附形态发生了变化,具体的吸附形态还有待谱学研究进一步证实.     

Distribution function of comminution kinetics — Modelling and experimental study

A mathematical model for distribution function is developed considering the distribution of the number of fractures that can occur in a particle. It is shown as a consequence of the model that selection and distribution functions are intimately related through a single parameter — expected number of fractures per unit original size. This parameter can be comparatively easily obtained from batch experiments and can later be used to simulate industrial-scale grinding mills. Predictions of the model are amply confirmed by preliminary experimental results and other published observations. A correlation is developed to predict the parameter of the model from known equipment and operating variables for the particles used in the present study.     

The effect of coherency stress on the mechanism of the reaction albite+K+⇌K-feldspar+Na+ and on the mechanical state of the resulting feldspar

Coherency stress and coherency strain energy generated by Na⁺?K⁺ ion exchange in alkali feldspars are calculated using an isotropic model, and deformation of single crystals of alkali feldspars exposed to molten alkali chlorides at \(P_{H_2 O} \) < 1 bar is described. Coherency stress in alkali feldspars can reach 10–20 kb. When it is large, partial relaxation by fracture and/or plastic deformation takes place under anhydrous conditions, but temporary build-up of stress is unavoidable even under hydrothermal conditions. Because of coherency strain energy, a thin layer of an end-member alkali feldspar produced by cation exchange on a grain of the other end-member alkali feldspar would be unstable with respect to dissolution. Therefore, under hydrothermal conditions one end-member alkali feldspar replaces the other by dissolution and precipitation. The mechanism of the reaction $$Na_x K_{1 - x} AlSi_3 O_{8_{(feld.)} } + yK^ + \rightleftharpoons Na_{x - y} K_{1 + y - x} AlSi_3 O_{8_{(feld.)} } + yNa^ + $$ is primarily controlled by \(P_{H_2 O} \) and by ΔK/(Na + K), the difference between the equilibrium value and the initial value of the atomic K/(Na + K) ratio of the feldspar. When ¦ΔK/(Na + K)¦ is small, the reaction proceeds by cation exchange. When ¦ΔK/(Na + K)¦ is large, cation exchange still occurs if \(P_{H_2 O} \) is very low, but under hydrothermal conditions replacement by dissolution and precipitation occurs.     

An experimental study of illite dissolution kinetics as a function of ph from 1.4 to 12.4 and temperature from 5 to 50°C

Dissolution rates of natural illite (Illite du Puy) were measured from Si release rates during closed system experiments at pH ranging from 1.4 to 12.4 and temperatures ranging from 5 to 50°C. Experiments performed at 4<pH<11 exhibited reactive fluid Si/Al concentration ratios that were inconsistent with stoichiometric illite dissolution likely due to secondary phase precipitation. In contrast, after an initial preferential release of aluminum relative to silicon, the reactive fluid Si/Al concentration ratio evolution was consistent with stoichiometric illite dissolution for all experiments conducted at 4>pH>11. Si release rate decreased with time during all experiments; for those experiments performed at 4>pH>11 this observation can be attributed to either 1) changing reactive surface area; 2) the effect of initial fine particle dissolution; or 3) a negative order of the illite dissolution reaction with respect to aqueous Al and/or Si. Measured dissolution rates exhibited a typical variation with pH; rates decrease with increasing pH at acid conditions, minimize at near to neutral pH and increase with increasing pH at basic conditions. An empirical expression describing rates obtained in the present study is given by

     

Structural states of natural potassium feldspar: An infrared spectroscopic study

Natural samples of K-feldspar representing various states of Al, Si order were characterised using X-ray methods, transmission electron microscopy, and Fourier transform infrared spectroscopy. Line profiles of infrared absorption bands were observed to show strong correlation with the degree of Al, Si order present. In particular, the absorption frequencies of the 540 cm^?1 and 640 cm^?1 bands were seen to vary by ca. 10 cm^?1 between sanidine and microcline, with modulated samples respresenting intermediate behaviour. Linewidths of these modes also decrease by ca. 50% in this series. The experimental results are discussed within the framework of Hard Mode Infrared Spectroscopy (HMIS), and it is shown that the absorption frequencies vary with the short range order parameter τ = (4t₁-1)² and the symmetry breaking order parameter describing Al, Si order, Q _od=(t₁ 0?t₁ m)/Q _od=(t₁ 0+t₁ m), where t₁ is the average Al occupancy on the T₁ sites and t₁ o and t₁ m are the individual site occupancies of the T₁ o and T₁ m sites, respectively. The structural state of orthoclase is characterised by strain-induced modulations with large spatial variations of the modulation wavelength. No such modulations were observed in the degree of local Al, Si order. Sanidine shows mode hardening in excess of the extrapolated effect of symmetry breaking Al, Si order, which is presumably related to nonsymmetry breaking ordering between T₁ and T₂ sites and/or as yet unobserved short range order of the symmetry breaking ordering scheme. The possibility of an additional phase transition in K-feldspar at temperatures above 1300 K is discussed.     

An experimental study of interaction between pure water and alkaline feldspar at high temperatures and pressures

Due to the important scientific significance of the interaction between alkaline feldspar and high-temperature and high-pressure fluids. We have conducted a series of autoclave experiments of feldspar dissolution and secondary mineral precipitation in conditions of 250–500 °C, 8–50 MPa, and pH = 3.0 and 5.5. Based on the interaction experiments between alkaline feldspar and fluid of high-temperatures and high-pressures, we get the main results as follows: (1) The law that people have grasped below the critical point about the influence of temperature, pressure, and pH value on the alkaline feldspar dissolution behavior is still held above the critical point. (2) Due to the experimental techniques of autoclave flip 180°—sharp quenching and based on electron microprobe analysis of mineral new formed, theoretical analysis has determined that the new altered minerals distributed on the island dissolution surface of feldspar are products of precipitation on a feldspar surface after saturation of the relative ion concentration in water fluid.     

Dissolution rates of phyllosilicates as a function of bacterial metabolic diversity

Weathering experiments using biotite and phlogopite in the presence of bacteria were conducted to better understand biotic dissolution kinetics and processes (proton- and ligand-promoted dissolution) under aerobic conditions. Miniature batch reactors (300 μl in microplate wells) were used at 24 °C for 3 days with and without bacterial strains. Abiotic experiments were performed with organic and nitric acids in order to calibrate the biotite-phlogopite chemical dissolution. An empirical model was used to fit the pH dependence for iron release rate (r_Fe) considering the influence of both protons and ligands from acidic to neutral conditions (pH ranging from 3 to 7): r_Fe=k_H(a_H+)^m+k_L(a_L)¹ where k is the apparent rate constant, a_H+ and a_L are the activities of protons and ligands, and m and l are the reaction orders. For both minerals in most cases at a given pH, the iron release rates in the presence of bacteria were in good agreement with rates determined by the chemical model and could be explained by a combination of proton- and ligand-promoted processes. Bacteria affect mineral dissolution and iron release rates through the quantities and nature of the organic acids they produce. Three domains were differentiated and proposed as biochemical models of mica dissolution: (1) below pH 3, only proton-promoted dissolution occurred, (2) in weakly acidic solutions both ligand- and proton-promoted mechanisms were involved, and (3) iron immobilization occured, at pH values greater than 4 for biotite and greater than 5 for phlogopite. This model allows us to distinguish the “weathering pattern phenotypes” of strains. Bacteria that are isolated from horizons poor in carbon appear more efficient at weathering micas than bacterial strains isolated from environments rich in carbon. Moreover, our results suggest that the mineral could exert a control on the release of organic acids and the “weathering pattern phenotypes” of bacteria.     

离子交换反应合成铅长石的实验研究

对长石与Pb(NO_3)_2粉末在380℃条件下反应48h的产物进行XRD分析,显示出现了d值分别为6.54、3.42、3.32、3.27,2.57的铅长石的5个特征峰。XPS分析表明Pb4f7/2在长石矿物中的结合能为138.39~138.44eV。实验证明Pb2 与长石结构中的碱性或碱土性离子发生了离子交换反应,生成了铅长石。     

硫酸盐还原菌及其代谢物的接触作用影响石膏分解的实验研究

采用透析的方法,研究了硫酸盐还原菌(SRB)及不同分子量(0~200、200~2 000、2 000~10 000)代谢产物与石膏接触时对其还原分解的影响。实验结果表明,SRB代谢产生了更多的碱性物质,导致体系pH值明显上升;随着SRB及其代谢产物与石膏的接触作用逐渐增强,石膏的还原分解能力逐渐提高;SRB及其代谢产物可以诱导形成具有良好结晶形态的方解石和无定形态碳酸盐沉淀;代谢产物除可促进石膏还原分解外,一定条件下也可抑制石膏溶解。研究结果表明,SRB及其代谢物与石膏的接触作用对其还原分解有一定的影响,影响机制主要为络合作用和营造pH值、HCO-3浓度不同于溶液的SRB-石膏界面微环境。     

Dissolution kinetics of magnesite in acidic aqueous solution: a hydrothermal atomic force microscopy study assessing step kinetics and dissolution flux

Magnesite (104) dissolution kinetics were studied in acidic aqueous solutions (2.0 < pH < 4.2) at temperatures between 60 and 90°C by atomic force microscopy (AFM). Comparison of dissolution fluxes obtained by AFM and chemical methods revealed six to seven times larger dissolution fluxes obtained by chemical analysis. Corresponding empirical activation energies were found to be 74 ±22 kJ/mol and 41 ± 4 kJ/mol (at pH 4.2) for the AFM and chemical methods, respectively. The empirical reaction order with respect to proton concentration was 0.36 ± 0.13 and 0.47 ± 0.03 for AFM and chemical methods, respectively. These comparisons suggest that the two experimental measurement methods differ as a result of the different sampling length scales associated with the methods. Negligible changes in step dissolution velocity with changes in bulk pH were found, suggesting that the principal source of increasing dissolution flux with decreasing pH is an increase in step density. However, the observed stable step orientation, which is dependent on pH, suggests that more than one proton adsorption equilibrium should be used to describe the surface chemistry of magnesite in acidic solution.     

Low-grade metamorphic alteration of feldspar minerals: a CL study

ABSTRACT Two styles of feldspar alteration – carbonatization and albitization – were investigated using a cathodoluminescence (CL) technique. The nature of the alteration depends on the composition of the fluids. The infiltration of CO₂-rich fluids causes decomposition of An-rich zones in plagioclase followed by the formation of secondary calcite, albite and white mica. K-feldspar is more resistant to CO₂-induced alteration. The circulation of aqueous fluids results in decomposition of primary oligoclase into albite and clinozoisite. Secondary K-feldspar exsolved as small independent grains on the rim of the primary oligoclase, if the primary plagioclase was enriched in the orthoclase component. The fluids easily penetrate the crystals using, crystallographic plains, e.g., twinning or cleavage or simply along cracks. These migration pathways enable the fluids to enter the inner parts of the grain, which would otherwise not be affected by grain-surface alteration.