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1.
The results of established crystal growth theory and silicate dissolution experiments are combined in developing a new model for mineral/water reactions controlled by surface processes. The overall reaction rate at steady-state is determined by coupling equations for the velocities of mass transport and interface detachment processes. Non-steady state processes can be successfully treated when interface reactions control the rate. For most sparingly soluble minerals, diffusion through the solution can be neglected as a rate-determining factor.Many surface processes are driven by the total interface under saturation, but only processes facilitating detachment contribute to dissolution. Other, non-detachment related, surface reactions result in lower dissolution rates. Slow rates of many mineral/solution reactions are attributed to the surface processes which consume the energy that would otherwise drive detachment.An analysis of the time dependence of interface reaction velocities indicates that linear rate laws apply when uniform detachment or layer-source generation mechanisms such as screw dislocations control the dissolution rate. At low interfacial undersaturations, first-order, logarithmic rate laws prevail. A parabolic time dependence occurs if surface detachment parameters vary as a function of (time)12.  相似文献   

2.
J. Wheeler 《地学学报》1991,3(2):123-136
Textures in rocks reflect the interactions of driving forces and the mechanisms allowing them to induce change. The driving forces are excess chemical energy induced by changing pressure and temperature, deviatoric stress, and surface energy. The mechanisms whereby they are manifest include diffusion (in grains, fluids and grain boundaries), surface reaction, dislocation creep and nucleation. Emphasis is put on the first two processes in this discussion. Diffusion is frequently important in metamorphic reactions and is the dominant chemical means whereby stress induces shape change (pressure solution). Conversely, surface and interface reaction (and not surface energy anisotropy) control growth and dissolution of euhedral grains. Processes of texture development in turn affect the driving forces, in particular creating new transient forces. Thus a purely chemical driving force induced by, for example, temperature change, can lead to the buildup of stresses whose chemical effect reaches a comparable magnitude. Similarly, surface-reaction controlled growth of grains can give rise to large local surface energies which themselves drive further changes. Detailed grain-scale models are required to describe these phenomena; attempts to 'average' properties such as diffusion or reaction on the scale of many grains can give rise to misleading inferences. Instead, local buffering of species in individual grain boundaries can have a great effect on overall transport properties and texture development. Not only measurements of diffusion and reaction rate parameters, but also consistent qualitative models for texture development are required to characterize these processes.  相似文献   

3.
The dissolution of pyrite is of interest in the formation of acid mine drainage and is a complex electrochemical process. Being able to measure the rate of dissolution of particular pyrite samples under particular conditions is important for describing and predicting rates of AMD generation. Electrochemical techniques offer the promise of performing such measurements rapidly and with small samples. The oxidation of pyrite and the reduction of Fe3+ ions and/or O2 half reactions involved in the pyrite dissolution process were investigated by cyclic voltammetry and steady-state voltammetry using three pyrite materials formed in both sedimentary and hydrothermal environments. For each sample, two kinds of pyrite working electrodes (conventional constructed compact solid electrode, and carbon paste electrode constructed from fine-grained pyrite particles) were employed. Results indicated that for both the hydrothermal and sedimentary pyrite samples the oxidation and reduction half reactions involved in dissolution were governed by charge transfer processes, suggesting that hydrothermal and sedimentary pyrites obey the same dissolution mechanism despite their different formation mechanisms. In addition, the results showed that it is feasible to use a C paste electrode constructed from fine-grained or powdered pyrite to study the pyrite dissolution process electrochemically and to derive approximate rate expressions from the electrochemical data.  相似文献   

4.
We present an experimental investigation on the dissolution of uniaxially stressed crystals of NaClO3 in contact with brine. The crystals are immersed in a saturated fluid, stressed vertically by a piston and monitored constantly in situ with a CCD camera. The experiments are temperature-controlled and uniaxial shortening of the sample is measured with a high-resolution capacitance analyzer. Once the crystal is stressed it develops dissolution grooves on its free surface. The grooves are oriented with their long axis perpendicular to the direction of compressive stress and the initial distance between the parallel grooves is in accordance with the Asaro-Tiller-Grinfeld instability. We observe a novel, transient evolution of this roughness: The grooves on the crystal surface migrate upwards (against gravity), grow in size and the inter-groove distance increases linearly with time. During the coarsening of the pattern this switches from a one-dimensional geometry of parallel grooves to a two-dimensional geometry with horizontal and vertical grooves. At the end of the experiment one large groove travels across the crystal and the surface becomes smooth again. Uniaxial shortening of the crystal by pressure solution creep decays exponentially with time and shows no long term creep within the range of the resolution of the capacitance analyzer (accuracy of 100nm over a period of 14 days). This indicates that, while active, the fast transient processes on the free surface increase the solution concentration and thereby significantly slow down or stop pressure solution at the top of the crystal. This novel feedback mechanism can explain earlier results of cyclic pressure solution creep and demands development of a more complex theory of pressure-solution creep including processes that act on free surfaces.  相似文献   

5.
Deep dissolution affects great part of soluble rocks (e.g. gypsum and anhydrite) of the Western Italian Alps. The related superficial phenomena (sinkholes, gravity-induced processes and a local worsening of geomechanical rock properties) are not limited to typical karsts landscape and cause slope instability also affecting populated sites and infrastructures. The paper aims to describe general characteristic of dissolution phenomena, to interpret their conditioning factors and evolutionary stages and to assess possible hazards due to their superficial effects.The search for evidences of deep dissolution leads to the selection of representative sites in the central part of the Western Italian Alps (Piemonte and Valle d'Aosta Region). Detailed geological and geomorphological studies have been used to classify the selected sites by type, size and variable state of activity. Very different evolutionary stages of dissolution phenomena have been interpreted by comparison of case-studies: some are early “embryonic”; others are more evolved, up to typical sinkholes, or even remodelled by other phenomena. Some cases show an extreme complexity in the interactions between corrosion phenomena and other geomorphic processes: slope deformations, from one side, and karst, fluvial and glacial phenomena, to the other. A wide range of movement rates on slope instabilities induced by deep dissolution have been estimated by topographic and geomorphic data. Geochemical data on removed rocks by dissolution indicate 0.4 mm/year values for local subsidence. Historical and technical data indicate low frequency of major dissolution-induced collapses, but highlight widespread damages to tunnels, roads and buildings, especially along slopes.  相似文献   

6.
The dissolution of Iceland spar in CO2-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.  相似文献   

7.
Dissolution?Cprecipitation phenomena induced by CO2 injection to Altmark Permian sandstone were observed through laboratory experiments carried out under simulated reservoir conditions (125?°C and 50 bars of pressure). The rock sample was collected from the Altmark gas reservoir, which is being considered for enhanced gas recovery. Two sets of experiments were performed with pulverized rock samples in a closed batch reactor with either pure water (run 1) or 3?M aqueous NaCl solution (run 2) and reacted with injected CO2 for 3, 5, and 9?days. The liquid samples were analyzed by inductively coupled plasma optical emission spectroscopy and total reflection X-ray fluorescence, where the latter proved to be a feasible alternative to conventional analytical techniques, especially since only small sample volumes (about 10???l) are needed. Chemical analysis for both fluids (water and NaCl brine) indicated a significant dissolution of calcite and anhydrite in the solution, which might be a crucial process during CO2 injection. The brine solution enhanced the dissolution of calcite and anhydrite compared to pure water at the beginning of the reaction. Moreover, the progressive higher Si4+/Al3+ molar ratios (in average by a factor of 3) in the brine experiments indicated quartz dissolution. Thermodynamic calculations of mineral saturation indices highlighted the dissolution of the Ca-bearing minerals, which was in agreement with experimental results. Modeling enabled an evaluation of the dissolution processes of minerals in a low-salinity region, yet hindrances to model more saline conditions emphasize the need for further laboratory studies in order to parameterize models for deep aquifer conditions.  相似文献   

8.
Oxidative dissolution of natural rhodochrosite by the Mn(II) oxidizing bacterium Pseudomonas putida strain MnB1 was investigated based on batch and electrochemical experiments using natural rhodochrosite as the working electrode. Tafel curves and batch experiments revealed that bacterial exopolymers (EPS) significantly increased dissolution of natural rhodochrosite. The corrosion current significantly increased with reaction time for EPS treatment. However, the corrosion process was blocked in the presence of cells plus extra EPS due to formation of the passivation layer. Moreover, the scanning electron microscopy and the energy dispersive spectroscopy (SEM–EDS) results showed that the surface of the natural rhodochrosite was notably changed in the presence of EPS alone or/and bacterial cells. This study is helpful for understanding the role of EPS in bacterially oxidation of Mn(II). It also indicates that the Mn(II) oxidizing bacteria may exert their effects on Mn(II) cycle and other biological and biogeochemical processes much beyond their local ambient environment because of the catalytically dissolution of solid Mn(II) by EPS and the possible long distance transport of the detached EPS.  相似文献   

9.
《Chemical Geology》2003,193(1-2):93-107
In situ atomic force microscopy (AFM) experiments, scanning electron microscopy (SEM) imaging and composition analysis, and X-ray diffraction have provided information about the growth, dissolution and transformation processes promoted by Sr2+–Ca2+–CO32− aqueous solutions in contact with calcite {101̄4} surfaces. Experiments have shown a wide variety of surface phenomena, such as the influence of the Sr-bearing newly-formed surface on the subsequent growth (template effect), the growth and subsequent dissolution of surfaces and the nucleation of secondary three-dimensional nuclei on calcite surfaces. These phenomena reveal the metastability of the crystallisation system and are a consequence of the interplay between thermodynamics (the relative stability of the two calcite and aragonite structure solid solutions that can be formed), supersaturation of the aqueous solution with respect to the two possible solid solutions, and the crystallographic control of the surfaces on cation incorporation.  相似文献   

10.
A numerical model is presented to describe the evolution of fracture aperture (and related permeability) mediated by the competing chemical processes of pressure solution and free‐face dissolution/precipitation; pressure (dis)solution and precipitation effect net‐reduction in aperture and free‐face dissolution effects net‐increase. These processes are incorporated to examine coupled thermo‐hydro‐mechano‐chemo responses during a flow‐through experiment, and applied to reckon the effect of forced fluid injection within rock fractures at geothermal and petroleum sites. The model accommodates advection‐dominant transport systems by employing the Lagrangian–Eulerian method. This enables changes in aperture and solute concentration within a fracture to be followed with time for arbitrary driving effective stresses, fluid and rock temperatures, and fluid flow rates. This allows a systematic evaluation of evolving linked mechanical and chemical processes. Changes in fracture aperture and solute concentration tracked within a well‐constrained flow‐through test completed on a natural fracture in novaculite (Earth Planet. Sci. Lett. 2006, in press) are compared with the distributed parameter model. These results show relatively good agreement, excepting an enigmatic abrupt reduction in fracture aperture in the early experimental period, suggesting that other mechanisms such as mechanical creep and clogging induced by unanticipated local precipitation need to be quantified and incorporated. The model is applied to examine the evolution in fracture permeability for different inlet conditions, including localized (rather than distributed) injection. Predictions show the evolution of preferential flow paths driven by dissolution, and also define the sense of permeability evolution at field scale. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

11.
Dissolution experiments of a tholeiite basalt glass carried out at different pH and T (up to 300°C) using a rotatingdisc apparatus show that, depending on pH and T, dissolution can be controlled by one of the following steps: (1) surface reaction; (2) transport of reactants in solution; and (3) mixed reaction. The activation energies of these different processes were found to be 60, 9 and 15–50 kJ mol−1, respectively. Taking account of these results, it appears likely that surface reactions are not rate limiting for the hydrolysis of most crystalline silicate minerals in hydrothermal and metamorphic processes, and that caution should be exercised when predicting rate of reactions at high temperatures solely on the basis of activation energies measured at low temperatures.

Comparison of experimental and theoretical potentiometric titrations of the basalt glass and its constituent oxides indicates that the adsorption of H+ and OH− ions at the basalt surface is metal cation specific and that the net adsorption can be predicted from the sole knowledge of the acidity constants of the network-forming constituent oxides. We found that in the acidic pH region dissolution is promoted by the adsorption of H+ on al and Fe surface sites while in the basic region, dissolution is promoted by the adsorption of OH− on Si sites. The combination of the two distinct types of surface sites, Al and Fe on the one hand, and Si on the other hand, results in a dissolution rate minimum at a pH-value between the pHzpc of the two groups of oxide components. Linear regressions with a slope n=3.8 are observed both in acid and alkaline solutions in logarithmic plots of the rate of dissolution vs. the surface charge. The value of n, which represents the number of protonation or hydroxylation steps prior to metal detachment, has been found equal to the mean valence of the network-forming metals.

Combining concepts of surface coordination chemistry with transition state theory afforded characterisation of the activated complexes involved in basalt dissolution processes. From the values obtained for the thermodynamic properties of activation for basalt dissolution it is assumed that the activated complexes formed during the H2O-promoted dissolution of the basalt glass are more tightly bonded than those formed during H+- or OH−-promoted dissolution.  相似文献   


12.
《Chemical Geology》2006,225(3-4):322-335
This work deals with the growth behaviour of calcite {101¯4} surfaces in contact with multicomponent aqueous solutions containing divalent cations (Ba2+, Sr2+, Mn2+, Cd2+, or Mg2+). The result is the formation of solid solutions, with calcite or aragonite as one of the end-members. In situ atomic force microscopy has revealed a wide variety of surface phenomena occurring during the formation of these solid solutions. Among them are: (1) the thickening of growth steps and the subsequent dissolution of surfaces followed by the nucleation of secondary three-dimensional nuclei on calcite surfaces, (2) the transition between growth mechanisms, (3) the formation of an epitaxial layer that armours the substrate from further dissolution and (4) the inhibitory effect of the newly formed surface on the subsequent growth (template effect). The two last phenomena can considerably limit coprecipitation as an effective mechanism for divalent metal uptake. All the phenomena described are a consequence of the interplay between thermodynamics, supersaturation of the aqueous solution with respect to the possible solid solutions and the crystallographic control of the surfaces on the cation incorporation, and indicates that there are many differences between the crystal growth of solid solutions and phases with fixed composition.  相似文献   

13.
The kinetics of dissolution of natural enargite in ammoniacal solution has been investigated. Unlike other copper sulfide minerals, the dissolution of copper from enargite is very slow and only 60% of the copper is extracted after 24 hours. The rate of dissolution is favored by high temperatures and high oxygen pressures. The experimental data seem to fit an electrochemical mechanism.  相似文献   

14.
Chalcopyrite bio-dissolution plays an important role in the processing of copper sulfide ores. However, due to the slow dissolution rates of CuFeS2, bio-dissolution processes have not yet found widespread application. In order to enhance the dissolution of chalcopyrite, a novel method for enhancing the dissolution using ozone was proposed and verified. The generated products in chalcopyrite dissolution process in the presence of Leptospirillum ferrooxidans and Acidithiobacillus thiooxidans was studied. The X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) results indicate that a surface layer mainly consisting of jarosite and polysulfide (Snn−/S0) might be formed during biotic stage, which can be eliminated with the introduction of ozone. Electrochemical results show that ozone significantly increased the electrochemical reactivity of bioleached chalcopyrite, further proving that ozone enhanced the dissolution through destroying the surface layer. Hence, a bi-stage method for dissolution of chalcopyrite can be proposed.  相似文献   

15.
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.  相似文献   

16.
Little or no information is available in the literature about reaction processes of co-sorbing metals and arsenate [As(V)] on variable-charged surfaces or factors influencing these reactions. Arsenic and metal contamination are, however, a common co-occurrence in many contaminated environments. In this study, we investigated the co-sorption kinetics of 250 μM As(V) and zinc [Zn(II)] in 10, 100, and 1000 mg goethite L−1 0.01 M NaCl solution at pH 7, collected complementary As and Zn K-edge extended X-ray absorption fine structure (EXAFS) data after various aging times, and performed a replenishment desorption/dissolution study at pH 4 and 5.5 after 6 months of aging time. Arsenate and Zn(II) formed adamite-like and koritnigite-like precipitates on goethite in 100- and 10-ppm goethite suspensions, respectively, whereas in 1000-ppm goethite suspensions, As(V) formed mostly double-corner sharing complexes and Zn(II) formed a solid solution on goethite according to EXAFS spectroscopic analyses. In all goethite suspension densities, surface adsorption reactions were part of the initial reaction processes. In 10- and 100-ppm goethite suspensions, a heterogeneous nucleation reaction occurred in which adamite-like precipitates began to form 48 h earlier than koritnigite-like surface precipitates. Arsenate and Zn(II) uptake from solution decreased after 4 weeks. Replenishment desorption studies showed that the precipitates and surface adsorbed complexes on goethite were susceptible to proton-promoted dissolution resulting in many cases in more than 80% loss of Zn(II) and ∼ 60% to 70% loss of arsenate. The molar Zn:As dissolution ratio was dependent on the structure of the precipitate and was cyclic for the adamite and koritnigite-like surface precipitates, reflecting the concentric and plane-layered structures of adamite and koritnigite, respectively.  相似文献   

17.
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.  相似文献   

18.
In situ measurements of mineral surface evolution during the process of pressure solution are possible with the high brightness of synchrotron X-ray sources. This capability has been explored through the use of newly developed reaction vessels that allow transmission of the incident and scattered X-ray beam through a low atomic weight piston. Several new vessels are described, along with details of computational algorithms that are used to simulate X-ray scattering in this unconventional geometry. Results using calcite (CaCO3) and halite (NaCl) as reactant crystals are presented and compared to other atomic-scale measurements of surface dissolution processes. Calcite was reacted with an unsaturated fluid at 30 bars of pressure for approximately 24 h. During reaction the root mean square surface roughness (σ) evolved from 13.7 Å (± 0.5 Å) to 19.5 Å (± 1.0 Å), giving a roughening rate of: dσ/dt = +6.3 × 10− 5 Å s− 1. This is consistent with other measurements made with free calcite surfaces and is driven almost entirely by chemical disequilibrium. Analysis of the surface ex situ post-reaction gives an identical σ value, showing that the in situ measurements are well-constrained. Experiments also at 30 bars but in a saturated solution indicate that the calcite surface does not significantly roughen, giving the result that pressure solution of calcite at this pressure cannot be monitored in experiments of several days duration. Experiments with halite, a much more reactive phase, in saturated solutions showed the reflectivity profile to be dynamic on a time scale of hours. This experiment was left to reach equilibrium over 108 days and then re-analyzed, showing that σ had increased from 34 Å (± 2 Å) to 41 Å (± 2 Å), giving a roughening rate of: dσ/dt ≤ +6.4 × 10− 7 Å s− 1. This is two orders of magnitude smaller than the calcite roughening rate caused by chemical disequilibrium and provides the first direct in situ atomic-scale measurement of the rate of surface roughening due to pressure solution.  相似文献   

19.
The dissolution of crinoid columnals during tectonic deformation of the Appalachian Plateau was enhanced by stress-induced changes of chemical potential of calcite in solution at the surface of the crinoid columnal. Pressure solution on the outside surface occurred within areas of highest normal stress developed at grain to grain contacts whereas free-face dissolution on the inside bore (the axial canal) of the columnal occurred where parts of the crystal lattice next to the surface were subject to the highest strain, as indicated by the presence of mechanical twins. For free-face dissolution, the chemical potential of the solute is affected more by the larger strain energy associated with mechanical twinning than strain energy from elastic strain prior to mechanical twinning of the crystal lattice. These observations suggest that free-face dissolution as well as pressure solution may contribute significantly to dissolution during rock deformation by diffusive mass transfer.  相似文献   

20.
Early stage processes of Mg-rich chlorite (clinochlore) dissolution were examined, focusing especially on the structural modification at grain edges during dissolution. Focused ion beam transmission electron microscopy sample preparation was applied to crystals dissolved in a flow-through reaction system at pH 3.0 and 25°C for 31 days. The obtained Si and Mg dissolution rates are −11.49 and −11.14 (logR, mol/(m2/s)), respectively, implying dissolution is non-stoichiometric. TEM-EDX analyses of dissolved samples reveal the development of 20–50-nm thick amorphous zone at an outermost rim with a chemical gradient of Mg, lower towards the solid surface, and Si enrichment in this amorphous zone. Crystalline material is partially interwoven with amorphous one at the interface between the amorphous and crystalline regions. These results indicate that the amorphous zone was produced by selective leaching of cations except for Si. Chlorite dissolution may proceed via the formation and thickening of leached layer as a by-product of release to solution of Si at slightly slower rate than Mg.  相似文献   

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