Carbonate dissolution in the guts of benthic deposit feeders: A numerical model

We present a numerical model to quantify calcite dissolution in the guts of deposit feeding invertebrates. Deposit feeder guts were modeled as constantly stirred reactors (CSTRs) following terminology from digestion theory. Saturation state and dissolution of calcium carbonate were calculated from changes in total dissolved carbon dioxide and alkalinity resulting from sediment passage through the digestive tract, while accounting for dissolution of calcite and respiration of organic carbon. Typical dissolution rates for a gut volume of 1 ml ranged between 0.5-4 mg calcite d⁻¹. Sensitivity analysis revealed gut pH, sediment organic matter (OM) content and OM reactivity to be the critical parameters determining calcite dissolution rate. Carbonate dissolution rate was inversely related to gut pH. However, calcite dissolution was found to be possible even at alkaline gut pH due to respiration by intestinal microbes. The kinetics of calcite dissolution had only marginal influence on daily calcite dissolution rates: Varying the calcite dissolution rate constant κ by six orders of magnitude affected calcite dissolution rates by less than a factor of 10. Calcite dissolution rates were calculated for 4 different hydrographic regimes that differed in their content of sedimentary calcite and OM and furthermore in their OM reactivity. Highest dissolution rates were calculated for the shallow water setting, where relatively high OM content facilitated high microbial respiration rates depressing gut pH. However, dissolution rates for the deep sea setting were only slightly lower, due to greatly elevated ingestion rates resulting from low OM content. As a consequence of much higher faunal abundances, shallow-water benthos is likely to contribute the vast majority of gut-mediated carbonate dissolution. Nevertheless, the fraction of sedimentary calcite that dissolves during one gut passage is probably too small to be observable by simple gravimetric analysis. This may explain the notable scarcity of evidence for gut-mediated carbonate dissolution in the literature to date. Assuming depth-dependent calcite dissolution rates and deposit feeder abundances, we estimate gut-mediated carbonate dissolution to contribute approximately 5% of the annual global sedimentary carbonate dissolution rate, which corresponds to an average calcite dissolution rate of approximately 0.5 mg m⁻² d⁻¹ for the entire ocean floor.     

Quantification of mineral dissolution rates and applicability of rate laws: Laboratory studies of mill tailings

Reliable quantification of mineral weathering rates is a key to assess many environmental problems. In this study, the authors address the applicability of pure mineral laboratory rate laws for dissolution of mill tailings samples. Mass-normalised sulfide and aluminosilicate mineral dissolution rates, determined in oxygenated batch experiments, were found to be different between two samples from the same ∼50-year-old, carbonate-depleted mill tailings deposit. Consideration of difference in particle surface area and mineralogy between the samples resolved most of this discrepancy in rates. While the mineral surface area normalised dissolution rates of pyrite in a freshly crushed pure pyrite specimen and a sulfide concentrate derived from the tailings were within the range of abiotic literature rates of oxidation by dissolved molecular O₂, as were rates of sphalerite and chalcopyrite dissolution in the tailings, dissolution rates of pyrite and aluminosilicates in the tailings generally differed from literature values. This discrepancy, obtained using a consistent experimental method and scale, is suggested to be related to difficulties in quantifying individual mineral reactive surface area in a mixture of minerals of greatly varying particle size, possibly due to factors such as dependence of surface area-normalised mineral dissolution rates on particle size and time, or to non-proportionality between rates and BET surface area.     

Bridging the gap between laboratory measurements and field estimations of silicate weathering using simple calculations

Weathering rates of silicate minerals observed in the laboratory are in general up to five orders of magnitude higher than those inferred from field studies. Simple calculations show that even if the field conditions were fully simulated in standard laboratory experiments, it would be impossible to measure the slow rates of mineral dissolution that are observed in the field. As it is not possible to measure the dissolution rates under typical field conditions, one should extrapolate the available data to the field conditions. To do this, a rate law for the dissolution of plagioclase in the field was formulated by combining the far from equilibrium dissolution rate of weathered natural oligoclase at 25°C with the effect of deviation from equilibrium on dissolution rate of fresh albite at 80°C. In contrast to the common view that laboratory experiments predict dissolution rates that are faster than those in the field, the simulation based on this rate law indicates that laboratory dissolution experiments actually predict slower rates than those observed in the field. This discrepancy is explained by the effect of precipitation of secondary minerals on the degree of saturation of the primary minerals and therefore on their dissolution rate. Indeed, adding kaolinite precipitation to the simulation significantly enhances the dissolution rate of the plagioclase. Moreover, a strong coupling between oligoclase dissolution and kaolinite precipitation was observed in the simulation. We suggest that such a coupling must exist in the field as well. Therefore, any attempt to predict the dissolution rate in the field requires knowledge of the rate of the secondary mineral precipitation.     

The effect of oxalate on the dissolution rates of oligoclase and tremolite

The effect of oxalate, a strong chelator for Al and other cations, on the dissolution rates of oligoclase feldspar and tremolite amphibole was investigated in a flow-through reactor at 22°C. Oxalate at concentrations of 0.5 and 1 mM has essentially no effect on the dissolution rate of tremolite, nor on the steady-state rate of release of Si from oligoclase. The fact that oxalate has no effect on dissolution rate suggests that detachment of Si rather than Al or Mg is the rate-limiting step. At pH 4 and 9, oxalate has no effect on the steady-state rate of release of Al, and dissolution is congruent. At pH 5 and 7, oligoclase dissolution is congruent in the presence of oxalate, but in the absence of oxalate Al is preferentially retained in the solid relative to Si.Large transient “spikes” of Al or Si are observed when oxalate is added to or removed from the system. The cause of the spikes is unknown; we suggest adsorption on feldspar surfaces away from sites of active dissolution as a possibility. Solutions in the reactors are undersaturated with respect to both gibbsite and kaolinite, so neither the spikes nor the incongruent dissolution can be explained by formation of a secondary precipitate.The rate of dissolution of tremolite is independent of pH over the pH range 2–5, and decreases at higher pH. The rate of dissolution of oligoclase in our experiments was independent of pH over the pH range 4–9. Since the dissolution rate of these minerals is independent of pH and organic ligand concentration, the effect of acid deposition from the atmosphere on the rate of supply of cations from weathering of granitic rocks should be minor.     

Do clay mineral dissolution rates reach steady state?

The temporal evolution of natural illite du Puy dissolution rates was measured from Si release rates in single-pass flow-through experiments lasting at least 100 days at 25°C and pH ranging from 2 to 12. Si release rates decreased by a factor of five and three at pH 12 and 2, respectively, during the experiments. These observations are interpreted to stem from changes in illite du Puy reactive surface area during these experiments. As the edges of clay minerals dissolve faster than the basal planes, dissolution tends to change clay mineral morphology decreasing the percentage of reactive edge sites. This continuously changing morphology prevents illite dissolution rates from attaining steady state during laboratory experiments lasting 100 to 200 days. A similar temporal decrease in dissolution rates is evident for many different sets of clay mineral dissolution rate data available in the literature. It seems reasonable, therefore, to expect that clay mineral dissolution does not attain steady state in nature, but rather their dissolution rates decrease continuously during their dissolution.     

石英溶解动力学研究进展

综述了石英在纯水、电解质和有机酸溶液中的溶解动力学实验技术和研究成果，着重阐述了电解质浓度、离子强度、ｐＨ阳离子和有机酸对石英溶解的动力学促进作用，并指出这种催化效应与石英表面负电性络合物的反应性有关。     

Surface evolution of dissolving minerals investigated with a kinetic Ising model

In natural weathering systems, both the chemistry and the topography of mineral surfaces change as rocks and minerals equilibrate to surface conditions. Most geochemical research has focused on changes in solution chemistry over time; however, temporal changes in surface topography may also yield information about rates and mechanisms of dissolution. We use stochastic dissolution simulations of a regular 2-D lattice with reaction mechanisms defined in terms of nearest neighbor interactions to elucidate how the surface area and reactivity of a crystal evolve during dissolution. Despite the simplicity of the model, it reproduces key features observed or inferred for mineral dissolution. Our model results indicate that: (i) dissolving surfaces reach a steady-state conformation after sufficient dissolution time, (ii) linear defects cause surface area and dissolution rate to vary in concert with one another, (iii) sigmoidal and non-sigmoidal rate vs. free-energy of reaction (ΔG_rxn) behavior can be rationalized in terms of the multiple steps occurring during dissolution, and (iv) surface roughness as a function of ΔG_rxn is highly sensitive to the reaction mechanism. When simulated times to reach steady-state are compared to published time series rate data using suitable scaling, good agreement is found for silicate minerals while the model significantly over-predicts the duration of the transient for Fe and Al oxides. The implication of our simple model is that many aspects of mineral dissolution behavior, including approach to steady-state, sigmoidal vs. non-sigmoidal rate vs. ΔG_rxn behavior, and development of rougher surfaces in conditions further from equilibrium can be explained by nearest neighbor interactions and simple Kossel-type models where reactivity of a surface is defined in terms of perfect surface, step, and kink sites.     

Stoichiometry of smectite dissolution reaction

The dissolution stoichiometry of smectite-rich bentonites SAz-1, STx-1 and SWy-1 was studied at 50°C and pH 2 and 3 using flow-through reactors. In addition to smectite, these samples contain considerable amounts of silica phases (quartz, cristobalite and/or amorphous silica). As a result, the molar Al/Si ratios of the bulk samples are significantly lower than those of the pure smectite.Smectite dissolution was highly incongruent during the first few hundred to few thousand hours of the experiments. Release rates of Si, Mg, Ca and Na underwent a distinct transition from an initial period of rapid release to significantly lower release rate at steady state. A reversed trend was observed for release of Al, which gradually increased from very low starting release rate to higher release rate at steady state. At steady state the ratio of released Al to released Si was found to be constant and independent of the experimental conditions. We suggest that this ratio represents the Al/Si ratio of the smectite itself, and it is not influenced by the presence of accessory phases in the sample.The rapid release of calcium, sodium and magnesium from the interlayer sites is explained by ion-exchange reactions, whereas the fast release of silicon is explained by dissolution of amorphous silica. We interpret the initial slow release of Al as the result of inhibition of smectite dissolution due to coating or cementation of the smectite aggregates by amorphous silica. As the silica is dissolved, the aggregates fall apart and more smectite surfaces are exposed, resulting in an increase in the smectite dissolution rate. Thereafter, the system approaches steady state, in which the major tetrahedral and octahedral cations of smectite are released congruently.     

Multisite surface reaction versus transport control during the hydrolysis of a complex oxide

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 pH_zpc 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.     

Oxidative dissolution of metacinnabar (β-HgS) by dissolved oxygen

The oxidative dissolution rate of metacinnabar by dissolved O₂ was measured at pH ∼5 in batch and column reactors. In the batch reactors, the dissolution rate varied from 3.15 (±0.40) to 5.87 (±0.39) × 10⁻² μmol/m²/day (I=0.01 M, 23°C) and increased with stirring speed, a characteristic normally associated with a transport-controlled reaction. However, theoretical calculations, a measured activation energy of 77 (±8) kJ/mol (I=0.01 M), and the mineral dissolution literature indicate reaction rates this slow are unlikely to be transport controlled. This phenomenon was attributed to the tendency of the hydrophobic source powder to aggregate and minimize the effective outer surface area. However, in a column experiment, the steady-state dissolution rate ranged from 1.34 (±0.11) to 2.27 (±0.11) x 10⁻² μmol/m²/day (I=0.01 M, 23°C) and was also influenced by flow rate, suggesting hydrodynamic conditions may influence weathering rates observed in the field. The rate of Hg release to solution, under a range of hydrogeochemical conditions that more closely approximated those in the subsurface, was 1 to 3 orders of magnitude lower than the dissolution rate due to the adsorption of released Hg(II) to the metacinnabar surface. The measured dissolution rates under all conditions were slow compared to the dissolution rates of minerals typically considered stable in the environment, and the adsorption of Hg(II) to the metacinnabar surface further lowered the Hg release rate.     

A New Analytic Integration of the Rate Equation for Batch Dissolution of Salts in the Presence of Common Ion

Following a recent suggestion of a new rate equation specifically for the batch dissolution of salts in solutions containing a common ion, this paper describes an analytic solution to its integration. The equation has been tested by dissolving 250???m gypsum- rock particles in water (26.7?g?l^?1) containing various mixtures of sodium and calcium chlorides, all at an ionic strength of 0.060?M. The model fitted the experimental curves very well and showed that the dissolution slowed slightly overall when the initial calcium concentration was increased from 0 to 0.020?M. The dissolution curves were also modelled as a simple exponential, whence the fit was comparable to that with the new equation, with the exponential rate constant varying between 0.025 and 0.019 (±0.0004) for 0 and 0.020?M initial calcium concentration, respectively. Conventional Electrolyte theory from thermodynamics is used to show that the new equation is an inevitable consequence of modelling the net rate of dissolution in terms of a back reaction that is first order with respect to the dissolved substance, as per the recently described Shrinking Object model. Moreover, it is shown how the simple exponential model (which is a well-used plot in dissolution kinetics) provides the linear end-member to an infinite number of curvilinear plots of rate of dissolution versus reaction progress developed by the new model??it is the special case where common ion is absent. The results are now judged good enough to identify a generic batch dissolution rate equation for all salts dissolving without significant complication from either contaminants or their own gaseous species, as in calcium carbonate dissolution.     

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.     

Calcite Dissolution Kinetics

We compare the canonical treatment of calcite’s dissolution rate from the literature in a closed system, particle batch reactor, with the alternative approach suggested by Truesdale (Aquat Geochem, 2015). We show that the decay of rate over time can be understood in terms of the evolution and distribution of reactive sites on the surface of these particles. We also emphasize that interpretation of observed rates must not exclude the fundamental role of crystal defects, whose importance is already implicitly reflected in the common form of rate laws in geochemistry. The empirical behavior of overall rate in closed systems, such as those described by Truesdale, may thus reflect relationships between defect centers and the generation of steps over the calcite surface (previously documented for silicates), such that below a critical free energy limit, there is insufficient driving force to open hollow cores and thus a loss of reaction mechanism. Dissolution in this very-near-equilibrium regime will be dependent on the distribution of extant steps and the energetics of new kink site nucleation. However, these sensitivities are complicated in the case of particle systems by grain boundaries, edges, corners, and other terminations. Such discontinuities constitute a defect class whose overall kinetic importance will be strongly tied to particle diameter and which can act independently of the internal strain field imposed by screw and edge dislocations.     

Role of electrochemical reactions in pressure solution

Using a Surface Forces Apparatus we have measured changes in the electrical potential difference between quartz and mica surfaces that correlate with the changing quartz dissolution rate when surfaces are pressed together at relatively low pressures (2-3 atm) in aqueous electrolyte solutions of 30 mM CaCl₂ at 25 °C. No detectable dissolution or voltage potential difference is measured in symmetrical systems (e.g. mica-mica or quartz-quartz) or between dry surfaces subjected to similar pressures, indicating that the dissolution can not be attributed to a simple pressure effect, slow aging (creep), or plastic deformation of the quartz surface. In quartz-mica systems brought together under pressure or to close proximity in electrolyte solution, the onset of quartz dissolution is marked by a sudden, rapid decrease in the quartz thickness at initial rates in the range from 1 to 4 nm/min, which after several hours settles into a constant rate of approximately 0.01 nm/min (∼5 μm/yr). Concomitantly, the potential drops to a constant value once the dissolution rate has stabilized. The decrease in the decay rate is interpreted as being due to saturation of the confined aqueous film and/or to the buildup of a Stern layer on the quartz surface, and the constant rate as being due to the steady-state chemical dissolution and diffusion of the dissolving silica into the surrounding reservoir. The dissolution is ‘non-uniform’: the surfaces become rough as dissolution proceeds, with the appearance of pits in a manner analogous to corrosion. On occasions, the process of rapid dissolution followed by a gradual transition to steady dissolution repeats itself, suggesting that the pit structure and Stern layer are fragile and subject to collapse and/or expulsion from the gap. Preliminary experiments on the dissolution of multi-faceted milled quartz particles (∼1.0 μm diameter) compressed between two muscovite surfaces suggest an asymmetry in the dissolution rates at different crystallographic planes. The origin of the electrical potential is interpreted as arising from the overlapping of the electric double-layers of two dissimilar surfaces when they are forced into close proximity. This electrical potential difference, for as yet unknown reasons, appears to be the driving force for the dissolution, rather than pressure.     

The Occurrence of Sc,Co and Ni in Manganese Ore from Western China

China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.     

Mineral dissolution kinetics as a function of distance from equilibrium – New experimental results

We revisit a fundamental question in mineral dissolution kinetics, namely: is the function of dissolution rate versus the distance from equilibrium continuous, or does the “switch” between two different reaction mechanisms cause a discontinuity, i.e., a kinetic bifurcation? Based on new insight from experimental results, including direct observations of retreating crystal surfaces with vertical scanning interferometry (VSI), we present evidence that a discontinuity does indeed exist. Through a carefully designed near-equilibrium albite dissolution experiment, we show how a non-steady-state dissolution rate observed on a crystal surface reflects reactivity inherited from earlier episodes of undersaturation. This outcome forces us to re-think the common practice of extrapolating overall dissolution rates measured far-from-equilibrium to near-equilibrium conditions.     

The Rate-equation for Biogenic Silica Dissolution in Seawater – New Hypotheses

This paper investigates the kinetics of biogenic silica dissolution in seawater, through batch dissolution, where the reaction is observed as the increase in dissolved silicic acid concentration with time. It utilises new data from dissolution of the marine diatom Cyclotella cryptica, and the freshwater diatom C. meneghiniana, as well as literature results. The sum of exponentials form: , is hypothesised as the most general rate equation, with the single exponential form occurring in a minority of cases. The consistency of this behaviour with a near-exponential decay of surface area with time, an appropriate mathematical integration, and surface heterogeneity, is discussed. (Serious errors in some existing integrations are identified.) The rate of dissolution at constant surface area is shown to decrease non-linearly as the ambient concentration of silicic acid increases. A fractional order with respect to silicic acid in the back reaction, close to 0.5, leads to a mechanism in which an intermediate is formed from the surface and an, as yet, unidentified molecule, probably water. Good preliminary fits are found between the model and literature results found using entirely different methods. A parallel treatment of hydrogen ion dependency is suggested. The likely distortion of full reaction curves from exponential behaviour imposed by the back reaction, is considered in detail.     

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.     

Experimental knife-edge pressure solution of halite

Pressure solution experiments were carried out, using a quartz knife-edge 0.26 mm wide on halite single crystals in halite saturated solutions, to observe the detailed development of pressure solution contacts and the rates of pressure solution. A rate of about 3 μm/day was observed for initial knife-edge stresses ranging from 4.5 to 15 MPa. Close examination of the contact leads to the conclusion that the mechanism of pressure solution is a combination of plastic deformation at the contact and free surface pressure dissolution near its periphery. Free surface pressure dissolution increases the contact stress to about 18 MPa, high enough to cause plastic deformation, by changing the area of contact. This mechanism differs from a water film diffusion mechanism, previously suggested by many authors, but is similar in some ways to the undercutting hypothesis of Bathurst (1958). We infer a steady state plastic deformation instead of catastrophic grain crushing at the contact. Free surface dissolution plus the plastic deformation mechanism may be primarily responsible for pressure solution in relatively porous rocks.     

Mechanisms and rates of quartz dissolution in melts in the CMAS (CaO–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>) system

The dissolution rate of minerals in silicate melts is generally assumed to be a function of the rate of mass transport of the released cations in the solvent. While this appears to be the case in moderately to highly viscous solvents, there is some evidence that the rate-controlling step may be different in very fluid, highly silica undersaturated melts such as basanites. In this study, convection-free experiments using solvent melts with silica activity from 0.185–0.56 and viscosity from 0.03–4.6 Pa s show that the dissolution rate is strongly dependent on the degree of superheating, silica activity and the viscosity of the solvent. Dissolution rates increase with increasing melt temperature and decreasing silica activity and viscosity. Quartz dissolution in melts with viscosity <0.59–1.9 Pa s and silica activity <0.47 is controlled by the rate of interface reaction as shown by the absence of steady state composition and silica saturation in the interface melts. Only in the most viscous melt with the highest silica activity is quartz dissolution controlled by the rate of diffusion in the melt and only after a long initiation time. The results of this study indicate that although a diffusion-based model may be applicable to dissolution in viscous magmas, a different approach that combines the interplay between the degree of undersaturation of the melt and its viscosity is required in very fluid melts.This revised version was published online September 2004 with a correction to Figure 8.