A hydro-geochemical analysis of the saturation process with salt water of a bentonite crushed granite rock mixture in an engineered nuclear barrier

A MX-80 sodium bentonite crushed granite rock mixture is being saturated in the Äspö Hard Rock Laboratory managed by SKB (the Swedish Company of nuclear waste management) as part of the “Backfill and Plug Test Project”. The Äspö Hard Rock Laboratory is placed in the Swedish Island of Äspö, an underground full-scale laboratory where different testing construction procedures and handling techniques are being studied. The groundwater of Äspö has a variable salt concentration according to the zone considered. The added water during the mixing process of both materials had an average salt concentration of 6 g/L. However, backfill is being saturated with salt water containing higher salt content (up to 16 g/L, 50 / 50 of NaCl and CaCl₂ by mass) to speed up the saturation process. The mixture swelling capacity is small due to the low backfill bentonite content, but its activity is still large if compared with natural clayey soils. A coupled hydro-chemical approach was used to simulate the backfill hydration process, comparing the results with in situ measurements. An intrinsic permeability law, depending on salt concentration in the liquid phase, was incorporated into the model. The retention curve was also determined taking into account the effect of the chemical species on backfill behaviour. The simulation of the saturation process shows the importance of studying these problems with a HC (hydro-chemical) formulation, especially if long term behaviour of such mixtures is going to be reproduced.     

Influence of various factors on the difference in the liquid limit values determined by Casagrande’s and fall cone method

As there are many correlations linking the liquid limit directly or indirectly with various engineering properties of the soil, the accurate determination of the liquid limit is quite essential. Generally, two methods, i.e. Casagrande’s and fall cone are adopted to determine the liquid limit of soil. Research was carried out to study the influence of the properties of bentonite and the presence of the salt solution on the liquid limit values of soil-bentonite mixtures determined by the Casagrande’s and fall cone methods. The results showed that irrespective of the presence of the type of bentonite or salt solution, a higher value of the liquid limit was obtained by the Casagrande’s method as compared to the fall cone method. However, the difference between the two methods decreased with the decrease in the liquid limit, clay fraction, specific surface area and free swelling capacity of the bentonite present in the mixture. Similarly, the difference in the liquid limit values obtained by both these methods is reduced with an increase in the salt concentration.     

Effect of alkaline solutions on bentonite properties

The influence of alkaline aqueous solutions on the properties of bentonite was investigated to evaluate the performance of bentonitic engineered barriers when contacted with alkaline groundwater. Batch and hydraulic conductivity tests were conducted on Na-bentonite using six different alkaline aqueous solutions. For the batch tests, almost no change in the montmorillonite fraction of the bentonite was observed after reacting with alkaline solutions (pH = 8.4–13.1), regardless of the solution type. On the other hand, aluminosilicate minerals (e.g., albite) were dissolved and secondary minerals (e.g., anorthite) were formed in alkaline NaOH solutions (pH > 13). The cation (Ca or Na) concentration primarily affected the swelling properties of bentonite rather than the pH of the solution, which was comparable to the results of the hydraulic conductivity tests. For the Ca solutions, the hydraulic conductivity of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ solution (6.5 × 10^?9 cm/s) was approximately an order of magnitude lower than that of the bentonite specimen to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (5.0 × 10^?8 cm/s), whereas the hydraulic conductivity to the 0.02 mol/L Ca(OH)₂ + 1 mol/L CaCl₂ solution (pH = 11.3) (5.0 × 10^?8 cm/s) was slightly higher than that to the 1 mol/L CaCl₂ solution (pH_i = 8.4) (4.4 × 10^?8 cm/s). For the NaOH solutions with pH > 13, the hydraulic conductivity of the bentonite specimen decreased with increasing Na concentration, suggesting that the effect of Na concentration was more dominant than that of permeant pH.     

Effect of Water and Leachate on Hydraulic Behavior of Compacted Bentonite,Calcareous Sand and Tuff Mixtures for Use as Landfill Liners

Compacted soil–bentonite liners, consisting of a sandy soil mixed with bentonite as backfill, are used extensively as engineered barriers for contaminant containment. This paper studies the valorization of local materials containing calcareous sand, tuff obtained from Laghouat region (in the South Algeria), to associate with bentonite in order to improve their hydraulic characteristics for use as landfill liner material. Firstly, a geotechnical characterization of mixtures chooses from a fixed percentage to 10% bentonite and different percentages of calcareous sand and tuff so that they are complementary to 90% by not 10%. Thereafter, the determination of saturated hydraulic conductivity at falling-head permeability (K_v) and oedometer (K_id, indirect Measure) tests of all compacted mixtures at Optimum Normal Proctor have been carried out using both permeates by tap water and a landfill leachate in order to simulate long-term conditions. The results showed that the saturated hydraulic conductivity of tap water is relatively lower than the one saturated by leachate in the falling-head test, unlike the oedometer test. The B₁₀CS₂₀T₇₀ mixture has satisfied the hydraulic conductivity criterion of bottom barriers (i.e. water permeated: k_v20° = 1.97 × 10^?9 and k_id from 7 × 10^?9 to 1.83 × 10^?10 < 10^?9m/s; leachate permeated: k_v20° = 2.91 × 10^?9 and k_id from 7 × 10^?9 at 1.44 × 10^?10 < 10^?9 m/s). Finally, a comparison between direct measurements of the saturated hydraulic conductivity by triaxial (K_d) test and oedometer test (K_id) in the range of effective stress applied 100–800 kPa led to propose equations of correlations between these two methods. In conclusion, adopted formulation B₁₀CS₂₀T₇₀ perfectly meets the regulatory requirements in force and constitutes an economic product based on available local materials for engineers barriers.     

The solubility of fluorite in hydrothermal solutions,an experimental study

The solubility of fluorite in NaCl solutions increases with increasing temperature at all ionic strengths up to about 100°C. Above this temperature, the solubility passes through a maximum and possibly a minimum with increasing temperature at NaCl concentrations of 1.0M or less, and increases continuously with increasing temperature at NaCl concentrations above 1.0M. At any given temperature, the solubility of fluorite increases with increasing salt concentration in NaCl, KCl and CaCl₂ solutions. The solubility follows Debye-Hückel theory for KCl solutions. In NaCl and CaCl₂ solutions, the solubility of fluorite increases more rapidly than predicted by Debye-Hückel theory: the excess solubility is due to the presence of NaF^c, CaF⁺, and possibly of Na₂F⁺. The solubility of fluorite in NaCl-CaCl₂ and in NaCl-CaCl₂-MgCl₂ solutions is controlled by the common ion effect and by the presence of NaF^c, CaF⁺, and MgF⁺. The solubility of fluorite in NaCl-HCl solutions increases rapidly with increasing initial HCl concentration; the large solubility increase is due to the presence of HF^c. It seems likely that complexes other than those identified in this study rarely play a major role in fluoride transport and fluorite deposition at temperatures below 300°C.     

Prediction leaching of potassium using the convective–dispersive and the convective log-normal transfer function models

There is increasing concern about soil enrichment with K⁺ and subsequent potential losses following long-term application of poor quality water to agricultural land. Different models are increasingly being used for predicting or analyzing water flow and chemical transport in soils and groundwater. The convective–dispersive equation (CDE) and the convective log-normal transfer function (CLT) models were fitted to the potassium (K⁺) leaching data. The CDE and CLT models produced equivalent goodness of fit. Simulated breakthrough curves for a range of CaCl₂ concentration based on parameters of 15 mmol l⁻¹ CaCl₂ were characterised by an early peak position associated with higher K⁺ concentration as the CaCl₂ concentration used in leaching experiments decreased. In another method, the parameters estimated from 15 mmol l⁻¹ CaCl₂ solution were used for all other CaCl₂ concentrations, and the best value of retardation factor (R) was optimised for each data set. A better prediction was found. With decreasing CaCl₂ concentration the value of R is required to be more than that measured (except for 10 mmol l⁻¹ CaCl₂), if the estimated parameters of 15 mmol l⁻¹ CaCl₂ are used. The two models suffer from the fact that they need to be calibrated against a data set, and some of their parameters are not measurable and cannot be determined independently.     

Characterization of locally available soil as a liner material for solid waste landfills in Sri Lanka

This study aimed to develop a low-cost and effective clay liner material for solid waste landfills in Sri Lanka. A locally available clayey soil and its admixtures with 5 and 10% bentonite were examined for this purpose. Laboratory experiments to determine soil plasticity and swell index were carried out on the tested samples. Hydraulic conductivity (k) tests were carried out in the laboratory using water and an aqueous solution of CaCl₂ on unconsolidated samples prepared by either dry or slurry packing and pre-consolidated samples with five different consolidation pressures (p) from 10 to 200 kPa. Measured liquid limits for tested admixtures increased with increasing bentonite contents and correlated well with measured values of the swell index. The difference in permeant solutions had little effect on measured k values for both unconsolidated and pre-consolidated samples. The hydraulic conductivities were highly affected by changing p, i.e., the k values decreased on two orders of magnitude as p increased from 10 to 200 kPa. The Kozeny–Carman equation, a theoretical permeability model that expresses the k-porosity relationship, was applied to measured data including reported values. Results showed the Kozeny–Carman equation captured well the porosity-dependent k values for tested soils and their admixtures with bentonite under a wide range of void ratios, suggesting that the Kozeny–Carman equation is a useful tool to estimate the magnitude of k values for differently compacted soil and its bentonite admixtures.     

The dissolution kinetics of atacamite in the acid range and the stability of atacamite containing soils from Namaqualand,South Africa

The Cu hydroxy mineral, atacamite, is commonly associated with saline environments and is generally thought to dissolve rapidly in the presence of fresh water. A Cu contaminated soil from the arid Namaqualand region, South Africa, shows atacamite as the dominant Cu containing mineral. The stability of the Cu phase in this soil was determined through equilibrium and leaching studies using both deionised water (DI) and a concentrated (0.5 M) NaCl solution. Initially a high concentration of exchangeable Cu was released from the soils leached with NaCl. Continued leaching with NaCl resulted in a substantial decrease in Cu release as atacamite equilibria started to control dissolved Cu. This suggests that an initial spike of Cu laden water will leach from the soils at the onset of a large rainfall event. Further additions of water will result in a lower but sustained release of Cu from the soil. The Cu contaminated soils are exposed to acidic sulphate leachate thus the dissolution kinetics of synthetic atacamite in the acidic range (pH 5.5–4.0) was determined in both NaCl and DI solutions. The kinetic data showed that atacamite dissolution rates are significantly higher in DI than in NaCl but the rates converge at pH 4. In comparison to common acid soluble minerals, atacamite displays a moderate dissolution rate (10^−9.55–10^−7.14 mol m⁻² s⁻¹) within the acid range (pH 5.5–4.0). The atacamite dissolution reaction order with respect to pH is 1.3 and 1.6 in DI and NaCl solutions, respectively, suggesting that dissolution rates of atacamite are highly pH dependent in the acid range. The type of acid used to lower the pH had no effect on the reaction kinetics, with HNO₃ and H₂SO₄ resulting in comparable dissolution rates of atacamite at pH 4.5.     

Nature of fluids and regional implications for Lesser Himalayan carbonates and associated mineralization

Fluid inclusion data are presented for the successive stages of limestone, dolomite, magnesite and sulphide-bearing quartz veins in Proterozoic carbonate rocks of the Lesser Himalaya. Subsurface fluids were H₂O–NaCl–KCl ± MgCl₂ ± CaCl₂ and showed successive increase in salinity and temperature. The salinity of the pore fluid during limestone diagenesis was in the range of 7.5–15 eq wt.% NaCl and the magnesite-forming fluids had a salinity of about 9 to 19 eq wt.% NaCl. This progressive rise in salinity is attributed to a more saline fluid in the deeper zones. The inverse relation between homogenization temperatures and final melting temperatures suggests mixing of the fluids during diagenesis, and highly depleted δ¹⁸O values rule out participation of magmatic fluid in the mixing. A late stage carbonic fluid is linked with talc formation. The low temperature of sulphide-forming epigenetic solutions, as obtained from fluid inclusions, is also substantiated by the chemical data from these sulphides. δ³⁴S values in galena infer that magmatic sulphur was probably not involved, and the sulphur of the galena is derived from an isotopically heavy source.     

Salting-out of methane in single-salt solutions at 25°C and below 800 psia

Aqueous solubilities of methane at 25°C have been determined in single-salt solutions equilibrated with a CH₄ gas phase at 350, 550, and 750 psia. Measurements were made over a range of ionic strengths in NaCl, KCl, CaCl₂, MgCl₂, Na₂SO₄, K₂SO₄, MgSO₄, Na₂CO₃, K₂CO₃, NaHCO₃, and KHCO₃ aqueous solutions.At 25°C and constant pressure and methane fugacity, methane solubilities were largely controlled by the stoichiometric ionic strength, I, and the cation of the salt. Except for an increased salting-out due to HCO₃^?, the anion effect was relatively insignificant. Different but consistent solubility trends were followed in monovalent and divalent cation salt solutions as a function of I. Solubilities increased in salt solutions having a common anion in the following cation sequence: Na⁺ < K⁺ ? Ca²⁺ < Mg²⁺.The molal salting coefficient, k_m, for each salt was constant under the experimental conditions of the study, k_m is defined by $\text{log}\text{γ}\text{ch}{}_4\text{I}$ where $\text{γ}\text{ch}{}_4$, the molal activity coefficient, is the methane solubility ratio () measured at constant temperature, pressure, and CH₄ fugacity. Single-salt k_m values are as follows: 0.121, NaCl (4m); 0.121, Na₂SO₄ (1m); 0.118, Na₂CO₃ (1.5m); 0.146, NaHCO₃ (0.5m); 0.101, KCl (4m); 0.108, K₂SO₄ (0.5m); 0.111, K₂CO₃ (2m); 0.145, KHCO₃ (0.5m); 0.071, CaCl₂ (2m); 0.063, MgCl₂ (2m); and 0.066, MgSO₄ (1.5m) where the molalities in parentheses refer to the maximum salt concentrations used in this study.     

Potassium leaching in undisturbed soil cores following surface applications of gypsum

Displacement studies on leaching of potassium (K⁺) were conducted under unsaturated steady state flow conditions in nine undisturbed soil columns (15.5 cm in diameter and 25 cm long). Pulses of K⁺ applied to columns of undisturbed soil were leached with distilled water or calcium chloride (CaCl₂) at a rate of 18 mm h⁻¹. The movement of K⁺ in gypsum treated soil leached with distilled water was at a similar rate to that of the untreated soil leached with 15 mM CaCl₂. The Ca²⁺ concentrations in the leachates were about 15 mM, the expected values for the dissolution of the gypsum. When applied K⁺ was displaced with the distilled water, K⁺ was retained in the top 10–12.5 cm depth of soil. In the undisturbed soil cores there is possibility of preferential flow and lack of K⁺ sorption. The application of gypsum and CaCl₂ in the reclamation of sodic soils would be expected to leach K⁺ from soils. It can also be concluded that the use of sources of water for irrigation which have a high Ca²⁺ concentration can also lead to leaching of K⁺ from soil. Average effluent concentration of K⁺ during leaching period was 30.2 and 28.6 mg l⁻¹ for the gypsum and CaCl₂ treated soils, respectively. These concentrations are greater than the recommended guideline of the World Health Organisation (12 mg K⁺ l⁻¹).     

Plagioclase-aqueous solution equilibrium: Concentration dependence

The plagioclase-(NaCl + CaCl₂) exchange equilibrium was examined experimentally at 700°C, 0.5 GPa in aqueous solutions with salt concentrations from 1 to 64 m. The Ca/(Ca + Na) distribution between plagioclase and solution (salt melt) is illustrated in five diagrams constructed for concentrations of 1, 4, 8, 16, and 64 m. The elevated bulk salinity of the fluid at a constant Ca/(Ca + Na) ratio results in plagioclase albitization, with this effect reaching a maximum in relatively dilute solutions (1–4 m). In concentrated solutions (salt melts), the shift in the plagioclase composition with variations in the salinity is relatively insignificant. The simple hydration of basic rocks (purely metamorphic reaction) is associated with the albitization of plagioclase, and calculations suggest a possible shift from anorthite to oligoclase. This is also applicable to chemically more complex mineral associations: an increase in the overall salinity of the fluid should result in an increase in the activity of monovalent cations relative to that of bivalent ones and, correspondingly, stimulate reactions in which alkali earth cations (Ca + Mg + Fe) are substituted for alkalis (Na + K + Li). Although our experiments were carried out at temperatures 50°C lower than the melting point of albite under a pure water pressure (0.5 GPa), the addition of CaCl₂ solution to albite (i.e., plagioclase anorthitization and a decrease in the water activity in the salt solutions) induced the appearance of melt because of quartz formation by the reaction 2Ab + CaCl₂ → An + 2NaCl + 4Qtz and the eutectic phase proportions in the Ab + Qtz system.     

A New Method for Determining Fluid Compositions in the H20-NaCl-CaCl2 System with Cryogenic Raman Spectroscopy

Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, mainly due to the difficulty to freeze the solutions. This problem was solved by adding alumina powder to the solutions to facilitate nucleation of crystals. Cryogenic （-185℃） Raman spectroscopic studies of alumina-spiced solutions indicate that XNaCl is linearly correlated with the total peak area fraction of hydrohalite. Capsules of solutions made from silica capillary were prepared to simulate fluid inclusions. Most of these artificial fluid inclusions could not be totally frozen even at temperatures as low as -185℃, and the total peak area fraction of hydrohalite is not correlated linearly with XNaCI. However, the degree of deviation （△XNaCl） from the linear correlation established earlier is related to the amount of residual solution, which is reflected by the ratio （r） of the baseline ＂bump＂ area, resulting from the interstitial unfrozen brine near 3435 cm^-1, and the total hydrate peak area between 3350 and 3600 cm^-1. A linear correlation between △XNaCl and r is established to estimate XNaCl from cryogenic Raman spectroscopic analysis for fluid inclusions.     

Determination of hydraulic conductivity of sand-bentonite mixtures for engineering purposes

Pollution of the environment due to leakage from waste repositories is a well-known and wide spread problem. Emphasis has therefore been put on design of liners for such repositories, focusing on hydraulic conductivity and its variation with time, liner composition, water content, compaction etc. The paper addresses the hydraulic conductivity of sand/bentonite mixtures, especially the variation of the hydraulic conductivity as a function of bentonite content, compaction and degree of saturation. In order to better understand the variation of the hydraulic conductivity of a sand–bentonite mixture a new parameter k ₁ has been proposed. The parameter reflects the amount of bentonite per pore volume and can easily be calculated based on the amount of bentonite and the dry density of the soil mixture. Thereby, the hydraulic conductivity can be predicted as a function of different degres of compaction. This method can be used for engineering purposes to predict the hydraulic conductivity at an early stage of a design to get an idea of the required design and hence, cost.     

Studies on Hydraulic Conductivity of Fly Ash-Stabilised Expansive Clay Liners

Earthen barriers or clay liners are a major concern in geo-environmental engineering. They are designed to preclude or reduce leachate migration. Hence, a low hydraulic conductivity (k) is an important parameter in the design of clay liners. Materials such as bentonite and lateritic clays, which have a low hydraulic conductivity at high dry densities, are used in the construction of clay liners. Compacted expansive clays which are high in montmorillonite content also have a very low hydraulic conductivity. When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as an innovative clay liner material. It is, therefore, required to study various physical and engineering properties of this new clay liner material. Liquid limit (LL) and free swell index (FSI) are important index properties to be studied in the case of this clay liner material. The hydraulic conductivity of this new clay liner material depends on the fly ash content in the blend. Further, parameters such as solute concentration and kinematic viscosity also influence hydraulic conductivity of clay liners. This paper presents experimental results obtained on hydraulic conductivity (k) of fly ash-stabilised expansive clay liner at varying fly ash content and solute concentration. The tests were performed with deionised water (DIW), CaCl₂, NaCl and KCl as permeating fluids. Fly ash content in the blend was varied as 0, 10, 20 and 30 % by weight of the expansive clay, and the solute concentration was varied as 5 mM (milli molar), 10, 20, 50, 100 and 500. It was found that hydraulic conductivity (k) decreased with increasing fly ash content, solute concentration and kinematic viscosity. Further, hydraulic conductivity (k) was correlated with LL and FSI of the clay liner material for different fly ash contents and solute concentrations. Useful correlations were obtained.     

A study of factors affecting on the zeta potential of kaolinite and quartz powder

The purpose of this study was to determine the effects of pH, ion type (salt and metal cations), ionic strength, cation valence, hydrated ionic radius, and solid concentration on the zeta potential of kaolinite and quartz powder in the presence of NaCl, KCl, CaCl₂, CuCl₂, BaCl₂, and AlCl₃ solutions. The kaolinite and quartz powder have no isoelectric point (iep) within the entire pH range (3 < pH < 11). In the presence of hydrolysable metal ions, kaolinite and quartz powder have two ieps. As the cationic valence increases, the zeta potential of kaolinite and quartz powder becomes less negative. Monovalent cation, K⁺, yields more negative zeta potential values than the divalent cation Ba²⁺. As concentration of solid increases, the zeta potential of the minerals becomes more positive under acidic conditions; however, under alkaline conditions as solid concentration increases the zeta potential becomes more negative. Hydrated ionic radius also affects the zeta potential; the larger the ion, the thicker the layer and the more negative zeta potential for both kaolinite and quartz powder.     

Heave Studies on Fly Ash-Stabilised Expansive Clay Liners

Clay liners or compacted earthen barriers are important barrier materials used for preventing contaminant transport through soils. A low hydraulic conductivity (k) is a significant parameter that governs the design and construction of clay liners. Compacted expansive clays, which are montmorillonite clays, also have a very low hydraulic conductivity (k). When expansive clays are blended with fly ash, an industrial waste, the hydraulic conductivity (k) further reduces as the ash-clay blends result in increased dry densities at increased fly ash contents. Hence, fly ash-stabilised expansive clay can also be proposed as a unique clay liner material. As expansive clays undergo heave when they come into contact with water, it is necessary to study the heave behaviour of fly ash-stabilised expansive clay liners. This paper presents heave studies on fly ash-stabilised expansive clay liners. Fly ash in different contents by dry weight of the expansive clay was added to the clay, and the ash-clay blend was compacted as a liner overlying a natural field soil layer. Compacted lateritic clay was used for simulating the natural field soil into which contaminants migrate. Calcium chloride (CaCl₂) solution of varying concentration (5, 10, 20, 50, 100 and 500 mM) was used as the permeating fluid in the heave studies. The rate of heave and the amount of heave of the fly ash-stabilised expansive clay liners were monitored. Deionised water (DIW) was also used as inundating fluid for comparative study. Heave (mm) decreased with increase in solute concentration for all fly ash contents. For a given solute concentration, heave decreased up to a fly ash content of 20 % and thereafter it increased when the fly ash content was increased to 30 %. Heave of the fly ash-stabilised expansive clay liners was correlated with their permeability, liquid limit (LL) and free swell index (FSI) pertaining to the respective fly ash content and CaCl₂ concentration.     

In situ AFM study on barite (0 0 1) surface dissolution in NaCl solutions at 30 °C

This paper reports in situ observations on barite (0 0 1) surface dissolution behavior in 0.1–0.001 M NaCl solutions at 30 °C using atomic force microscopy (AFM). The step retreating on barite (0 0 1) surfaces changed with increasing NaCl solution concentrations. In solutions with a higher NaCl concentration (⩾0.01 M), many steps showed curved or irregular fronts during the later experimental stage, while almost all steps in solutions with a lower NaCl concentration exhibited straight or angular fronts, even during the late stage. The splitting phenomenon of the initial 〈h k 0〉 one-layer steps (7.2 Å) into two half-layer steps (3.6 Å) occurred in all NaCl solutions, while that of the initial [0 1 0] one-layer steps observed only in the 0.1 M NaCl solution. The step retreat rates increased with an increasing NaCl solution concentration. We observed triangular etch pit and deep etch pit formation in all NaCl solutions, which tended to form late in solutions with lower NaCl concentrations. The deep etch pit morphology changed with increasing NaCl solution concentrations. A hexagonal form elongated in the [0 1 0] direction was bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces in a 0.001 M NaCl solution, and a rhombic form was bounded by the {5 1 0} and (0 0 1) faces in 0.01 M and 0.1 M NaCl solutions. An intermediate form was observed in a 0.005 M NaCl solution, which was defined by {1 0 0}, a curved face tangent to the [0 1 0] direction, {3 1 0}, and (0 0 1) faces: the intermediate form appeared between the hexagonal and rhombic forms in solutions with lower and higher NaCl concentrations, respectively. The triangular etch pit and deep etch pit growth rates also increased with the NaCl solution concentration. Combining the step and face retreat rates in NaCl solutions estimated in this AFM study as well as the data on the effect of water temperature on the retreat rates reported in our earlier study, we produced two new findings. One finding is that the retreat rates increase by approximately two-fold when the NaCl solution concentration increases by one order of magnitude, and the other finding is that the retreat rate increase due to a one order of magnitude increase in the NaCl concentration corresponds to an increase of approximately 8 °C in water temperature. This correlation may help to understand and evaluate increasing dissolution kinetics induced by the different mechanisms where barite dissolution is promoted by the catalytic effect of Na⁺ and Cl⁻ ions (through an increase in the NaCl solution concentration) or by an increase in the hydration of Ba²⁺ and SO₄²⁻ (through an increase in water temperature).     

Calcite dissolution kinetics in saline waters

The effect of ionic strength (I), pCO₂, and temperature on the dissolution rate of calcite was investigated in magnesium-free, phosphate-free, low calcium (m_Ca2+ ≈ 0.01 m) simple KCl and NaCl solutions over the undersaturation range of 0.4 ≤ Ω_calcite ≤ 0.8. First-order kinetics were found sufficient to describe the rate data where the rate constant (k) is dependent on the solution composition. Rates decreased with increasing I and were faster in KCl than NaCl solutions at the same I indicating that Na⁺ interacts more strongly with the calcite surface than K⁺ or that water is less available in NaCl solutions. Rates increased with increasing pCO₂ and temperature, and their influences diminished at high I. Arrhenius plots yielded a relatively high activation energy (E_a ≈ 20 ± 2 kJ mol^− 1) which indicated that dissolution was dominated by surface-controlled processes. The multiple regression model (MR) of Gledhill and Morse (2006a) was found to adequately describe the results at high I in NaCl solutions, but caution must be used when extrapolating to low I or pCO₂ values. These results are consistent with the hypothesis that the mole fraction of “free” solvent (X_{“free”H2O}) plays a significant role in the dissolution kinetics of calcite with a minimum value of  45–55% required for dissolution to proceed in undersaturated solutions at 25–55 °C and pCO₂ = 0.1–1 atm. This hypothesis has been incorporated into a modified version of the MR model of Gledhill and Morse (2006a) where X_{“free”H2O} has replaced I and the Ca²⁺ and Mg²⁺ terms have been dropped: