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1.
This experimental study determined the effect of ionic strength (IS) on the uptake of Mg into calcites that grew by the classical step propagation process. Using flow-through AFM and defined solution chemistry, calcite was grown in NaCl and KCl solutions of known supersaturation state while measuring the corresponding growth kinetics. Analysis of the resulting calcite compositions by SIMS shows that Mg content is inversely correlated with IS for both electrolytes. A sixfold increase in IS decreases the Mg-content by up to 40%. Overgrowths that developed in NaCl solutions contain more Mg than samples that grew in KCl solutions. The corresponding kinetic measurements reveal that step propagation rates are independent of IS within experimental error but are electrolyte-specific. In NaCl solutions, steps with the obtuse geometry move significantly faster than acute steps, but in KCl solutions, the acute and obtuse steps move at similar rates.Analysis of the data suggests that the decrease in Mg content with increasing IS arises from the interplay of ion-kink interactions between the background cations (Na+ or K+), the primary solute cation (Ca2+), and the impurity (Mg2+). A simple physical model proposes that increasing levels of electrolytes block the attachment of the strongly hydrated Mg2+ ion relative to Ca2+ but the effects are step-specific for each type of electrolyte. Whereas K+ interacts weakly with kink sites along both step directions, Na+ interacts preferentially with acute steps and, consequently, slows their rate of step propagation relative to obtuse steps. Because Na+ increases the fraction of the surface that develops from acute steps and because Mg is preferentially incorporated into the kink sites of acute steps, calcite overgrowths developed in NaCl solutions contain more Mg than those in grown in KCl. Thus, the salt-specific Mg contents measured in this study can be explained by shifts in the distribution of step types and the ability of each step type to incorporate Mg. The findings reconcile apparent discrepancies regarding the effect of IS on calcite kinetics and Mg incorporation observed in laboratory-based studies.  相似文献   

2.
Barium sulfate is used as a model system to illustrate how solution composition can affect processes of crystal dissolution and growth. Rates and modes of reactions as well as morphological features can be modified by the introduction of simple ionic salts (KCl, NaCl, LiCl, CsCl, NaF, NaNO3), due to the effects of these electrolytes on water structure dynamics and solute hydration. Based on the results of AFM in situ experiments performed at supersaturation (Ω) = 10.6 ± 0.1 and ionic strength (IS) in the range of 0.005-0.1 M we show that growth and dissolution behavior of barite changes under conditions of constant thermodynamic driving force (Ω) and constant IS in a systematic way depending on the specific background electrolyte used to adjust IS. The results are interpreted in terms of the relationships between solution composition, ion properties and the consequent growth and dissolution behavior. Island spreading rate is affected by salt-specific effects on the activation energy barrier of expelling water molecules from solvation shells of barite building units. Dissolution kinetics depends on the balance between the energy expended on breaking solvent structure and the energy gain on hydrating Ba2+ and ions, which are specific for different electrolyte solutions. Nucleation rates are determined by the frequency of water exchange around a barium cation which also depends on solution composition. Relating the structure of the solution to its composition can help to understand phenomena such as growth and dissolution in the presence of organic additives or impurity incorporation.  相似文献   

3.
The dissolution rate of illite, a common clay mineral in Australian soils, was studied in saline-acidic solutions under far from equilibrium conditions. The clay fraction of Na-saturated Silver Hill illite (K1.38Na0.05)(Al2.87Mg0.46Fe3+0.39Fe2+0.28Ti0.07)[Si7.02Al0.98]O20(OH)4 was used for this study. The dissolution rates were measured using flow-through reactors at 25 ± 1 °C, solution pH range of 1.0-4.25 (H2SO4) and at two ionic strengths (0.01 and 0.25 M) maintained using NaCl solution. Illite dissolution rates were calculated from the steady state release rates of Al and Si. The dissolution stoichiometry was determined from Al/Si, K/Si, Mg/Si and Fe/Si ratios. The release rates of cations were highly incongruent during the initial stage of experiments, with a preferential release of Al and K over Si in majority of the experiments. An Al/Si ratio >1 was observed at pH 2 and 3 while a ratio close to the stoichiometric composition was observed at pH 1 and 4 at the higher ionic strength. A relatively higher K+ release rate was observed at I = 0.25 in 2-4 pH range than at I = 0.01, possibly due to ion exchange reaction between Na+ from the solution and K+ from interlayer sites of illite. The steady state release rates of K, Fe and Mg were higher than Si over the entire pH range investigated in the study. From the point of view of the dominant structural cations (Si and Al), stoichiometric dissolution of illite occurred at pH 1-4 in the higher ionic strength experiments and at pH ?3 for the lower ionic strength experiments. The experiment at pH 4.25 and at the lower ionic strength exhibited lower RAl (dissolution rate calculated from steady state Al release) than RSi (dissolution rate calculated from steady state Si release), possibly due to the adsorption of dissolved Al as the output solutions were undersaturated with respect to gibbsite. The dissolution of illite appears to proceed with the removal of interlayer K followed by the dissolution of octahedral cations (Fe, Mg and Al), the dissolution of Si is the limiting step in the illite dissolution process. A dissolution rate law showing the dependence of illite dissolution rate on proton concentration in the acid-sulfate solutions was derived from the steady state dissolution rates and can be used in predicting the impact of illite dissolution in saline acid-sulfate environments. The fractional reaction orders of 0.32 (I = 0.25) and 0.36 (I = 0.01) obtained in the study for illite dissolution are similar to the values reported for smectite. The dissolution rate of illite is mainly controlled by solution pH and no effect of ionic strength was observed on the dissolution rates.  相似文献   

4.
The heat of precipitation, the mean crystal size and the broadness of crystal size distribution of barium sulfate precipitating in aqueous solutions of different background electrolytes (KCl, NaCl, LiCl, NaBr or NaF), was shown to vary at constant thermodynamic driving force (supersaturation) and constant ionic strength depending on the salt present in solution. The relative inversion in the effect of respective background ions on the characteristics of barite precipitate was observed between two studied supersaturation (Ω) and ionic strength (IS) conditions. The crystal size variance (β2) increased in the presence of background electrolytes in the order LiCl < NaCl < KCl at Ω = 103.33 and IS = 0.03 M and KCl < NaCl < LiCl at Ω = 103.77 and IS = 0.09 M. At a given Ω and IS the respective size of barite crystals decreased with increasing β2 in chloride salts of different cations and remained constant in sodium salts of different anions.We suggest that ionic salts affect the kinetics of barite nucleation and growth due to their influence on water of solvation and bulk solvent structure. This idea is consistent with the hypothesis that the kinetic barrier for barium sulfate nucleation depends on the frequency of water exchange around respective building units that can be modified by additives present in solution. In electrolyte solution the relative switchover between long range electrostatic interactions and short range hydration forces, which influence the dynamics of solvent exchange between an ion solvation shell and bulk fluid, results in the observed inversion in the effect of differently hydrated salts on nucleation rates and the resulting precipitate characteristics.  相似文献   

5.
The subsurface mobility of Np is difficult to predict in part due to uncertainties associated with its sorption behavior in geologic systems. In this study, we measured Np adsorption onto a common gram-positive soil bacterium, Bacillus subtilis. We performed batch adsorption experiments with Np(V) solutions as a function of pH, from 2.5 to 8, as a function of total Np concentration from 1.29 × 10−5 M to 2.57 × 10−4 M, and as a function of ionic strength from 0.001 to 0.5 M NaClO4. Under most pH conditions, Np adsorption is reversible and exhibits an inverse relationship with ionic strength, with adsorption increasing with increasing pH. At low pH in the 0.1 M ionic strength systems, we observed irreversible adsorption, which is consistent with reduction of Np(V) to Np(IV). We model the adsorption reaction using a nonelectrostatic surface complexation approach to yield ionic strength dependent NpO2+-bacterial surface stability constants. The data require two bacterial surface complexation reactions to account for the observed adsorption behavior: R-L1− + NpO2+ ↔ R-L1-NpO2° and R-L2− + NpO2+ ↔ R-L2-NpO2°, where R represents the bacterium to which each functional group is attached, and L1 and L2 represent the first and second of four discrete site types on the bacterial surface. Stability constants (log K values) for the L1 and L2 reactions in the 0.001 M system are 2.3 ± 0.3 and 2.3 ± 0.2, and in the 0.1 M system the values are 1.7 ± 0.2 and 1.6 ± 0.2, respectively. The calculated neptunyl-bacterial surface stability constants are not consistent with values predicted using the linear free energy correlation approach from Fein et al. (2001), suggesting that possible unfavorable steric interactions and the low charge of NpO2+ affects Np-bacterial adsorption.  相似文献   

6.
Numerous studies have utilized surface complexation theory to model proton adsorption behaviour onto mesophilic bacteria. However, few experiments, to date, have investigated the effects of pH and ionic strength on proton interactions with thermophilic bacteria. In this study, we characterize proton adsorption by the thermophile Anoxybacillus flavithermus by performing acid-base titrations and electrophoretic mobility measurements in NaNO3 (0.001-0.1 M). Equilibrium thermodynamics (Donnan model) were applied to describe the specific chemical reactions that occur at the water-bacteria interface. Acid-base titrations were used to determine deprotonation constants and site concentrations for the important cell wall functional groups, while electrophoretic mobility data were used to further constrain the model. We observe that with increasing pH and ionic strength, the buffering capacity increases and the electrophoretic mobility decreases. We develop a single surface complexation model to describe proton interactions with the cells, both as a function of pH and ionic strength. Based on the model, the acid-base properties of the cell wall of A. flavithermus can best be characterized by invoking three distinct types of cell wall functional groups, with pKa values of 4.94, 6.85, and 7.85, and site concentrations of 5.33, 1.79, and 1.42 × 10−4 moles per gram of dry bacteria, respectively. A. flavithermus imparts less buffering capacity than pure mesophilic bacteria studied to date because the thermophile possesses a lower total site density (8.54 × 10−4 moles per dry gram bacteria).  相似文献   

7.
《Applied Geochemistry》2003,18(10):1573-1582
The effects of the ionic strength (maintained by LiCl, NaCl or KCl) and Ca2+ and Mg2+ concentration on the coagulation of purified humic acids (HA) was studied. Solutions of known ionic strengths, pcH, Ca2+ and Mg2+ concentrations were prepared with HA and filtered to obtain the fraction with a size smaller than 100 kD. After a 50 day storage, samples of these solutions were filtered again (100 kD) and the total organic C (TOC) of the filtered solutions measured. The HA coagulation increased with salt concentration, with the cationic charge, and for cations of the same charge, with the cationic charge density. The coagulation decreased for pcH values of 4 to 7–8 in the absence of and presence of Mg2+ and Ca2+. In the absence of the divalent cations, the coagulation has a constant value for pcH>8, but, in the presence of Mg2+ and Ca2+, increases at pcH values greater than 9. The coagulation of humic materials occurs whether the samples are exposed to light or kept in the dark, although the coagulation kinetics are slower for the samples kept in the dark. The size distribution of size-fractionated humic solutions changes over time to a size distribution similar to that of the original humic solution before it was size-fractionated. The results are explained by the DLVO theory.  相似文献   

8.
In this study, we conducted electrophoretic mobility, potentiometric titration, and metal sorption experiments to investigate the surface charge characteristics of Bacillus subtilis and the electrostatic interactions between metal cations and the cell surface electric field. Electrophoretic mobility experiments performed as a function of pH and ionic strength show an isoelectric point of pH 2.4, with the magnitude of the electrokinetic potential increasing with increasing pH, and decreasing with increasing ionic strength. Potentiometric titration experiments conducted from pH 2.4 to 9 yield an average surface charge excess of 1.6 μmol/mg (dry mass). Corresponding cell wall charge density values were used to calculate the Donnan potential (ΨDON) as function of pH and ionic strength. Metal sorption experiments conducted with Ca(II), Sr(II), and Ba(II) exhibit strong ionic strength dependence, suggesting that the metal ions are bound to the bacterial cell wall via an outer-sphere complexation mechanism. Intrinsic metal sorption constants for the sorption reactions were determined by correcting the apparent sorption constant with the Boltzmann factor. A 1:2 metal-ligand stoichiometry provides the best fit to the experimental data with log K2int values of 5.9 ± 0.3, 6.0 ± 0.2, 6.2 ± 0.2 for Ca(II), Sr(II), and Ba(II) respectively. Electrophoretic mobility measurements of cells sorbed with Ca(II), Sr(II), and Ba(II) support the 1:2 sorption stoichiometry. These results indicate that electrical potential parameters derived from the Donnan model can be applied to predict metal binding onto bacterial surfaces over a wide range of pH and ionic strength conditions.  相似文献   

9.
Rate laws reported for the oligomerization of silica in natural environments are often contradictory, and the kinetics of monosilicic acid condensation are poorly understood. Here we present rate expressions that systematically describe the initial oligomerization of silica in terms of concentration of initial silica, ionic strength, and pH for a natural brine solution. The oligomerization of silica in dilute aqueous solutions was examined in solutions with ionic strengths of 0.01 and 0.24 molal, from pH 3 to 11, and with initial silica concentrations of 4.2, 12.5, and 20.8 millimolal (250, 750, and 1250 ppm SiO2 respectively). The decrease in concentration of molybdate-reactive silica was monitored over time to determine the extent of oligomerization. This decrease in concentration of molybdate-reactive silica is accompanied by the appearance of a transient population of nanocolloidal particles with diameter ∼3 nm, as determined by atomic force microscopy (AFM). The oligomerization rate increases as pH approaches near neutral and as ionic strength increases. Early in the reaction where the concentration of molybdate-reactive silica, [SiO2]n≤3, is assumed to equal the concentration of monosilicic acid, [H4SiO4], the rate of change of monosilicic acid as a function of time, R, shows a fourth-order dependence:
R=k44[H4SiO4]  相似文献   

10.
This work reports on a concerted study of diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii= TW, Skeletonema costatum= SC) and two freshwater periphytic species (Achnanthidium minutissimum= AMIN, Navicula minima= NMIN). Proton surface adsorption was measured at 25°C, pH of 3 to 11 and ionic strength of 0.001 to 1.0 M via potentiometric titration using a limited residence time reactor. Electrophoretic mobility of living cells and their frustules was measured as a function of pH and ionic strength. Information on the chemical composition and molecular structure of diatoms surfaces was obtained using FT-IR (in situ attenuated total reflectance) and X-ray Photoelectron Spectroscopy (XPS). The surface area of living cells and their frustules in aqueous solutions was quantified using Small Angle X-ray Scattering Spectroscopy (SAXS).These observations allowed us to identify the nature and to determine the concentration of the major surface functional groups (carboxyl, amine and silanol) responsible for the amphoteric behavior of cell surfaces in aqueous solutions. Taking into account the relative proportion of surface sites inferred from XPS and FT-IR measurements, a surface complexation model of diatom-solution interfaces was generated on the basis of surface titration results. The cell-normalized ratios of the three major surface sites {>COOH}: {>NH3}: {>SiOH} are 1:1:0.1, 1:10:0, 1:1:0.4 and 1:1:0.3 for TW, SC, AMIN and NMIN, respectively. The total amount of proton/hydroxyl active surface sites for investigated species ranges from 1 (NMIN) to 9 (SC) mmol/g dry weight. Normalization of these site densities to the area of siliceous skeleton yields values between 0.3 (NMIN) and 0.9 mmol/m2 (SC) which are an order of magnitude higher than corresponding values for organic-free frustules or amorphous silica. This suggests that the amphoteric properties and possibly the affinity for metal adsorption of diatom cultures are essentially controlled by the 3-D organic layers covering the silica frustule.  相似文献   

11.
Steady-state silica release rates (rSi) from basaltic glass and crystalline basalt of similar chemical composition as well as dunitic peridotite have been determined in far-from-equilibrium dissolution experiments at 25 °C and pH 3.6 in (a) artificial seawater solutions under 4 bar pCO2, (b) varying ionic strength solutions, including acidified natural seawater, (c) acidified natural seawater of varying fluoride concentrations, and (d) acidified natural seawater of varying dissolved organic carbon concentrations. Glassy and crystalline basalts exhibit similar rSi in solutions of varying ionic strength and cation concentrations. Rates of all solids are found to increase by 0.3-0.5 log units in the presence of a pCO2 of 4 bar compared to CO2 pressure of the atmosphere. At atmospheric CO2 pressure, basaltic glass dissolution rates were most increased by the addition of fluoride to solution whereas crystalline basalt rates were most enhanced by the addition of organic ligands. In contrast, peridotite does not display any significant ligand-promoting effect, either in the presence of fluoride or organic acids. Most significantly, Si release rates from the basalts are found to be not more than 0.6 log units slower than corresponding rates of the peridotite at all conditions considered in this study. This difference becomes negligible in seawater suggesting that for the purposes of in-situ mineral sequestration, CO2-charged seawater injected into basalt might be nearly as efficient as injection into peridotite.  相似文献   

12.
Spectrophotometric measurements of the pH in natural waters such as seawater have been shown to yield precise results. In this paper, the sulfonephthalein indicator m-cresol purple (mCP, H2I) has been used to determine the pH of NaCl brines. The indicator has been calibrated in NaCl solutions from 5 to 45 °C and ionic strengths from 0.03 to 5.5 m. The calibrations were made using TRIS buffers (0.03 m, TRIS/TRIS-HCl) with known dissociation constants pKTRIS in NaCl solutions [Foti C., Rigano C. and Sammartano S. (1999) Analysis of thermodynamic data for complex formation: protonation of THAM and fluoride ion at different temperatures and ionic strength. Ann. Chim. 89, 1-12]. The values of pH were determined from
pH=pKmCP+log{(R-e1)/(e2-Re3)}  相似文献   

13.
High concentrations of naturally occurring radium pose environmental and health concerns in natural and industrial systems. The adsorption of Ra2+ in saline water is limited compared to its adsorption in fresh water, but the process of co-precipitation may be effective in decreasing its concentration. However, despite its importance, Ra co-precipitation has rarely been studied in high ionic strength environments such as those in evaporitic systems.The fate of Ra in the reject brine of a desalination plant was studied via evaporation batch experiments at ionic strengths (I) ranging from 0.7 to 7.0 mol kg−1. Precipitation sequences revealed that Ra co-precipitated with barite, even though the latter was a trace mineral compared to the precipitated gypsum. The concentration-based effective partition coefficient, , for the co-precipitation reaction was 1.04 ± 0.01. This value of is significantly lower than the value for relatively diluted solutions (1.8 ± 0.1). This low value of is mainly the result of a kinetic effect but is also slightly affected by the ionic strength.Both effects are quantitatively examined in the present paper. It is suggested that a kinetic effect influences the nucleation of (Ra,Ba)SO4, reducing the value of the partition coefficient. This kinetic effect is caused by the favorable nucleation of a more soluble phase (i.e., a phase with a higher BaSO4 fraction). An additional decrease in the partition coefficient results from the ionic strength effect. Considering the activity of Ra2+ and Ba2+ in the solution (rather than their concentration) makes it possible to determine the activity-based partition coefficient (), which accounts for the ionic strength effect. was calculated empirically from the experiments and theoretically via a kinetic model. The two derived values are consistent with one another and indicate the combined effect of ionic strength and precipitation kinetics.Finally, the common assumption that γRa2+/γBa2+=1 was re-examined using a numerical model to predict the experimental results. As the ionic strength increases, this assumption becomes less appropriate for predicting the change in as calculated in the experiments. Understanding the co-precipitation of Ra in such systems is crucial for risk assessments in which both Ra concentration and ionic strength are relatively high.  相似文献   

14.
The influence of background electrolytes on the mechanism and kinetics of calcite dissolution was investigated using in situ Atomic Force Microscopy (AFM). Experiments were carried out far from equilibrium by passing alkali halide salt (NaCl, NaF, NaI, KCl and LiCl) solutions over calcite cleavage surfaces. This AFM study shows that all the electrolytes tested enhance the calcite dissolution rate. The effect and its magnitude is determined by the nature and concentration of the electrolyte solution. Changes in morphology of dissolution etch pits and dissolution rates are interpreted in terms of modification in water structure dynamics (i.e. in the activation energy barrier of breaking water-water interactions), as well as solute and surface hydration induced by the presence of different ions in solution. At low ionic strength, stabilization of water hydration shells of calcium ions by non-paired electrolytes leads to a reduction in the calcite dissolution rate compared to pure water. At high ionic strength, salts with a common anion yield similar dissolution rates, increasing in the order Cl− < I− < F− for salts with a common cation due to an increasing mobility of water around the calcium ion. Changes in etch pit morphology observed in the presence of F− and Li+ are explained by stabilization of etch pit edges bonded by like-charged ions and ion incorporation, respectively. As previously reported and confirmed here for the case of F−, highly hydrated ions increased the etch pit nucleation density on calcite surfaces compared to pure water. This may be related to a reduction in the energy barrier for etch pit nucleation due to disruption of the surface hydration layer.  相似文献   

15.
  相似文献   

16.
A modified commercial (Setaram C80) calorimeter has been used to measure the isobaric volumetric heat capacities of concentrated alkaline sodium aluminate solutions at ionic strengths from 1 to 6 mol kg−1, with up to 40 mol.% substitution of hydroxide by aluminate, at temperatures from 50 to 300 °C and a pressure of 10 MPa. Apparent molar heat capacities for the mixtures, Cp?, derived from these data were found to depend linearly on the aluminate substitution level, i.e., they followed Young’s rule. These quantities were used to estimate the apparent molar heat capacities of pure, hypothetical sodium aluminate solutions, Cp? (‘NaAl(OH)4’(aq)). Slopes of the Young’s rule plots were invariant with ionic strength at a given temperature but depended linearly on temperature. The heat capacities of ternary aqueous sodium hydroxide/aluminate mixtures could therefore be modelled using only two parameters in addition to those needed for the correlation of Cp? (NaOH(aq)) reported previously from these laboratories. An assessment of the standard thermodynamic quantities for boehmite, gibbsite and the aluminate ion yielded a set of recommended values that, together with the present heat capacity data, accurately predicts the solubility of gibbsite and boehmite at temperatures up to 300 °C.  相似文献   

17.
《Applied Geochemistry》1997,12(2):203-211
The metal attenuation capacities of secondary acid mine water precipitates is dependent upon such factors as pH, ionic strength, the presence of competing ions, and tailings mineralogy. At the abandoned Spenceville Cu mine in Nevada County, California, approximately 6800 m3 of jarosite overburden and 28,000 m3 of hematite residue are potential sources of heavy metals loading to infiltrating surface waters. A column study was performed to assess the ability of the overburden and the residue to attenuate heavy metals from acidic mine drainage. The study information was needed as part of a remedial design for the abandoned mine, and was designed to simulate a worst-case scenario to examine the plausibility of backfilling a large open pit with the waste materials. Ten pore volumes of acidic mine drainage were allowed to pass through the materials, and the column effluents were analyzed for dissolved Fe, Al, Ca, Mg, Na, K, Mn, Cu, Zn, Pb and Ni using ICP-AES. The oxidation-reduction potential (Eh) was measured with a combination PtAg/AgCl electrode and also calculated from Fe(II) and Fe(III) measurements using the Nernst equation. Ion activities in solution and saturation index (SI) values for various solid phases were calculated using the geochemical speciation model MINTEQA2, and mineralogical compositions of fine (< 2 mm) and coarse ( > 2 mm) fractions were determined by XRD. Geochemical modeling of the column effluent compositions indicate that goethite, jarosite, jurbanite and gypsum are potential solid phases that may control metal solubilities in the column effluents. Excellent agreement was observed between the measured Eh values and those calculated from the activity ratio of Fe2+(aq) to Fe3+(aq). The large attenuation capacities for Cu and Zn exhibited by the jarosite overburden also suggest that solid solution substitution plays a large role in controlling metal concentrations in the pore waters. Relatively little metal attenuation, however, was provided by the hematite residue.  相似文献   

18.
The mechanisms by which background electrolytes modify the kinetics of non-equivalent step propagation during calcite growth were investigated using Atomic Force Microscopy (AFM), at constant driving force and solution stoichiometry. Our results suggest that the acute step spreading rate is controlled by kink-site nucleation and, ultimately, by the dehydration of surface sites, while the velocity of obtuse step advancement is mainly determined by hydration of calcium ions in solution. According to our results, kink nucleation at acute steps could be promoted by carbonate-assisted calcium attachment. The different sensitivity of obtuse and acute step propagation kinetics to cation and surface hydration could be the origin of the reversed geometries of calcite growth hillocks (i.e., rate of obtuse step spreading < rate of acute step spreading) observed in concentrated (ionic strength, IS = 0.1) KCl and CsCl solutions. At low IS (0.02), ion-specific effects seem to be mainly associated with changes in the solvation environment of calcium ions in solution. With increasing electrolyte concentration, the stabilization of surface water by weakly paired salts appears to become increasingly important in determining step spreading rate. At high ionic strength (IS = 0.1), overall calcite growth rates increased with increasing hydration of calcium in solution (i.e., decreasing ion pairing of background electrolytes for sodium-bearing salts) and with decreasing hydration of the carbonate surface site (i.e., increasing ion pairing for chloride-bearing salts). Changes in growth hillock morphology were observed in the presence of Li+, F− and , and can be interpreted as the result of the stabilization of polar surfaces due to increased ion hydration. These results increase our ability to predict crystal reactivity in natural fluids which contain significant amounts of solutes.  相似文献   

19.
The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs+, Ni2+ and 14 lanthanides (Ln3+) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni2+ and Ln3+ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol−1 and 39 ± 15 kJ.mol−1 for Ni2+ and Eu3+, respectively. On the other hand, the temperature effect on Cs+ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs+ on the montmorillonite is −19 ± 5 kJ.mol−1.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.  相似文献   

20.
Geotechnical characterisation is undertaken for 3 broad units comprising the bulk of the stratigraphy identified on White Island Volcano, Bay of Plenty, New Zealand, an active island stratovolcano. Field and laboratory measurements were used to describe rock mass characteristics for jointed lava flow units, and ring shear tests were undertaken to derive residual strength parameters for joint infilling materials within the lavas. Rock Mass Rating (RMR) and Geological Strength Index (GSI) values were calculated and converted to Mohr-Coulomb strength parameters using the Hoek-Brown criterion. Backanalysis of known landslide scarps was used to derive strength parameters for brecciated rock masses and hydrothermally altered rock masses. Andesite lava flows have high intact strength (σci = 184 ± 50 MN m− 2; γ = 24.7 ± 0.3 kN m− 3) and typically 3 wide, infilled joint sets, one parallel to flow direction and two steeply inclined, with spacings of 0.3-1.7 m. Joints are rough, with estimated friction angles for clean joints of ?j = 42-47°. Joint infill materials are clayey silts derived from weathering of wall rocks and primary volcanic sources; they have low plastic (54%) and liquid (84%) limits and residual strength values of cr = 0 kN m− 2 and ?r = 23.9 ± 3.1°. RMR values range from 70 to 73, giving calculated strength parameters of c′ = 1161-3391 kN m− 2 and ?′ = 50.5-62.3°. Backanalysis suggests brecciated rock masses have c′ = 0 kN m− 2 and ?′ = 35.4°, whereas GSI observations in the field suggest higher cohesion (c′ = 306-719 kN m− 2) and a range of friction angles bracketing the backanalysed result (?′ = 30.6-41.7°). Hydrothermally altered rock masses have c′ = 369 kN m− 2 and ?′ = 14.9°, indicating considerable loss of strength, especially frictional resistance, compared with the fresh lava units. Values measured at outcrop scale in this study are in keeping with other published values for similar volcanic edifices; backanalysed data suggest weaker rock mass properties than those determined at outcrop. This is interpreted as a scale issue, whereby rock mass characteristics of a large rock mass (crater wall scale) are weaker than those of small outcrops, due in part to the overestimation of friction angle from measurements on small exposures.  相似文献   

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