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1.
The aim of the present work was to study the thermodynamic equilibria between water and a homo-ionic montmorillonite SWy-1 saturated by different cations. The choice of this smectite is justified by the large set of experimental data available from the literature for eight different interlayer cations: Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, and Ba2+. In particular, studies by [Cases et al., 1992], [Cases et al., 1997] and [Bérend et al., 1995] are providing heat of adsorption data, pairs of desorption-adsorption isotherms, and information about the partition of adsorption-desorption water molecules between external surfaces and internal spaces. By calculating the effective amount of hydration water as the difference between the so-called gravimetric water and the surface covering water, a thermodynamic model was then developed, based on the concept of Ransom and Helgeson (1994) considering an asymmetric subregular binary solid solution between a fully hydrated and a anhydrous smectite. A set of six thermodynamic parameters ( and four Margules parameters) was extracted by a least square method from measurements of enthalpies of adsorption and paired adsorption-desorption isotherms for each interlayer cation. These six initial parameters were then used to determine a complete set of standard thermodynamic hydration parameters (, heat capacity, molar volume, and number of interlayer H2O) and quantify, for each cation, the number of moles of hydration water molecules as a function of relative humidity and temperature. The validation of the standard state thermodynamic properties of hydration for each end member was carried out using three approaches: (1) a comparison with experimental isotherms obtained on hetero-ionic and homo-ionic SWy-1 smectite at different temperatures; (2) a comparison with the experimental integral enthalpy and entropy of hydration of the SWy-1 smectite; and (3) a comparison with experimental isotherms acquired on various smectites (Upton, MX80, Arizona) with different layer charges.Eventually, the present work demonstrates that, from a limited number of measurements, it is possible to provide the hydration thermodynamic parameters for hydrated smectites with different compositions and under different conditions of temperature and relative humidity, using the newly developed predictive model.  相似文献   

2.
Highly mineralized waters of different chemical types and origin occur in the flysch formations and their bedrocks in the western part of the Polish Carpathians. The marine sedimentation water of the flysch formations is not preserved, as the most mineralized and the heaviest isotopic values of flysch waters are characterized by δ18O and δ2H values in the ranges of 5–7‰ and −(20–30)‰, respectively. Their origin is related to the dehydration of clay minerals during burial diagenesis, with molecules of marine water completely removed by molecules of released bound water. They are relatively enriched in Na+ in respect to the marine water, supposedly due to the release of Na+ during the illitization of smectites and preferable incorporation of other cations from the primary brine into newly formed minerals. In some parts of younger formations, i.e. in the Badenian sediments, brines occur with isotopic composition close to SMOW and Cl− contents greatly exceeding the typical marine value of about 19.6 g/L, supposedly due to ultrafiltration. Most probably, the marine water of the flysch formations was similarly enriched chemically in its initial burial stages. Final Cl− contents in diagenetic waters depend on different Cl− contents in the primary brines and on relationships between diagenetic and further ultrafiltration processes. In some areas, diagenetic waters migrate to the surface along fault zones and mix with young local meteoric waters becoming diluted, with the isotope composition scattering along typical mixing lines. In areas with independent CO2 flow from great depths, they form chloride CO2-rich waters. Common CO2-rich waters are formed in areas without near-surface occurrences of diagenetic waters. They change from the HCO3–Ca type for modern waters to HCO3–Mg–Ca, HCO3–Na–Ca and other types with elevated TDS, Mg2+ and/or Na− contents for old waters reaching even those of glacial age. Bedrocks of the flysch are represented by Mesozoic and Paleozoic mudstones, sandstones and carbonates, and in some areas by Badenian sediments. Brines of the Mesozoic and Paleozoic bedrocks are usually significantly enriched in Ca2+ and Mg2+ in comparison with the Badenian brines. By analogy to the deepest brines in the adjacent Upper Silesian Coal Basin, they are supposed to originate from paleometeoric waters of a hot climate.  相似文献   

3.
Tri-octahedral Li-Mg smectites (hectorites) were synthesized at temperatures ranging from 25 to 250 °C, in the presence of solutions highly enriched in lithium. After removing all the exchangeable lithium from the synthesized clays, Li isotope fractionation (Δ7Liclay-solution) was determined. This fractionation was linked to Li incorporation into the structural octahedral site, substituting for Mg2+. As predicted, experimental Δ7Liclay-solution inversely correlates with temperature, and ranges from −1.6‰ ± 1.3‰ at 250 °C to −10.0‰ ± 1.3‰ at 90 °C, and then stays relatively constant down to 25 °C. The relatively constant isotope fractionation factor below 90 °C may be due to high concentrations of edge octahedra in low crystallinity smectites. The isotopic fractionation factor (α), for a given temperature, does not depend on the solution matrix, nor on the amount of structural Li incorporated into the clay. Empirical linear laws for α as a function of 1/T (K) were inferred. Smectite Li contents and smectite-solution distribution coefficients (DLi/Mg) increase with temperature, as expected for a substitution process. The fractions of dissolved Li incorporated into the smectite octahedral sites are small and do not depend on the duration of the experiment. In a seawater-like matrix solution, less Li is incorporated into the smectites, probably as a result of competition with dissolved Mg2+ ions for incorporation into the octahedral sites. The high Li contents observed in marine smectites are therefore best explained either by a significant contribution from basalts, by adsorption processes, or by the influence of seawater chemical composition on distribution coefficients. We also calculate, using present-day estimates of hydrothermal water and river fluxes, that a steady-state ocean would require a relatively large global clay-water Li isotope fractionation (−12‰ to −21‰). This study demonstrates the ability of laboratory experiments to quantify the impact of secondary phases on the Li geochemical cycle and associated isotope fractionations.  相似文献   

4.
The effects of heating and cation exchange on the solid acidity of montmorillonite were investigated using n-butylamine titration in non-aqueous system and diffuse reflectance Fourier transform infrared spectroscopy. The number of total, Brønsted, and Lewis acid sites showed the same modulation tendency with increasing heating temperature, reaching a maximum at 120 °C and subsequently decreasing until it reaches a minimum at 600 °C. The Lewis acid sites result from unsaturated Al3+ cations, and their number increased with the heating temperature due to the dehydration and dehydroxylation of montmorillonite. The generation and evolution of Brønsted acidity were mainly related to interlayer-polarized water molecules. Water adsorbed on the unsaturated Al3+ ions also acted as a Brønsted acid. The acid strength of the Brønsted acid sites was dependent on the polarization ability of the exchangeable cation, the amount of interlayer water, and the degree of dissociation of the interlayer water coordinated to exchangeable cations. All cation-exchanged montmorillonites exhibited different numbers of acid sites and various distributions of acid strength. Brønsted acidity was predominant in Al3+-exchanged montmorillonite, whereas the Na+- and K+-exchanged montmorillonites showed predominantly Lewis acidity. Moreover, Mg2+- and Li+-exchanged montmorillonites exhibited approximately equal numbers of Brønsted and Lewis acid sites. The Brønsted acidity of cation-exchanged montmorillonite was positively correlated with the charge-to-radius ratios of the cations, whereas the Lewis acidity was highly dependent on the electronegativity of the cations. The acid strengths of Al3+- and Mg2+-exchanged montmorillonites were remarkably higher than those of monovalent cation-exchanged montmorillonites, showing the highest acid strength (H 0 ≤ ?3.0). Li+- and Na+-exchanged montmorillonites exhibited an acid strength distribution of ?3.0 < H 0 ≤ 4.8, with the acid strength ranging primarily from 1.5 to 3.3 in Li+-exchanged montmorillonite, whereas only weaker-strength acid sites (1.5 < H 0 ≤ 4.8) were present in K+-exchanged montmorillonite. The results of the catalysis experiments indicated that montmorillonite promoted the thermal decomposition of the model organic. The catalytic activity showed a positive correlation with the solid acidity of montmorillonite and was affected by cation exchange, which occurs naturally in geological processes.  相似文献   

5.
In situ Atomic Force Microscopy, AFM, experiments have been carried out using calcite cleavage surfaces in contact with solutions of MgSO4, MgCl2, Na2SO4 and NaCl in order to attempt to understand the role of Mg2+ during calcite dissolution. Although previous work has indicated that magnesium inhibits calcite dissolution, quantitative AFM analyses show that despite the fact that Mg2+ inhibits etch pit spreading, it increases the density and depth of etch pits nucleated on calcite surfaces and, subsequently, the overall dissolution rates: i.e., from 10−11.75 mol cm−2 s−1 (in deionized water) up to 10−10.54 mol cm−2 s−1 (in 2.8 M MgSO4). Such an effect is concentration-dependent and it is most evident in concentrated solutions ([Mg2+] >> 50 mM). These results show that common soluble salts (especially Mg sulfates) may play a critical role in the chemical weathering of carbonate rocks in nature as well as in the decay of carbonate stone in buildings and statuary.  相似文献   

6.
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7.
Formation of todorokite from vernadite in Ni-rich hemipelagic sediments   总被引：1，自引：0，他引：1  
Todorokite is considered to form from vernadite in nature and commonly concentrates nickel. However, this mineralogical transformation has never been imaged nor explained mechanistically, and its effect on the uptake of nickel has never been quantified at the molecular-level. We have characterized these reactions at the macroscopic, microscopic, nanoscopic and atomic scales in a marine manganese concretion by combining transmission electron microscopy, electron and X-ray microprobe analysis, powder and micro X-ray diffraction, and Mn and Ni K-edge EXAFS spectroscopy. The concretion was collected during the Ticoflux II expedition near the Nicoya Peninsula, Costa Rica, and is representative of Mn deposits in hemipelagic sediments. It consists of 5 to 25 μm aggregates, shaped like sea-urchins, with a core of 7Å-vernadite (1.0 wt% Ni), a rim of 10Å-vernadite (3.8 wt% Ni), and an outermost region of todorokite fibers (1.9 wt% Ni) that extend outwards. The crystallites of 7Å-vernadite are single- to bi-layered, with hexagonal layer symmetry (a = b = 2.83 Å), and an average structural formula of . The crystallites of 10Å-vernadite contain 10 to 20 layers semi-coherently stacked in the ab plane and uniformly separated in the [0 0 1] direction by ∼9 Å due to the intercalation of hydrated Mg2+ cations. The average structural formula of 10Å-vernadite is if the layers contain vacancy sites, or alternately , if they contain Mn3+. The average formula of todorokite is .A genetic model is proposed based on combining these new data with previously published results. The thermodynamically unstable 7Å-vernadite transforms via dissolution-recrystallization to semi-ordered Mg-rich 10Å-vernadite. Nickel is released from dissolved biogenic silica or reduced organic matter, and taken up mainly in the Mn layer of 10Å-vernadite. Interlayer magnesium serves as a template to the further topotactic transformation of 10Å-vernadite to todorokite. The dimension of the todorokite tunnels in the [0 0 1] direction is uniform and determined by the size of the hydrated Mg2+ ion (8.6 Å). The tunnel dimension in the [1 0 0] direction depends on the density of Mg2+ in the interlayer and the superstructure of the phyllomanganate layer. If the parent phyllomanganate contains high amounts of Mg2+ (i.e., high layer charge), or Mn3+ and Mn4+ cations ordered following the Mn3+-Mn4+-Mn4+ sequence as in synthetic triclinic birnessite, then the tunnel dimension is ideally 3 × 3 octahedral chain widths in both crystallographic directions. Otherwise, the tunnel dimension is incoherent in the [1 0 0] direction (i.e., T(3,n) tunnel structure), as has been observed in all natural todorokites. Natural todorokite is defective because the precursor natural phyllomanganates either have a layer charge deficit below 0.33e per octahedral site, or rarely are triclinic birnessite. The abundance of Mg in seawater and its key role in converting phyllomanganate to tectomanganate with T(3,n) tunnel structure explain why todorokite is common in marine ferromanganese oxides, and seldom present in terrestrial environments. The topotactic phase transformation described here is the only known route to todorokite crystallization. This implies that all natural todorokites may be authigenic because they are formed in situ from a phyllomanganate precursor.  相似文献   

8.
Drying induced pH changes were quantified on the surface of Na+, Ca2+, Mg2+ and Al3+ saturated smectite and kaolinite clays. This was achieved using attenuated total reflectance Fourier transform infrared (ATR-FTIR) spectroscopy to measure real time changes to a pH indicator, sorbed to the clay mineral surface, during wetting and drying events. Using this technique it was possible to measure how low the pH of the surface drops during dehydration, the critical water content at which acidification of the surface begins and lastly how reversible the pH decrease is. The results show that only Al3+-smectite shows acidification below pH 4.8 with drying. The pH starts to decrease on the Al3+-smectite surface even when significantly hydrated (gravimetric water content ∼ 125 mg/m2), and falls to between 1.2 and 1.4 when completely air dry. The drying induced pH decrease is completely reversible on rewetting, suggesting large pH oscillations may occur on smectite surfaces with appreciable exchangeable Al3+. Aluminium saturated kaolinite did not show significant acidification in response to drying (pH > 3.5), however, a 0.1 M AlCl3 solution evaporated to a final pH of 2.8. The enhanced acidification observed on an Al-smectite clay compared to a solution containing free Al3+ ions highlights the role of highly charged surfaces in the hydrolysis reaction that occurs within the hydration shell of exchangeable Al3+ ions.  相似文献   

9.
Aragonite was precipitated in the laboratory at 0, 5, 10, 25, and 40 °C to determine the temperature dependence of the equilibrium oxygen isotope fractionation between aragonite and water. Forced CO2 degassing, passive CO2 degassing, and constant addition methods were employed to precipitate aragonite from supersaturated solutions, but the resulting aragonite-water oxygen isotope fractionation was independent of the precipitation method. In addition, under the experimental conditions of this study, the effect of precipitation rate on the oxygen isotope fractionation between aragonite and water was almost within the analytical error of ±∼0.13‰ and thus insignificant. Because the presence of Mg2+ ions is required to nucleate and precipitate aragonite from Na-Ca-Cl-HCO3 solutions under these experimental conditions, the influence of the total Mg2+ concentration (up to ∼0.9 molal) on the aragonite-water oxygen isotope fractionation was examined at 25 °C. No significant Mg2+ ion effect, or oxygen isotope salt effect, was detected up to 100 mmolal total Mg2+ but a noticeable isotope salt effect was observed at ∼0.9 molal total Mg2+.On the basis of results of the laboratory synthesis experiments, a new expression for the aragonite-water fractionation is proposed over the temperature range of 0-40 °C:
1000lnαaragonite-water=17.88±0.13(103/T)-31.14±0.46  相似文献   

10.
The mineralogy of natural ferromanganese coatings on quartz grains and the crystal chemistry of associated trace elements Ni, Zn, Ba, and As were characterized by X-ray microfluorescence, X-ray diffraction, and EXAFS spectroscopy. Fe is speciated as ferrihydrite and Mn as vernadite. The two oxides form alternating Fe- and Mn-rich layers that are irregularly distributed and not always continuous. Unlike naturally abundant Fe-vernadite, in which Fe and Mn are mixed at the nanoscale, the ferrihydrite and vernadite are physically segregated and the trace elements clearly partitioned at the microscopic scale. Vernadite consists of two populations of interstratified one-water layer (7 Å phyllomanganate) and two-water layer (10 Å phyllomanganate) crystallites. In one population, 7 Å layers dominate, and in the other 10 Å layers dominate. The three trace metals Ni, Zn, and Ba are associated with vernadite and the metalloid As with ferrihydrite. In vernadite, nickel is both substituted isomorphically for Mn in the manganese layer and sorbed at vacant Mn layer sites in the interlayer. The partitioning of Ni is pH-dependent, with a strong preference for the first site at circumneutral pH and for the second at acidic pH. Thus, the site occupancy of Ni in vernadite may be an indicator of marine vs. continental origin, and in the latter, of the acidity of streams, lakes, or soil pore waters in which the vernadite formed. Zinc is sorbed only in the interlayer at vacant Mn layer sites. It is fully tetrahedral at a Zn/Mn molar ratio of 0.0138, and partly octahedral at a Zn/Mn ratio of 0.1036 consistent with experimental studies showing that the VIZn/IVZn ratio increases with Zn loading. Barium is sorbed in a slightly offset position above empty tetrahedral cavities in the interlayer. Arsenic tetrahedra are retained at the ferrihydrite surface by a bidentate-binuclear attachment to two adjacent iron octahedra, as commonly observed. Trace elements in ferromanganese precipitates are partitioned at a few, well-defined, crystallographic sites that have some elemental specificity, and thus selectivity. The relative diversity of sorption sites contrasts with the simplicity of the layer structure of vernadite, in which charge deficit arises only from Mn4+ vacancies (i.e., no Mn3+ for Mn4+ substitution). Therefore, sorption mechanisms primarily depend on physical and chemical properties of the sorbate and competition with other ions in solution, such as protons at low pH for Ni sorption.  相似文献   

11.
The interfacial structures of the basal surface of muscovite mica in solutions containing (1) 5 × 10−3 m BaCl2, (2) 500 ppm Elliott Soil Fulvic Acid I (ESFA I), (3) 100 ppm Elliott Soil Fulvic Acid II (ESFA II), (4) 100 ppm Pahokee Peat Fulvic Acid I (PPFA), and (5) 5 × 10−3 m BaCl2 and 100 ppm ESFA II were obtained with high resolution in-situ X-ray reflectivity. The derived electron-density profile in BaCl2 shows two sharp peaks near the mica surface at 1.98(2) and 3.02(4) Å corresponding to the heights of a mixture of Ba2+ ions and water molecules adsorbed in ditrigonal cavities and water molecules coordinated to the Ba2+ ions, respectively. This pattern indicates that most Ba2+ ions are adsorbed on the mica surface as inner-sphere complexes in a partially hydrated form. The amount of Ba2+ ions in the ditrigonal cavities compensates more than 90% of the layer charge of the mica surface. The electron-density profiles of the fulvic acids (FAs) adsorbed on the mica surface, in the absence of Ba2+, had overall thicknesses of 4.9-10.8 Å and consisted of one broad taller peak near the surface (likely hydrophobic and positively-charged groups) followed by a broad humped pattern (possibly containing negatively-charged functional groups). The total interfacial electron density and thickness of the FA layer increased as the solution FA concentration increased. The sorbed peat FA which has higher ash content showed a higher average electron density than the sorbed soil FA. When the muscovite reacted with a pre-mixed BaCl2-ESFA II solution, the positions of the two peaks nearest the surface matched those in the BaCl2 solution. However, the occupancy of the second peak decreased by about 30% implying that the hydration shell of surface-adsorbed Ba2+ was partially substituted by FA. The two surface peaks were followed by a broad less electron-dense layer suggesting a sorption mechanism in which Ba2+ acts dominantly as a bridging cation between the mica surface and FA. When the muscovite reacted first with FA and subsequently with BaCl2, more Ba2+ could be adsorbed on the FA-coated mica surface. The peak closest to the mica included Ba2+ ions adsorbed directly on the mica in an amount similar to that in the BaCl2 solution but more broadly distributed. A second peak observed within the FA layer suggests that the FA coating provides additional sites for Ba2+ sorption. The results indicate that enhanced uptake of heavy metals can occur when an organic coating already exists on a mineral surface.  相似文献   

12.
Many waters sampled in Yellowstone National Park, both high-temperature (30–94 °C) and low-temperature (0–30 °C), are acid–sulfate type with pH values of 1–5. Sulfuric acid is the dominant component, especially as pH values decrease below 3, and it forms from the oxidation of elemental S whose origin is H2S in hot gases derived from boiling of hydrothermal waters at depth. Four determinations of pH were obtained: (1) field pH at field temperature, (2) laboratory pH at laboratory temperature, (3) pH based on acidity titration, and (4) pH based on charge imbalance (at both laboratory and field temperatures). Laboratory pH, charge imbalance pH (at laboratory temperature), and acidity pH were in close agreement for pH < 2.7. Field pH measurements were predominantly used because the charge imbalance was <±10%. When the charge imbalance was generally >±10%, a selection process was used to compare acidity, laboratory, and charge balance pH to arrive at the best estimate. Differences between laboratory and field pH can be explained based on Fe oxidation, H2S or S2O3 oxidation, CO2 degassing, and the temperature-dependence of pK2 for H2SO4. Charge imbalances are shown to be dependent on a speciation model for pH values <3. The highest SO4 concentrations, in the thousands of mg/L, result from evaporative concentration at elevated temperatures as shown by the consistently high δ18O values (−10‰ to −3‰) and a δD vs. δ18O slope of 3, reflecting kinetic fractionation. Low SO4 concentrations (<100 mg/L) for thermal waters (>350 mg/L Cl) decrease as the Cl− concentration increases from boiling which appears inconsistent with the hypothesis of H2S oxidation as a source of hydrothermal SO4. This trend is consistent with the alternate hypothesis of anhydrite solubility equilibrium. Acid–sulfate water analyses are occasionally high in As, Hg, and NH3 concentrations but in contrast to acid mine waters they are low to below detection in Cu, Zn, Cd, and Pb concentrations. Even concentrations of SO4, Fe, and Al are much lower in thermal waters than acid mine waters of the same pH. This difference in water chemistry may explain why certain species of fly larvae live comfortably in Yellowstone’s acid waters but have not been observed in acid rock drainage of the same pH.  相似文献   

13.
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14.
The effect of the Si/Al distribution in the tetrahedral sheets of the vermiculite mineral has been investigated employing density functional theory. The structures of six models for vermiculite with the structural formula (Mg4)(Mg12)(Si8Al8)O40(OH)8·24(H2O) per unit cell were fully optimized. The models differ by the T···Mg2+···T coordination of the interlayer Mg2+ cations by two central cations from the adjacent tetrahedral sheets of the 2:1 vermiculite layers (T,T=Si,Al). We observed the formation of very strong hydrogen bonds between water molecules solvating the interlayer Mg2+ cations and the surface basal oxygen atoms of the 2:1 layers. The directionality of hydrogen bonds is the major factor determining the layer stacking in the vermiculite structure. Results showed that the most stable model is that where only silicon atoms in the tetrahedral sheets coordinate all interlayer Mg2+ cations.  相似文献   

15.
To explore the effects of layer-charge distribution on the thermodynamic and microscopic properties of Cs-smectites, classical molecular dynamic simulations are performed to derive the swelling curves, distributions and mobility of interlayer species, and Cs binding structures. Three representative smectites with distinct layer-charge distributions are used as model clay frameworks and interlayer water content is set within a wide range from 0 to 380 mgwater/gclay. All the three smectites swell in a similar way, presenting the characteristic swelling plateaus and similar trends of swelling energetic profiles. The full-monolayer hydrate, corresponding to the global minima of the immersion energy, is the most stable hydrated state of Cs-smectites. The calculated diffusion coefficients of interlayer species disclose the confining effects in all smectites: both water molecules and ions diffuse slower than corresponding bulk cases and they are much more mobile in the direction parallel to the clay surfaces than perpendicular to them. The formed inner-sphere complex structures are very similar in different smectites: ions bind on the H-sites or T-sites and water molecules form cage-like caps covering the ions. Layer-charge distribution is found to have significant influences on the mobility of interlayer species and preference of ion binding sites. A general sequence is proposed to elucidate the preferences of various hexagonal sites (H-sites) and triangular sites (T-sites), that is, tetrahedrally substituted H-sites > nonsubstituted H-sites > tetrahedrally substituted T-sites > nonsubstituted T-sites, but the influence of octahedral substitutions on the preference of the neighboring sites is not obvious. Analysis of mobility indicates that H-sites are more stable Cs-fixation positions than T-sites and smectite with higher fraction of octahedral charges seems to be the most effective barrier material no matter how water content varies although all smectites can immobilize Cs ions in relatively dry conditions. These findings will not only facilitate basic research in geochemistry and material sciences, but also promote the barrier material designing.  相似文献   

16.
The interaction of Pu3+ bearing solutions with the muscovite (0 0 1) basal plane is explored using a combination of ex-situ approaches including alpha-counting, to determine the Pu3+ adsorption isotherm, and X-ray reflectivity (XR) and resonant anomalous X-ray reflectivity (RAXR), to probe the interfacial structure and Pu-specific distribution, respectively. Pu uptake to the muscovite (0 0 1) surface from Pu3+ solutions in a 0.1 M NaClO4 background electrolyte at pH 3 follows an approximate Langmuir isotherm with an apparent adsorption constant, Kapp = 5 × 104 M−1, and with a maximum coverage that is consistent with the amount needed to fully compensate the surface charge by trivalent Pu. The XR results show that the muscovite surface reacted with a 10−3 M Pu3+ solution (at pH 3 with 0.1 M NaClO4) and dried in the ambient environment, maintains a 30-40 Å thick layer, indicating the presence of a residual hydration layer (possibly including adventitious carbon). The RAXR results indicate that Pu sorbs on the muscovite surface with an intrinsically broad distribution with an average height of 18 Å, substantially larger than heights expected for any specifically adsorbed inner- or outer-sphere complexes. These results are discussed in the context of recent studies of cation adsorption trends on muscovite and the possible roles of Pu hydrolysis species in controlling the Pu-muscovite interactions.  相似文献   

17.
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   

18.
Monte Carlo simulations show that the adsorption position of the Sr2+ or Ba2+ ion on the cleaved muscovite surface is determined by the radius of the ion’s first hydration shell, hydrogen bonding of the first shell water molecules with the basal oxygens of muscovite as well as a requirement of minimization of the number of muscovite’s lattice cations in the ion’s first coordination shell. Accordingly, Sr2+ or Ba2+ adsorbs in ditrigonal cavities at a distance of 1.12 Å or 1.35 Å, respectively, from the basal surface on dehydrated mica and above tetrahedral substitutions at a height of 1.93 ± 0.02 Å or 2.15 ± 0.03 Å, respectively, at the highest simulated water coverage of 28 H2O per ion. The ion’s displacement from a ditrigonal cavity occurs upon adsorption of 2 H2O per ion for Sr2+ and 3 H2O per ion for Ba2+. At a coverage of 28 H2O per ion, outer-sphere adsorption of Sr2+ or Ba2+ at a height of 3.9 ± 0.2 Å or 4.17 ± 0.07 Å, respectively, is possible albeit unfavorable on the free energy scale by 107 ± 7 kJ/mol or 89 ± 13 kJ/mol, respectively, as compared to inner-sphere adsorption. Activation energies for the transformation between inner-sphere and outer-sphere adsorptions are calculated to be 121 ± 3 kJ/mol for Sr2+ and 99 ± 10 kJ/mol for Ba2+. A comparison of these values with those reported recently for Mg2+ and Ca2+ results in an adsorption affinity sequence Mg2+ > Ca2+ > Sr2+ > Ba2+ in agreement with the sequence predicted recently for low dielectric constant solids (which include mica) (Sverjensky, 2006). A recent resonant anomalous X-ray reflectivity study of Sr2+ adsorption on muscovite (Park et al., 2006) has questioned the common assumption (Stumm, 1992), which is supported by the present simulation results, that inner-sphere adsorption is stronger than outer-sphere adsorption. A modification of the cleaved muscovite surface as a result of Sr2+ adsorption in muscovite’s ditrigonal cavities and related destabilization of muscovite’s hydroxyl groups is proposed as a possible reason for this controversy.  相似文献   

19.
A thermodynamic model is presented to calculate methane solubility, liquid phase density and gas phase composition of the H2O-CH4 and H2O-CH4-NaCl systems from 273 to 523 K (possibly up to 573 K), from 1 to 2000 bar and from 0 to 6 mol kg−1 of NaCl with experimental accuracy. By a more strict theoretical approach and using updated experimental data, this model made substantial improvements over previous models: (1) the accuracy of methane solubility in pure water in the temperature range between 273 and 283 K is increased from about 10% to about 5%, but confirms the accuracy of the Duan model [Duan Z., Moller N., Weare J.H., 1992a. Prediction of methane solubilities in natural waters to high ionic strength from 0 to 250 °C and from 0 to 1600 bar. Geochim. Cosmochim. Acta56, 1451-1460] above 283 K up to 2000 bar; (2) the accuracy of methane solubility in the NaCl aqueous solutions is increased from >12% to about 6% on average from 273 K and 1 bar to 523 K and 2000 bar; (3) this model is able to calculate water content in the gas phase and liquid phase density, which cannot be calculated by previous models; and (4) it covers a wider range of temperature and pressure space. With a simple approach, this model is extended to predict CH4 solubility in other aqueous salt solutions containing Na+, K+, Mg2+, Ca2+, Cl− and , such as seawater and geothermal brines, with excellent accuracy. This model is also able to calculate homogenization pressure of fluid inclusions (CH4-H2O-NaCl) and CH4 solubility in water at gas-liquid-hydrate phase equilibrium. A computer code is developed for this model and can be downloaded from the website: www.geochem-model.org/programs.htm.  相似文献   

20.
Sandstone dissolution is a common water–rock reaction in the Earth’s crust, but a thorough understanding of this phenomenon is constrained by poorly determined kinetic data. To this end, kinetic data were determined for the dissolution of arkosic sandstone powders in deionised water (pH was about 7.0–7.3 and electrical conductivity was between 0.95 and 1.00 μS/cm). Release rates of dissolved elements were determined over the range 50–350 °C at 20, 15, and 10 MPa using a column flow-through pressure vessel reactor. The conductivity of the outlet solution, measured at room temperature, is dependent on the charge of major cations such as Na+, K+, Ca2+ and Mg2+ at these conditions. The conductivity of the outlet solution was used to determine the steady state of the dissolution of sandstone powders. The pH values of the outlet solutions at the steady state, measured ex situ at room temperature, were about 7.7, 8.3, 8.4, 8.4 and 7.6 at 75, 100, 150, 200 and 250 °C, respectively, at 10 MPa. Silicon, Na, K, Ca, Al and Mg are the major ions found in the solution at low temperatures, but Si is the only major ion retained at higher temperatures (>150 °C). Compared with static experiments, the flowing dissolution experiments occurred at conditions far from equilibrium. The relationship between temperature and dissolution rates of arkosic sandstone powders was described as log R = 0.005469t − 10.50 where R is the dissolution rates of sandstone powders in kg/(m2 s), t is temperature in °C which ranged from 100 to 350 °C at 20 and 15 MPa, and the dissolution rates of sandstone powders were measured only for the major dissolved elements without oxygen in the outlet solutions.  相似文献   

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