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1.
To improve confidence in glass alteration models, as used in nuclear and natural applications, their long-term predictive capacity has to be validated. For this purpose, we develop a new model that couples geochemical reactions with transport and use a fractured archaeological glass block that has been altered for 1800 years under well-constrained conditions in order to test the capacity of the model.The chemical model considers three steps in the alteration process: (1) formation of a hydrated glass by interdiffusion, whose kinetics are controlled by a pH and temperature dependent diffusion coefficient; (2) the dissolution of the hydrated glass, whose kinetics are based on an affinity law; (3) the precipitation of secondary phases if thermodynamic saturation is reached. All kinetic parameters were determined from experiments. The model was initially tested on alteration experiments in different solutions (pure water, Tris, seawater). It was then coupled with diffusive transport in solution to simulate alteration in cracks within the glass. Results of the simulations run over 1800 years are in good agreement with archaeological glass block observations concerning the nature of alteration products (hydrated glass, smectites, and carbonates) and crack alteration thicknesses. External cracks in direct contact with renewed seawater were altered at the forward dissolution rate and are filled with smectites (400−500 μm). Internal cracks are less altered (by 1 or 2 orders of magnitude) because of the strong coupling between alteration chemistry and transport. The initial crack aperture, the distance to the surface, and sealing by secondary phases account for these low alteration thicknesses. The agreement between simulations and observations thus validates the predictive capacity of this coupled geochemical model and increases more generally the robustness and confidence in glass alteration models to predict long-term behavior of nuclear waste in geological disposal or natural glass in the environment.  相似文献   

2.
The dissolution kinetics of five chemically complex and five chemically simple sodium silicate glass compositions (Na-Si±Al±B) were determined over a range of solution saturation values by varying the flow-through rates (1-100 mL/d) in a dynamic single-pass flow-through (SPFT) apparatus. The chemically complex borosilicate glasses are representative of prospective hosts for radioactive waste disposal and are characterized by relatively high molar Si/(Si + Al) and Na/(Al + B) ratios (>0.7 and >1.0, respectively). Analysis by X-ray absorption spectroscopy (XAS) indicates that the fraction of ivB to iiiB (N4) varies from 0.66 to 0.70. Despite large differences in bulk chemistry, values of δ29Si peak shift determined by MAS-NMR varies only by about 7 ppm (δ29Si = −94 to −87 ppm), indicating small differences in polymerization state for the glasses. Forward rates of reaction measured in dynamic experiments converge (average log10 rate [40 °C, pH 9] = −1.87 ± 0.79 [g/(m2 d)]) at high values of flow-rate (q) to sample surface area (S). Dissolution rates are independent of total Free Energy of Hydration (FEH) and this model appears to overestimate the impact of excess Na on chemical durability. For borosilicate glass compositions in which molar Na > Al + B, further addition of Na appears to stabilize the glass structure with respect to hydrolysis and dissolution. Compared to other borosilicate and aluminosilicate glasses, the glass specimens from this study dissolve at nearly the same rate (0-∼56×) as the more polymerized glasses, such as vitreous reedmergnerite (NaBSi3O8), albite, and silica. Dissolution of glass follows the order: boroaluminosilicate glass > vitreous reedmergnerite > vitreous albite > silica glass, which is roughly the same order of increasingly negative 29Si chemical shifts. The chemical shift of 29Si is a measure of the extent of bond overlap between Si and O and correlates with the forward rate of reaction. Thus, dissolution appears to be rate-limited by rupture of the Si-O bond, which is consistent with the tenants of Transition State Theory (TST). Therefore, dissolution at far from equilibrium conditions is dependent upon the speed of the rate-controlling elementary reaction and not on the sum of the free energies of hydration of the constituents of boroaluminosilicate glass.  相似文献   

3.
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4.
The present study investigates the alteration of a fractured glass block in contact with iron and Callovo-Oxfordian claystone at 90 °C under anoxic and water-saturated conditions. The alteration rates and the nature of glass alteration products at the different compact interfaces (glass-clay, glass-iron) and in cracks were assessed by solution chemistry and microscopic-scale techniques (scanning electron microscopy coupled with energy-dispersive X-ray microscopy, microRaman spectroscopy, and X-ray absorption fine structure spectroscopy). A significant but modest (two-fold) increase in glass alteration in contact with steel was observed, leading to an average alteration rate over the experiment of about 0.007–0.014 g/m2/d. This rate is significantly lower than forward rate r0 in clay-equilibrated groundwater (1.7 g/m2/d), indicating that a decrease of the alteration rate was not hindered by the steel presence. The corrosion–alteration interface was made up of successive layers of corrosion products in contact with iron, a layer of Fe silicates, and an altered glass layer enriched in Fe. Characterization of the glass block in direct contact with claystone revealed that the thickness of altered glass was much more important than at the glass-iron interface. The altered glass layer in contact with clay was slightly enriched in Fe and Mg, and depleted in alkali cations. Altered glass layers in cracks were usually limited to fringes thinner than 2 μm, with a thickness decreasing from the crack mouth, indicating that alteration is controlled by transport in the cracks. The fractures were partially filled with calcite and lanthanide hydroxocarbonate precipitates. These results contribute to the understanding of nuclear vitrified waste-iron-corrosion products interactions in a deep geological repository.  相似文献   

5.
In order to use lithium isotopes as tracers of silicate weathering, it is of primary importance to determine the processes responsible for Li isotope fractionation and to constrain the isotope fractionation factors caused by each process as a function of environmental parameters (e.g. temperature, pH). The aim of this study is to assess Li isotope fractionation during the dissolution of basalt and particularly during leaching of Li into solution by diffusion or ion exchange. To this end, we performed dissolution experiments on a Li-enriched synthetic basaltic glass at low ratios of mineral surface area/volume of solution (S/V), over short timescales, at various temperatures (50 and 90 °C) and pH (3, 7, and 10). Analyses of the Li isotope composition of the resulting solutions show that the leachates are enriched in 6Li (δ7Li = +4.9 to +10.5‰) compared to the fresh basaltic glass (δ7Li = +10.3 ± 0.4‰). The δ7Li value of the leachate is lower during the early stages of the leaching process, increasing to values close to the fresh basaltic glass as leaching progresses. These low δ7Li values can be explained in terms of diffusion-driven isotope fractionation. In order to quantify the fractionation caused by diffusion, we have developed a model that couples Li diffusion with dissolution of the glassy silicate network. This model calculates the ratio of the diffusion coefficients of both isotopes (a = D7/D6), as well as its dependence on temperature, pH, and S/V. a is mainly dependent on temperature, which can be explained by a small difference in activation energy (0.10 ± 0.02 kJ/mol) between 6Li+ and 7Li+. This temperature dependence reveals that Li isotope fractionation during diffusion is low at low temperatures (T < 20 °C), but can be significant at high temperatures. However, concerning hydrothermal fluids (T > 120 °C), the dissolution rate of basaltic glass is also high and masks the effects of diffusion. These results indicate that the high δ7Li values of river waters, in particular in basaltic catchments, and the fractionated values of hydrothermal fluids are mainly controlled by precipitation of secondary phases.  相似文献   

6.
Multiple Internal Reflection Fourier Transform Infra-Red (MIR-FTIR) spectroscopy was developed and used for in situ flow-through experiments designed to study the process of organic acid promoted silicate dissolution. In tandem with the FTIR analysis, ex situ X-ray scattering was used to perform detailed analyses of the changes in the surface structure and chemistry resulting from the dissolution process. Phthalic acid and forsteritic glass that had been Chemically Vapour Deposited (CVD) onto an internal reflection element were used as reactants, and the MIR-FTIR results showed that phthalic acid may promote dissolution by directly binding to exposed Mg metal ion centers on the solid surface. Integrated infrared absorption intensity as a function of time shows that phthalic acid attachment apparently follows a t1/2 dependence, indicating that attachment is a diffusive process. The diffusion coefficient of phthalic acid was estimated to be approximately 7 × 10−6 cm2 s−1 in the solution near the interface with the glass. Shifts in the infrared absorption structure of the phthalate complexed with the surface compared to the solute species indicate that phthalate forms a seven-membered ring chelate complex. This bidentate complex efficiently depletes Mg from the glass surface, such that after reaction as much as 95% of the Mg may be removed. Surface depletion in Mg causes adsorbate density to fall after an initial attachment stage for the organic ligand. In addition, the infrared analysis shows that silica in the near surface polymerizes after Mg removal, presumably to maintain charge balance. X-ray reflectivity shows that the dissolution rate of forsteritic glass at pH 4 based on Mg removal in such flow-through experiments was equal to 4 × 10−12 mol cm−2 s−1 (geometric surface area normalized). Reflectivity also shows how the surface mass density decreases during reaction from 2.64 g cm−3 to 2.2 g cm−3, consistent with preferential loss of Mg from the surface. Auxiliary batch experiments with forsteritic glass films deposited onto soda glass were also completed to add further constraints to the mechanism of reaction. By combining reflectivity with diffuse scatter measurements it is shown that the primary interface changes little in terms of atomic-scale roughness even after removal of several hundred angstroms of material. These measurements unequivocally show how a dicarboxylic acid bonds to and may chelate the dissolution of a magnesium-bearing silicate. At the molecular level the solid surface retreat may best be described by a depinning model where Mg is preferentially removed and residual silica tetrahedra polymerize and act to episodically “pin” the surface.  相似文献   

7.
Glass-iron-clay setups were reacted at 90 °C for 6-18 months to investigate the coupled interactions between glass alteration, Fe corrosion and clay transformation. The reacted interfaces were probed at the microscopic level using complementary characterization methods (scanning electron microscopy coupled with energy-dispersive X-ray analysis, micro-Raman spectroscopy, micro X-ray diffraction, micro X-ray fluorescence spectroscopy, and micro X-ray absorption near-edge structure spectroscopy). The 10-μm thick Fe foil was fully corroded within 10 months, exposing glass to the pore solution. Iron corrosion led to the formation of a layer containing mostly magnetite, siderite and Fe-rich phyllosilicates with one tetrahedral and one octahedral sheet (TO) or two tetrahedral and one octahedral (TOT) sheet per layer. The clay in contact with this corrosion layer was enriched in siderite (FeCO3). Glass alteration resulted in the formation of a gel layer whose thickness increased with reaction time (from 20 μm after 6 months to 80 μm after 18 months) and a thin layer of secondary precipitates that concentrated lanthanides, P, and Mo. Assuming conservative behavior of Zr, the Si molar concentration in the gel is about 57% that in the glass. Glass dissolution remained at a rate close to the initial dissolution rate r0. The data are consistent with glass dissolution sustained by the uptake of dissolved Si and charge-compensating cations on secondary (corrosion) products, thus maintaining the gel porosity open and facilitating the leaching of easily soluble elements.  相似文献   

8.
Dolomite (CaMg(CO3)2) is one of the common rock-forming minerals in many geological media, in particular in clayey layers that are currently considered as potential host formations for a deep radioactive waste disposal facility. Magnesium in solution is one of the elements known to potentially enhance the alteration of nuclear glasses. The alteration of borosilicate glasses with dolomite as a Mg-bearing mineral source was investigated for 8 months in batch tests at 90 °C. Glass composition effects were investigated through two compositions (SiBNaAlCaZrO and SiBNaAlZrO) differing in their Ca content. The Ca-rich glass alteration is slightly enhanced in the presence of dolomite compared to the alteration observed in pure water. This greater alteration is explained by the precipitation of Mg silicate phases on the dolomite and glass surfaces. In contrast, the Ca-free glass alteration decreases in the presence of dolomite compared to the alteration observed in pure water. This behavior is explained by Ca incorporation in the amorphous layer (formed during glass alteration) coming from dolomite dissolution. Calcium acts as a layer reorganizer and limits glass alteration by reducing the diffusion of reactive species through the altered layer. Modeling was performed using the GRAAL model implemented within the CHESS/HYTEC geochemical code to discriminate and interpret the mechanisms involved in glass/dolomite interactions. Magnesium released by dolomite dissolution reacts with silica provided by glass alteration to form Mg silicates. This reaction leads to a pH decrease. The main mechanism controlling glass alteration is the ability of dolomite to dissolve. During the experiment the quantities of secondary phases formed were very small, but for longer time scales, this mechanism could supply sufficient Mg in solution to form large amounts of Mg silicates and sustain glass alteration. The ability of the GRAAL model to reproduce the concentrations of elements in solution and solid phases regardless of the amount of dolomite and the glass composition strongly supports the basic modeling hypothesis.  相似文献   

9.
This investigation was carried out to assess the protective properties of the alteration film that develops during aqueous alteration of the French SON 68 (R7T7-type) nuclear glass, notably by examining the behavior of some network-forming cations in the presence of complexing anions. Glass alteration was studied here in the presence of orthophosphate ions. Comparisons were established between two series of tests performed with a solution containing orthophosphate ions and control tests performed under the same conditions but without phosphates. The first series of experiments was performed under initial rate conditions (i.e. in dilute media) to assess the effect of pH and phosphate concentration on the initial glass dissolution rate. Under these conditions, which ensure maximum chemical affinity of the glass dissolution reaction, phosphate adsorption occurs at the reaction interface only with acid pH values, at which the glass dissolution reaction is strongly inhibited. The elements that form complexes with the phosphates (Al, Fe, etc.) partially control glass dissolution in acidic media. Additional experiments carried out under saturated conditions — notably with respect to Si — in a solution enriched with phosphates showed that rare earth and Ca phosphates precipitated in the outer region of the alteration film, maintaining a glass dissolution rate significantly higher than in the control experiment. These observations have several implications. (1) Comparing the results obtained in the presence of phosphates and in the reference medium, the authors demonstrate deductively that glass dissolution is limited by the inner portion of the alteration film, i.e. the amorphous gel. (2) A kinetic law of SON 68 glass dissolution cannot be based on silica alone; the results of these experiments contradict Grambow’s model. (3) With regard to control of the glass dissolution kinetics by the protective properties of the gel, this type of experiment shows that the relation between the chemical composition and the microstructure of the gel is an important aspect in modeling the glass alteration kinetics, but that it is still poorly understood.  相似文献   

10.
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11.
We performed density measurements on a synthetic equivalent of lunar Apollo 17 74,220 “orange glass”, containing 9.1 wt% TiO2, at superliquidus conditions in the pressure range 0.5-8.5 GPa and temperature range 1723-2223 K using the sink/float technique. In the lunar pressure range, two experiments containing pure forsterite (Fo100) spheres at 1.0 GPa and 1727 K, and at 1.3 GPa-1739 K, showed neutral buoyancies, indicating that the density of molten orange glass was equal to the density of Fo100 at these conditions (3.09 ± 0.02 g cm−3). A third tight sink/float bracket using Fo90 spheres corresponds to a melt density of 3.25 ± 0.02 g cm−3 at ∼2.8 GPa and ∼1838 K.Our data predict a density crossover for the molten orange glass composition with equilibrium orthopyroxene at ∼2.8 GPa, equivalent to a depth of ∼600 km in the lunar mantle, and a density of ∼3.25 g cm−3. This crossover depth is close to the orange glass multiple saturation point, representing its minimum formation depth, at the appropriate oxygen fugacity (2.8-2.9 GPa). A density crossover with equilibrium olivine is predicted to fall outside the lunar pressure range (>4.7 GPa), indicating that molten orange glass is always less dense than its equilibrium olivines in the Moon. Our data therefore suggest that that lunar liquids with orange glass composition are buoyant with respect to their source region at P < ∼2.8 GPa, enabling their initial rise to the surface without the need for additional external driving forces.Fitting the density data to a Birch-Murnaghan equation of state at 2173 K leads to an array of acceptable solutions ranging between 16.1 and 20.3 GPa for the isothermal bulk modulus K2173 and 3.6-8 for its pressure derivative K′, with best-fit values K2173 = 18.8 GPa and K′ = 4.4 when assuming a model 1 bar density value of 2.86 g cm−3. When assuming a slightly lower 1 bar density value of 2.84 g cm−3 we find a range for K2173 of 14.4-18.0 and K′ 3.7-8.7, with best-fit values of 17.2 GPa and 4.5, respectively.  相似文献   

12.
In the present study, the dissolution and mobilization of Ce introduced in a simulated nuclear waste glass (MW) as a surrogate of Pu was investigated after leaching in pure water over 12 a at 90 °C and pH ∼ 9.6. The microscopic distribution and oxidation state of Ce in the altered glass were studied using micro-X-ray fluorescence (micro-XRF) mapping techniques and micro-X-ray near-edge absorption spectroscopy (micro-XANES). Distribution maps of CeIII and CeIV were obtained by recording the Lα fluorescence emission at two different incident X-ray energies, coinciding with the maximum contrast between CeIII and CeIV fluorescence intensities. The micro-XRF maps revealed that Ce was dominantly present as oxidized species (CeIV) in the original glass. After dissolution from the glass matrix, CeIV was partly reduced and re-immobilized as CeIII at grain boundaries or in the interstitial spaces between the glass particles. The concentration of CeIII was found to correlate with the spatial distribution of secondary Mg-clay formed during the aqueous corrosion as the main glass alteration product. Micro-XANES spectra collected at locations representative of both altered and non-altered glass domains confirmed the findings obtained by the redox mapping. Because redox-sensitive elements in the pristine MW glass (Fe, Cr, Se) occur almost exclusively as oxidized species, reduction of CeIV was probably mediated by an external source of reductants, such as Fe(0) from the steel reaction vessel.  相似文献   

13.
Calcium isotopes in tissues are thought to be influenced by an individual’s diet, reflecting parameters such as trophic level and dairy consumption, but this has not been carefully assessed. We report the calcium isotope ratios (δ44/42Ca) of modern and archaeological animal and human bone (n = 216). Modern sheep raised at the same location show 0.14 ± 0.08‰ higher δ44/42Ca in females than in males, which we attribute to lactation by the ewes. In the archaeological bone samples the calcium isotope ratios of the herbivorous fauna vary by location. At a single site, the archaeological fauna do not show a trophic level effect. Humans have lower δ44/42Ca than the mean site fauna by 0.22 ± 0.22‰, and the humans have a greater δ44/42Ca range than the animals. No effect of sex or age on the calcium isotope ratios was found, and intra-individual skeletal δ44/42Ca variability is negligible. We rule out dairy consumption as the main cause of the lower human δ44/42Ca, based on results from sites pre-dating animal domestication and dairy availability, and suggest instead that individual physiology and calcium intake may be important in determining bone calcium isotope ratios.  相似文献   

14.
The dissolution behavior of the barite (0 0 1) surface in pure water at 30 °C was investigated using in situ Atomic Force Microscopy (AFM), to better understand the dissolution mechanism and the microtopographical changes that occur during the dissolution, such as steps and etch pits. The dissolution of the barite (0 0 1) surface started with the slow retreat of steps, after which, about 60 min later, the <hk0> steps of one unit cell layer or multi-layers became two-step fronts (fast “f” and slow “s” steps) with a half-unit cell layer showing different retreat rates. The “f” step had a fast retreat rate (≈(14 ± 1) × 10−2 nm/s) and tended to have a jagged step edge, whereas the “s” step (≈(1.8 ± 0.1) × 10−2 nm/s) had a relatively straight front. The formation of the “f” steps led to the formation of a new one-layer step, where the front of the “s” step was overtaken by that of the immediate underlying “f” step. The “f” steps also led to the decrease of the <hk0> steps and the increase in the percentage of stable steps parallel to the [0 1 0] direction during the dissolution.Etch pits, which could be observed after about 90 min, were of three types: triangular etch pits with a depth of a half-unit cell, shallow etch pits, and deep etch pits. The triangular etch pits were bounded by the step edges parallel to [0 1 0], [1 2 0], and [] and had opposite orientations in the upper half and lower half layers. Shallow etch pits that had a depth of two or more half-unit cell layers had any two consecutive pits pointing in the opposite direction of each other. The triangular etch pit appeared to grow by simultaneously removal of a row of ions parallel to each direction from the three step edges. At first, deep etch pits were elongated in the [0 1 0] direction with a curved outline and then gradually developed to an angular form bounded by the {1 0 0}, {3 1 0}, and (0 0 1) faces. The retreat rate of the (0 0 1) face was much slower than those of the {1 0 0} and {3 1 0} and tended to separate into two rates ((0.13 ± 0.01) × 10−2 nm/s for the deep etch pits derived from a screw dislocation and (0.07 ± 0.01) × 10−2 nm/s for those from other line defects).The changes in the dissolution rate of a barite (0 0 1) surface during the dissolution were estimated using the retreat rates and densities of the various steps as well as the growth rates, density, and areas of the lateral faces of the deep etch pits that were obtained from this AFM analysis. Our results showed that the dissolution rate of the barite (0 0 1) surface gradually increased and approached the bulk dissolution rate because of the change in the main factor determining the dissolution rate from the density of the steps to the growth and the density of the deep etch pits on the surface.  相似文献   

15.
Determination of the area density of spontaneous fission tracks (ρs) in glass shards of Toba tephra is a reliable way to distinguish between the Youngest Toba Tuff (YTT) and the Oldest Toba Tuff (OTT). The ρs values for YTT, uncorrected for partial track fading, range from 70 to 181 tracks/cm2 with a weighted mean of 108 ± 5 tracks/cm2, based on 15 samples. Corrected ρs values for YTT are in the range of 77–140 tracks/cm2 with a weighted mean of 113 ± 8 tracks/cm2, within the range of uncorrected ρs values. No significant difference in ρs exists between YTT samples collected from marine and continental depositional settings. The uncorrected ρs for OTT is 1567 ± 114 tracks/cm2 so that confusion with YTT is unlikely.  相似文献   

16.
Microorganisms and higher plants produce biogenic ligands, such as siderophores, to mobilize Fe that otherwise would be unavailable. In this paper, we study the stability of arsenopyrite (FeAsS), one of the most important natural sources of arsenic on Earth, in the presence of desferrioxamine (DFO-B), a common siderophore ligand, at pH 5. Arsenopyrite specimens from mines in Panasqueira, Portugal (100-149 μm) that contained incrustations of Pb, corresponding to elemental Pb as determined by scanning electron microscopy-electron diffraction spectroscopy (SEM-EDX), were used for this study. Batch dissolution experiments of arsenopyrite (1 g L−1) in the presence of 200 μM DFO-B at initial pH (pH0) 5 were conducted for 110 h. In the presence of DFO-B, release of Fe, As, and Pb showed positive trends with time; less dependency was observed for the release of Fe, As, and Pb in the presence of only water under similar experimental conditions. Detected concentrations of soluble Fe, As, and Pb in suspensions containing only water were found to be ca. 0.09 ± 0.004, 0.15 ± 0.003, and 0.01 ± 0.01 ppm, respectively. In contrast, concentrations of soluble Fe, As, and Pb in suspensions containing DFO-B were found to be 0.4 ± 0.006, 0.27 ± 0.009, and 0.14 ± 0.005 ppm, respectively. Notably, the effectiveness of DFO-B for releasing Pb was ca. 10 times higher than that for releasing Fe. These results cannot be accounted for by thermodynamic considerations, namely, by size-to-charge ratio considerations of metal complexation by DFO-B. As determined by SEM-EDX, elemental sample enrichment analysis supports the idea that the Fe-S subunit bond energy is limiting for Fe release. Likely, the mechanism(s) of dissolution for Pb incrustations is independent and occurs concurrently to that for Fe and As. Our results show that dissolution of arsenopyrite leads to precipitation of elemental sulfur, and is consistent with a non-enzymatic mineral dissolution pathway. Finally, speciation analyses for As indicate variability in the As(III)/As(V) ratio with time, regardless of the presence of DFO-B or water. At reaction times <30 h, As(V) concentrations were found to be 50-70%, regardless of the presence of DFO-B. These results are interpreted to indicate that transformations of As are not imposed by ligand-mediated mechanisms. Experiments were also conducted to study the dissolution behavior of galena (PbS) in the presence of 200 μM at pH0 5. Results show that, unlike arsenopyrite, the dissolution behavior of galena shows coupled increases in pH with decreases in metal solubility at t > 80 h. Oxidative dissolution mechanisms conveying sulfur oxidation bring about the production of {H+}. However, dissolution data trends for arsenopyrite and galena indicate {H+} consumption. It is plausible that the formation of Pb species is dependent on {H+} and {OH−}, namely, stable surface hydroxyl complexes of the form (pH50 5.8) and for pH values 5.8 or above.  相似文献   

17.
With previous two-dimensional (2D) simulations based on surface-specific feldspar dissolution succeeding in relating the macroscopic feldspar kinetics to the molecular-scale surface reactions of Si and Al atoms ( [Zhang and Lüttge, 2008] and [Zhang and Lüttge, 2009]), we extended our modeling effort to three-dimensional (3D) feldspar particle dissolution simulations. Bearing on the same theoretical basis, the 3D feldspar particle dissolution simulations have verified the anisotropic surface kinetics observed in the 2D surface-specific simulations. The combined effect of saturation state, pH, and temperature on the surface kinetics anisotropy has been subsequently evaluated, found offering diverse options for morphological evolution of dissolving feldspar nanoparticles with varying grain sizes and starting shapes. Among the three primary faces on the simulated feldspar surface, the (1 0 0) face has the biggest dissolution rate across an extensively wide saturation state range and thus acquires a higher percentage of the surface area upon dissolution. The slowest dissolution occurs to either (0 0 1) or (0 1 0) faces depending on the bond energies of Si-(O)-Si (ΦSi-O-Si/kT) and Al-(O)-Si (ΦAl-O-Si/kT). When the ratio of ΦSi-O-Si/kT to ΦAl-O-Si/kT changes from 6:3 to 7:5, the dissolution rates of three primary faces change from the trend of (1 0 0) > (0 1 0) > (0 0 1) to the trend of (1 0 0) > (0 0 1) > (0 1 0). The rate difference between faces becomes more distinct and accordingly edge rounding becomes more significant. Feldspar nanoparticles also experience an increasing degree of edge rounding from far-from-equilibrium to close-to-equilibrium. Furthermore, we assessed the connection between the continuous morphological modification and the variation in the bulk dissolution rate during the dissolution of a single feldspar particle. Different normalization treatments equivalent to the commonly used mass, cube assumption, sphere assumption, geometric surface area, and reactive surface area normalizations have been used to normalize the bulk dissolution rate. For each of the treatments, time consistence and grain size dependence of the normalized dissolution rate have been evaluated and the results revealed significant dependences on the magnitude of surface kinetic anisotropy under differing environmental conditions. In general, the normalized dissolution rates are strongly dependent on grain size. Time-consistent normalization treatment varies with the investigated condition. The modeling results suggest that the sphere-, cube-, and BET-normalized dissolution rates are appropriate under the far-from-equilibrium conditions at low pH where these normalizations are time-consistent and are slightly dependent on grain size.  相似文献   

18.
Transport of iron (Fe) within hydrothermal and soil environments involves the transferral into aqueous solutions by leaching of complex, polyminerallic rocks. Understanding the isotope fractionation mechanisms during this process is key for any application of the Fe-isotope system to biogeochemical studies. Here, we reacted biotite granite and tholeiite-basalt with 0.5 M hydrochloric acid and 5 mM oxalic acid solutions at ambient temperature. Solution aliquots were recovered over a seven-day period and analysed for major and trace element concentrations and Fe isotopic compositions. In all experiments, Fe initially released into solution was isotopically lighter, with Δ56Fesolution-rock as low as −1.80‰ in the granite-hydrochloric acid system. The oxalic acid experiments showed similar patterns but smaller fractionation. In all experiments, the Δ56Fesolution-rock reduced over time, which would be in line with the formation of a leached layer as proposed before [Brantley S. L., Liermann L. J., Guynn R. L., Anbar A., Icopini G. A., and Barling J. (2004) Fe isotopic fractionation during mineral dissolution with and without bacteria. Geochim. Cosmochim. Acta68(15), 3189-3204]. Granite and basalts reacting with hydrochloric acid reached apparent steady-state values of −0.60 ± 0.15‰ and −0.40 ± 0.20‰, respectively, whilst experimental values with oxalic acid were −1.0 ± 0.15‰ and −0.50 ± 0.15‰. During the granite experiments, alteration of biotite to chlorite, followed by dissolution of chlorite, were likely the dominant processes, whilst in the basalt experiments, dissolution of pigeonite was likely the principal source of Fe. Variations in pH during the hydrochloric acid experiments were minimal, remaining below 0.5 at all times. In oxalic acid solutions, the pH increased to over 4, leading likely to precipitation of secondary minerals and adsorption/co-precipitation of Fe onto mineral surfaces. These processes could contribute to the greater fractionation observed in the final stages of the oxalic acid experiments. Our results highlight the importance of mineralogy and fluid composition on the Fe-isotope systematics during weathering. The fractionation processes identified for granites and basalts are in line with those inferred from field observations in soils, sediments, groundwater and hydrothermal deposits and from laboratory studies of single-mineral leaching.  相似文献   

19.
Solubility experiments were performed on nanocrystalline scorodite and amorphous ferric arsenate. Nanocrystalline scorodite occurs as stubby prismatic crystals measuring about 50 nm and having a specific surface area of 39.88 ± 0.07 m2/g whereas ferric arsenate is amorphous and occurs as aggregated clusters measuring about 50–100 nm with a specific surface area of 17.95 ± 0.19 m2/g. Similar to its crystalline counterpart, nanocrystalline scorodite has a solubility of about 0.25 mg/L at around pH 3–4 but has increased solubilities at low and high pH (i.e. <2 and >6). Nanocrystalline scorodite dissolves incongruently at about pH > 2.5 whereas ferric arsenate dissolution is incongruent at all the pH ranges tested (pH 2–5). It appears that the solubility of scorodite is not influenced by particle size. The dissolution rate of nanocrystalline scorodite is 2.64 × 10−10 mol m−2 s−1 at pH 1 and 3.25 × 10−11 mol m−2 s−1 at pH 2. These rates are 3–4 orders of magnitude slower than the oxidative dissolution of pyrite and 5 orders of magnitude slower than that of arsenopyrite. Ferric arsenate dissolution rates range from 6.14 × 10−9 mol m−2 s−1 at pH 2 to 1.66 × 10−9 mol m−2 s−1 at pH 5. Among the common As minerals, scorodite has the lowest solubility and dissolution rate. Whereas ferric arsenate is not a suitable compound for As control in mine effluents, nanocrystalline scorodite that can be easily precipitated at ambient pressure and temperature conditions would be satisfactory in meeting the regulatory guidelines at pH 3–4.  相似文献   

20.
The more rapid dissolution of Ca-rich feldspars relative to Na, K-rich feldspars has been attributed to the preferential leaching of Al deep within the feldspar structure. Evidence from surface microanalysis (e.g., Hellmann et al., 2003), however, shows that preferential dissolution of Al is confined to the top layers of the feldspar lattice and that the amorphous surface layer most likely results from precipitation versus dissolution. It is thus critical to examine the extent of preferential Al removal. Here we present a theoretical study of plagioclase dissolution behavior using parameterized Monte Carlo simulations. Two different dissolution mechanisms, a mechanism involving preferential leaching of Al and an interfacial dissolution-reprecipitation mechanism, are tested using compositions representing the entire plagioclase solid solution series. Our modeling results indicate that under the control of the preferential Al leaching mechanism, the influence of (Al, Si) disorder on the dissolution rate is significant. At a fixed composition, an increase in the degree of (Al, Si) disorder yields an increased dissolution rate, with an 8-fold increase in dissolution rate observed for highly disordered albite (An0) compared to low albite. Increasing anorthite content tends to decrease the variation in the dissolution rate due to disorder. The difference in the dissolution rate of 293 tested oligoclase configurations with a composition of An20 is 3-fold, and the difference is reduced to 2-fold among 107 andesine configurations of An30. Furthermore, feldspar configurations with completely disordered (Al, Si) distributions yield a consistent log-linear dependence of dissolution rate on the anorthite content (An), while other feldspar configurations with modest degrees of (Al, Si) disorder exhibit rates less than this trend. In contrast, when Al removal is confined to the top surface layers, a variety of feldspar configurations with different (Al, Si) disorder but a single fixed composition have similar dissolution rates; and the dissolution rate of Ca-rich feldspars departs positively from its log-linear relationship with anorthite content. This departure occurs around An80 and is in good agreement with previous experimental studies. Subsequent modeling results of aluminum inhibition, ΔG dependence, and formation of altered surface layers in the framework of the interfacial dissolution-reprecipitation mechanism are all comparable with experimental investigations, and these results suggest that an interfacial dissolution-reprecipitation mechanism governs the dissolution of plagioclase feldspars.  相似文献   

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