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1.
Diffusion experiments with HTO, 36Cl−, Br−, I−, 22Na+, 85Sr2+ and 134Cs+ at trace concentrations in a single sample of Opalinus Clay are modeled with PHREEQC’s multicomponent diffusion module. The model is used first in a classical approach to derive accessible porosities, geometrical factors (the ratio of pore tortuosity and constrictivity) and sorption behavior of the individual tracers assuming that the clay is homogeneous. The accessible porosity for neutral species and cations is obtained from HTO, the anion exclusion volume from 36Cl− and Br−, and the cation exchange capacity from 22Na+. The homogeneous model works well for tritium, the anions and 22Na+. However, the 85Sr2+ and 134Cs+ experiments show an early arrival of the tracer and a front-form that suggest a dual porosity structure. A model with 10% dead-end pores, containing 19% of the total exchange capacity, can satisfactorily calculate all the experimental data. The Cs+ diffusion model builds on a 3-site exchange model, constructed from batch sorption data. The excellent agreement of modeled and measured data contradicts earlier reports that the exchange capacity for Cs+ would be smaller in diffusion than in batch experiments.The geometrical factors for the anions are 1.5 times larger than for HTO, and for the cations 2-4 times smaller than for HTO. The different behavior is explained by a tripartite division of the porespace in free porewater, diffuse double layer (DDL) water, and interlayer water in montmorillonite. Differences between estimated and observed geometrical factors for cations are attributed to increased ion-pairing of the divalent cations in DDL water as a result of the low relative dielectric permittivity. Interlayer and/or surface diffusion contributes significantly to the diffusive flux of Cs+ but is negligible for the other solutes. The geometrical factors for anions are higher than estimated, because pore constrictions with overlapping double layers force the anions to take longer routes than HTO and the cations. Small differences among the anions can also be attributed to different ion-pairing in DDL water.  相似文献   

2.
Diffusion parameters for HTO, 36Cl−, and 125I− were determined on Upper Toarcian argillite samples from the Tournemire Underground Research Laboratory (Aveyron, France) using the through diffusion technique. The direction of diffusion was parallel to the bedding plane. The purpose of the present study was 3-fold; it was intended (i) to confirm the I− interaction with Upper Toarcian argillite and to verify the effects of initial I− concentration on this affinity, as previously observed by means of radial diffusion experiments, (ii) to highlight any discrepancy between Cl− and I− diffusivity, and (iii) to investigate the effect of an increase of the ionic strength of the solution on the anionic tracers’ diffusive behaviour. The results show that the effective diffusion coefficient (De) and diffusion accessible porosity (εa) values obtained with an ionic strength (I.S.) synthetic pore water of 0.01 eq L−1 are: De = 2.35–2.50 × 10−11 m2 s−1 and εa = 12.0–15.0% for HTO, and De = 14.5–15.5 × 10−13 m2 s−1 and εa = 2.5–2.9% for 36Cl−. Because of anionic exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than HTO, taken as a water tracer. The associated effective diffusion coefficient (De) and rock capacity factor (α) obtained for 125I are: De = 7.00–8.60 × 10−13 m2 s−1 and α = 4.3–7.2%. Such values make it possible to calculate low 125I distribution ratios (0.0057 < RD < 0.0192 mL g−1) which confirm the trend indicating that the 125I rock capacity factor increases with the decrease of the initial I− concentration. Additional through-diffusion experiments were carried out with a higher ionic strength synthetic pore water (I.S. = 0.11 eq L−1). No evolution of HTO diffusion parameters was observed. The anionic tracers’ effective diffusion coefficient increased by a factor of two but no clear evolution of their accessible porosity was observed. Such a paradox could be related to the particularly small mean pore size of the Upper Toarcian argillite of Tournemire. The most significant finding of this study is the large discrepancy (factor of two) between the values of the effective diffusion coefficient for 125I and 36Cl. Whatever the ionic strength of the synthetic solution used, 125I exhibited De values two times lower than those of 36Cl. A detailed explanation for this difference cannot be given at present even if a hypothesis based on ion-pairing or on steric-exclusion cannot be excluded. This makes questionable the assumption usually made for quantifying 125I sorption and postulating that 36Cl and 125I would diffuse in the same porosity. In other terms, at Tournemire, 125I sorption could be more pronounced than previously indicated.  相似文献   

3.
As a part of the safety assessment of the geological disposal of high-level radioactive waste, the effects of dry density and exchangeable cations on the diffusion process of Na+ ions in compacted bentonite were studied from the viewpoint of the activation energy for diffusion. The apparent self-diffusion coefficients of Na+ ions in compacted Na-montmorillonite and in a Na- and Ca-montmorillonite mixture were determined by one-dimensional, non-steady diffusion experiments at different temperatures and dry densities. A unique change in activation energy as a function of dry density was found for the Na+ ions in compacted Na-montmorillonite. The activation energy suddenly decreased from 18.1 to 14.1 kJ mol− 1 as the dry density increased from 0.9 to 1.0 Mg m− 3, whereas it increased to 24.7 kJ mol− 1 as the dry density increased to 1.8 Mg m− 3. Examination of the effect of exchangeable cations on the activation energies determined that the activation energies were almost constant, approximately 25 kJ mol− 1, for the montmorillonite specimens at a dry density of 1.8 Mg m− 3. However, three different activation energy values were obtained at a dry density of 1.0 Mg m− 3. These findings cannot be explained by the conventional diffusion model (the pore water diffusion model), which suggests that the predominant diffusion process alternates among pore water diffusion, interlayer diffusion, and external surface diffusion.  相似文献   

4.
《Applied Geochemistry》2005,20(5):961-972
The temperature dependence of the self-diffusion of HTO, 22Na+ and 36Cl− in Opalinus Clay (OPA) was studied using a through-diffusion technique, in which the temperature was gradually increased in the steady state phase of the diffusion. The measurements were done on samples from two different geological locations. The dependence of the effective diffusion coefficient on temperature was found to be of an Arrhenius type in the temperature range between 0 and 70 °C. A slight difference between the two locations could be observed. The average value of the activation energy of the self-diffusion of HTO in OPA was 21.1 ± 1.6 kJ mol−1, and 21.0 ± 3.5 and 19.4 ± 1.5 kJ mol−1 for 22Na+ and 36Cl−, respectively. The measured values for HTO are slightly higher than the values found for the bulk liquid water (HTO: 18.8 ± 0.4 kJ mol−1). This indicates that the structure of the confined water in OPA might be slightly different from that of bulk liquid water. Also for Na+ and Cl−, slightly higher values than in bulk liquid water (Na+: 18.4 kJ mol−1; Cl−: 17.4 kJ mol−1) were observed.The Stokes–Einstein relationship, based on the temperature dependency of the viscosity of bulk water, could not be used to describe the temperature dependence of the diffusion of HTO in OPA. This additionally indicates the slightly different structure of the pore water in OPA.  相似文献   

5.
《Applied Geochemistry》2003,18(10):1653-1662
The through- and out-diffusion of HTO, 36Cl− and 125I− in Opalinus Clay, an argillaceous rock from the northern part of Switzerland, was studied under different confining pressures between 4 and 15 MPa. The direction of diffusion and the confining pressure were perpendicular to the bedding. Confining pressure had only a small effect on diffusion. An increase in pressure from 4 to 15 MPa resulted in a decrease of the effective diffusion coefficient of ∼20%. Diffusion accessible porosities were not measurably affected. The values of the effective diffusion coefficients, De, ranged between (5.6±0.4)×10−12 and (6.7±0.4)×10−12 m2 s−1 for HTO, (7.1±0.5)×10−13 and (9.1±0.6)×10−13 m2 s−1 for 36Cl− and (4.5±0.3)×10−13 and (6.6±0.4)×10−13 m2 s−1 for 125I−. The rock capacity factors, α, measured were circa 0.14 for HTO, 0.040 for 36Cl− and 0.080 for 125I−. Because of anion exclusion effects, anions diffuse slower and exhibit smaller diffusion accessible porosities than the uncharged HTO. Unlike 36Cl−, 125I− sorbs weakly on Opalinus Clay resulting in a larger rock capacity factor. The sorption coefficient, Kd, for 125I− is of the order of 1–2×10−5 m3 kg−1. The effective diffusion coefficient for HTO is in good agreement with values measured in other sedimentary rocks and can be related to the porosity using Archie's Law with exponent m=2.5.  相似文献   

6.
It is important to clarify the migration behavior of hydrogen gas dissolved in water-saturated, compacted bentonite, which is a promising material for geologic disposal of high-level waste and TRU waste disposal. The diffusion coefficients of helium, which can be detected under extremely low background conditions, in water-saturated, compacted Na-montmorillonite were determined as a function of temperature by a transient diffusion method. The activation energies for diffusion of helium were then obtained. The activation energies were from 6.9 ± 4.8 to 19 ± 2.8 kJ mol− 1 and were regarded to be independent of dry density. The activation energies of helium in water-saturated Na-montmorillonite were roughly equal to those in bulk water, 14.9 kJ mol− 1, and in ice, from 11 to 13 kJ mol− 1. It is possible that helium diffuses not only in pore water but also in interlayer water.  相似文献   

7.
Diffusion of 36Cl− in compacted bentonite was studied using through-diffusion, out-diffusion and profile analysis techniques. Both the bulk dry density of the bentonite and the composition of the external solution were varied. Increasing the bulk dry density of the bentonite resulted in a decrease of both the effective diffusion coefficient and the Cl-accessible porosity. Increasing the ionic strength of the external solutions resulted in an increase of both the effective diffusion coefficient and the Cl-accessible porosity. This can be explained by anion exclusion effects (Donnan exclusion). At high ionic strength values (I ? 1 M NaCl) the Cl-accessible porosity approaches the interparticle porosity. This interparticle porosity is the difference between the total and interlayer porosity of the bentonite. The interlayer porosity was found to depend on the degree of compaction. Up to a bulk dry density of 1300 kg m−3 the interlayer is built up of 3 water layers. Between 1300 and 1800 kg m−3 the interlayer water is reduced from 3 to 2 layers of water. Above 1800 kg m−3 evidence for a further decrease to 1 layer of water was found. These findings are in agreement with X-ray data found in the literature showing a decrease of the basal spacing of montmorillonite (the main clay mineral in bentonite) with increasing degree of compaction. The relationship between the effective diffusion coefficient of Cl− and the diffusion-accessible porosity can be described by an empirical relationship analogous to Archie’s law. To predict the effective diffusion coefficient of Cl− in compacted bentonite, the diffusion coefficient of Cl− in water, the bulk dry density and the ionic strength of the pore water have to be known.  相似文献   

8.
The effect of temperature and ionic strength on the diffusion of HTO parallel to the direction of compaction through 5 highly compacted clay minerals (bulk dry density, ρb,d = 1.90 ± 0.05 Mg/m3), namely montmorillonite (Na- and Ca-form), illite (Na- and Ca-form), and kaolinite, was studied. The diffusion experiments were carried out at temperatures between 0 °C and 60 °C and at ionic strengths of 0.01 M and 1 M NaCl for the Na-form clays and kaolinite, and of 0.005 M and 0.5 M CaCl2 for the Ca-form. The ionic strength had an insignificant influence on the values of the effective diffusion coefficient (variation by less than 10%) for the clays under study at this degree of compaction. The effective diffusion coefficients followed the order Na-montmorillonite < Ca-montmorillonite < Ca-illite < Na-illite  kaolinite. It is thought that the differences between Na- and Ca-montmorillonite originate from the larger size particles, and thus the lower tortuosity of the latter; whereas the differences between Na- and Ca-illite are related to the different degree of solvation of the Na and Ca cations. The activation energies were successfully calculated using the Arrhenius law. Swelling clays (Na- and Ca-montmorillonite) had slightly larger activation energy values (20 kJ/mol) compared to bulk water (17 kJ/mol); Ca-illite (16 kJ/mol), Na-illite (13 kJ/mol) and kaolinite (14.4 kJ/mol) lower values than that of bulk water. The low activation energies of the last three clays may be related to weaker H-bonds between water and the clay surfaces compared to those in bulk water.  相似文献   

9.
Stable Cl isotope ratios (37Cl/35Cl) were measured in groundwater samples from the southwestern flow system of the Great Artesian Basin, Australia to gain a better understanding of the Cl− sources and transport mechanisms. δ37Cl values range from 0‰ to −2.5‰ (SMOC), and are inversely correlated with Cl− concentration along the inferred flow direction. The Cl isotopic compositions, in conjunction with other geochemical parameters, suggest that Cl− in groundwaters is not derived from salt dissolution. Mixing of the recharge water with saline groundwater cannot explain the relationship between δ37Cl and Cl− concentration measured. Marine aerosols deposited via rainfall and subsequent evapotranspiration appear to be responsible for the Cl− concentrations observed in wells that are close to the recharge area, and in groundwaters sampled along the southern transect. δ37Cl values measured in the leachate of the Bulldog shale suggest that the aquitard is the subsurface source of Cl− for the majority of groundwater samples studied. Diffusion is likely the mechanism through which Cl− is transported from the pore water of the Bulldog shale to the aquifer. However, a more detailed study of the aquitard rocks is required to verify this hypothesis.  相似文献   

10.
The transient diffusion of cationic and anionic tracers through clay-rocks is usually modeled with parameters like porosity, tortuosity (and/or constrictivity), sorption coefficients, and anionic exclusion. Recently, a new pore scale model has been developed by Revil and Linde [Revil A. and Linde N. (2006) Chemico-electromechanical coupling in microporous media. J. Colloid Interface Sci.302, 682-694]. This model is based on a volume-averaging approach of the Nernst-Planck equation. The influence of the electrical diffuse layer is accounted for by a generalized Donnan equilibrium model through the whole connected pore space that is valid for a multicomponent electrolyte. This new model can be used to determine the composition of the pore water of the Callovo-Oxfordian clay-rock, the osmotic efficiency of bentonite as a function of salinity, the osmotic pressure, and the streaming potential coupling coefficient of clay-rocks. This pore scale model is used here to model the transient diffusion of ionic tracers (22Na+, 36Cl−, and ) through the Callovo-Oxfordian clay-rock. Speciation of shows that ∼1/3 of the SO4 is tied-up in different complexes. Some of these complexes are neutral and are therefore only influence by the tortuosity of the pore space. Using experimental data from the literature, we show that all the parameters required to model the flux of ionic tracers (especially the mean electrical potential of the pore space and the formation factor) are in agreement with independent evaluations of these parameters using the osmotic pressure determined from in situ pressure measurements and HTO diffusion experiments.  相似文献   

11.
The accessible porosity for Cl− in bentonite is smaller than the the total porosity due to anion repulsion (exclusion) by the surface of montmorillonite, the main mineral in bentonite. The accessible porosity is a function of the bentonite density and the salt concentration. Anion exclusion data were gathered from the literature, reprocessed in a coherent data set, and modelled using four different models. Very simple models, with or without anion access to the interlayer space, are successful in reproducing trends in anion exclusion in bentonite as a function of ionic strength in the external solution and montmorillonite bulk dry densities in the bentonite. However, a model that considers clay microstructure changes as a function of bentonite compaction and ionic strength is necessary to reproduce observed trends in the data for all experimental conditions within a single model. Our predictive model excludes anions from the interlayer space and relates the interlayer porosity to the ionic strength and the montmorillonite bulk dry density. This presentation offers a good fit for measured anion accessible porosities in bentonites over a wide range of conditions and is also in agreement with microscopic observations.  相似文献   

12.
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13.
Chloride concentrations in waterways of northern USA are increasing at alarming rates and road salt is commonly assumed to be the cause. However, there are additional sources of Cl− in metropolitan areas, such as treated wastewater (TWW) and water conditioning salts, which may be contributing to Cl− loads entering surface waters. In this study, the potential sources of Cl− and Cl− loads in the Illinois River Basin from the Chicago area to the Illinois River’s confluence with the Mississippi River were investigated using halide data in stream samples and published Cl− and river discharge data. The investigation showed that road salt runoff and TWW from the Chicago region dominate Cl− loads in the Illinois Waterway, defined as the navigable sections of the Illinois River and two major tributaries in the Chicago region. Treated wastewater discharges at a relatively constant rate throughout the year and is the primary source of Cl− and other elements such as F− and B. Chloride loads are highest in the winter and early spring as a result of road salt runoff which can increase Cl− concentrations by up to several hundred mg/L. Chloride concentrations decrease downstream in the Illinois Waterway due to dilution, but are always elevated relative to tributaries downriver from Chicago. The TWW component is especially noticeable downstream under low discharge conditions during summer and early autumn when surface drainage is at a minimum and agricultural drain tiles are not flowing.  相似文献   

14.
The geochemistry of 5 salt springs in the southwestern Mamfe Basin was investigated in order to infer the mineral content of their source and to relate the genesis of the springs to the local geology. Field observations revealed that, they are cold springs (23–28 °C), and are composed of secondary brines that are neutral to alkaline with pH values ranging from 7 to 8.7. Results of chemical analysis show that the springs contain major ions that form evaporite minerals, as well as chalcophile elements. The dominant cation is Na+ (>96%), and the dominant anion is Cl− (>99%). Based on correlation coefficients between ions that form evaporites and field occurrence of efflorescences of halite, it is suggested that the ancient evaporites in the Mamfe Basin are composed entirely of carbonate and chloride salts. Meteoric and convective fluid flow processes are responsible for the dissolution of ancient evaporites and subsequent migration of brines to the surface from underground. The brines migrate through permeable strata with migration pathways resulting from a combination of fracture porosity created by post––Cretaceous tectonism and intergranular porosity enhanced by the chemically aggressive migrating brines.  相似文献   

15.
The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO4 solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10−6 mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni2+, Cs+ and Ln3+ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu2+ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu2+ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].  相似文献   

16.
Anthropogenic inputs have largely contributed to the increasing salinization of surface waters in central Ohio, USA. Major anthropogenic contributions to surface waters are chloride (Cl−) and sodium (Na+), derived primarily from inputs such as road salt. In 2012–2013, central Ohio rivers were sampled and waters analyzed for comparison with historical data. Higher Cl− and Na+ concentrations and fluxes were observed in late winter as a result of increased road salt application during winter months. Increases in both chloride/bromide (Cl−/Br−) ratios and nitrate (N-NO3−) concentrations and fluxes were observed in March 2013 relative to June 2012, suggesting a mixture of road salt and fertilizer runoff influencing the rivers in late winter. For some rivers, increased Cl− and Na+ concentrations and fluxes were observed at downstream sites near more urban areas of influence. Concentrations of Na+ were slightly lower than respective Cl− concentrations (in equivalents). High Cl−/Br− mass ratios in the Ohio surface waters indicated the source of Cl− was likely halite, or road salt. In addition, analysis of 36Cl/Cl ratios revealed low values suggestive of a substantial dissolved halite component, implying the addition of “old” Cl− into the water system. Temporal trend analysis via the Mann–Kendall test identified increasing trends in Cl− and Na+ concentration beginning in the 1960s at river locations with more complete historical datasets. An increasing trend in Cl− flux through the 1960s was also identified in the Hocking River at Athens, Ohio. Our results were similar to other studies that examined road salt impacts in the northern US, but a lack of consistent long-term data hindered historical analysis for some rivers.  相似文献   

17.
The silicon isotopic composition of dissolved silicon and suspended particulate matter (SPM) were systematically investigated in water samples from the mainstem of the Yellow River and 4 major tributaries. The SPM content of the Yellow River varied from 1.4 to 38,560 mg/L, averaging 3568 mg/L, and the δ30Si of suspended particulate matter (δ30SiSPM) varied from 0.3‰ to −0.4‰, averaging −0.02‰. The major factors affecting the SPM content and the δ30SiSPM values in the Yellow River were inferred to be the mineralogical, chemical and isotopic characteristics of the sediments from the Loess Plateau and a combination of the climate and the flow discharge of the river.The major ions in the Yellow River water were Na+, Ca2+, Mg2+, HCO3−, SO42− and Cl−. High salt concentration was observed in samples from the middle and lower reaches, likely reflecting the effects of evaporation and irrigation because the Na+, Mg2+, SO42− and K+ concentrations were correlated with the Cl− concentration. The dissolved Si concentration (DSi) increased downstream, varying from 0.016 to 0.323 mM. The δ30Si of dissolved Si (δ30SiDiss) varied from 0.4‰ to 2.5‰, averaging 1.28‰. The major processes controlling the DSi and δ30SiDiss of the Yellow River are (a) the weathering of silicate rocks, (b) the formation of phytoliths in plants, (c) the evaporation of water from and the addition of meteoric water to the river system, which only affects concentrations, (d) the adsorption and desorption of aqueous monosilicic acid on iron oxide, and (e) the dissolution of phytoliths in soils.The DSi and δ30SiDiss values of global rivers vary spatially and temporally in response to changes in climate, chemical weathering intensity and biological activity. The moderately positive δ30SiDiss values observed in the Yellow River may be attributed to the higher rates of chemical weathering and biological activities that have been observed in this catchment in comparison with those of other previously studied catchments, excluding the Yangtze River. Human activities may also potentially influence chemical weathering and biological activities and affect the DSi and δ30SiDiss values of the major rivers of the world. Further river studies should be performed to gain a better understanding of the global Si isotope budget.  相似文献   

18.
Diffusion coefficients for oxygen and hydrogen were determined from a series of natural uraninite-H2O experiments between 50 and 700 °C. Under hydrous conditions there are two diffusion mechanisms: (1) an initial extremely fast-path diffusion mechanism that overprinted the oxygen isotopic composition of the entire crystals regardless of temperature and (2) a slower volume-diffusive mechanism dominated by defect clusters that displace or eject nearest neighbor oxygen atoms to form two interstitial sites and two partial vacancies, and by vacancy migration. Using the volume diffusion coefficients in the temperature range of 400-600 °C, diffusion coefficients for oxygen can be represented by D = 1.90e−5 exp (−123,382 J/RT) cm2/s and for temperatures between 100 and 300 °C the diffusion coefficients can be represented by D = 1.95e−10 exp (−62484 J/RT) cm2/s, where the activation energies for uraninite are 123.4 and 62.5 kJ/mol, respectively. Hydrogen diffusion in uraninite appears to be controlled by similar mechanisms as oxygen. Using the volume diffusion coefficients for temperatures between 50 and 700 °C, diffusion coefficients for hydrogen can be represented by D = 9.28e−6 exp (−156,528 J/RT) cm2/s for temperatures between 450 and 700 °C and D = 1.39e−14 exp (−34518 J/RT) cm2/s for temperatures between 50 and 400 °C, where the activation energies for uraninite are 156.5 and 34.5 kJ/mol, respectively.Results from these new experiments have implications for isotopic exchange during natural UO2-water interactions. The exceptionally low δ18O values of natural uraninites (i.e. −32‰ to −19.5‰) from unconformity-type uranium deposits in Saskatchewan, in conjunction with theoretical and experimental uraninite-water and UO3-water fractionation factors, suggest that primary uranium mineralization is not in oxygen isotopic equilibrium with coeval clay and silicate minerals. The low δ18O values have been interpreted as resulting from the low temperature overprinting of primary uranium mineralization in the presence of relatively modern meteoric fluids having δ18O values of ca. −18‰, despite petrographic and U-Pb isotope data that indicate limited alteration. Our data show that the anomalously low oxygen isotopic composition of the uraninite from the Athabasca Basin can be due to meteoric water overprinting under reducing conditions, and meteoric water or groundwater can significantly affect the oxygen isotopic composition of spent nuclear fuel in a geologic repository, with minimal change to the chemical composition or texture. Moreover, the rather fast oxygen and hydrogen diffusion coefficients for uraninite, especially at low temperatures, suggest that oxygen and hydrogen diffusion may impart characteristic isotopic signals that can be used to track the route of fissile material.  相似文献   

19.
A one-dimensional transport model was developed to reconstruct historical conservative transport of chloride and δ37Cl in pore water of sediments from a former brackish lagoon in The Netherlands, an area now covered by the freshwater Lakes IJssel and Marken. Knowledge of the mechanism of historical solute transport in the sediments and environmental conditions during transport is critical in understanding observed pore water chemistry and will form a basis for simulating effects of changing environmental (climate change) conditions. The model synthesizes present knowledge of geology and historical information on storm surges in the area and takes into account processes such as erosion of sediments, mixing of pore water, sedimentation, and diffusion (EMSD). The chemistry of pore water from one particular boring in the area was found to be mainly controlled by alternating seawater and freshwater diffusion. Models with a constant (averaged) porosity (? = 0.55) and tortuosity factor (τ = 0.3) showed similar results as models incorporating the measured bulk porosity variations (? = 0.4-0.8) and variable tortuosity factors calculated with Archie’s law, τ = ?. The relatively small tortuosity factor either results from anion exclusion or from the heterogeneous build-up of the profile in which a peaty layer in the middle part may obstruct diffusion. Diffusion of 35Cl− was found to be 1.0017 times faster than of 37Cl−. Seawater diffusion into the sediments started at least 400 years ago and refreshening took place since the lagoon was isolated from the sea by a dam in 1932.  相似文献   

20.
The aqueous interfacial chemistry of kaolinite and Na-montmorillonite samples was investigated by potentiometric measurements using acid/base continuous titrations and batch experiments at 25 and 60 °C. Using the batch experimental method, a continuous drift of pH was observed reflecting the mineral dissolution. Consequently, the continuous titration method appears to be the best way of studying solid surface reactions. For each clay mineral, the net proton surface excess/consumption was calculated as a function of pH and ionic strength (0.025, 0.1 and 0.5 M). At 25 °C, and according to the literature data, the pH corresponding to zero net proton consumption for montmorillonite appears to depend on ionic strength, whereas the value for kaolinite is constant and close to 5. Similar results are obtained at 60 °C, which suggests that the point of zero net proton consumption for clay minerals does not depend on temperature, at least up to 60 °C. On the other hand, the temperature rise induces a slight increase of the net proton surface excess. Finally, the diffuse double layer formalism (DDLM) is used to model the experimental data. The model involves two processes: the protonation/deprotonation of two types of edge sites (aluminol and silanol) and H+/Na+ exchange reactions on basal surfaces, while a tiny proportion of the negative structural charge remains uncompensated. This last process maintains a negative surface potential whatever the pH of the solution, which is in agreement with electrokinetic data.  相似文献   

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