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1.
In this paper the solute retention properties of crystalline fractured rocks due to mixing-induced geochemical reactions are studied. While fractured media exhibit paths of fast flow and transport and thus short residence times for conservative solutes, at the same time they promote mixing and dilution due to strong heterogeneity, which leads to sharp concentration contrasts. Enhanced mixing and dilution have a double effect that favors crystalline fractured media as a possible host medium for nuclear waste disposal. Firstly, peak radionuclide concentrations are attenuated and, secondly, mixing-induced precipitation reactions are enhanced significantly, which leads to radionuclide immobilization. An integrated framework is presented for the effective modeling of these flow, transport and reaction phenomena, and the interaction between them. In a simple case study, the enhanced dilution and precipitation potential of fractured crystalline rocks are systematically studied and quantified and contrasted it to retention and attenuation in an equivalent homogeneous formation.  相似文献   

2.
《Applied Geochemistry》2000,15(2):141-155
A marine based argillaceous rock containing volcanic glass shards has been investigated to infer the long-term durability of vitrified nuclear waste in compacted bentonite, which is a candidate for buffer material constituting the engineered barrier system for nuclear waste disposal. Fission track ages indicate that the volcanic glass shards, andesitic scoria, have been buried in the argillaceous rock for about 1 Ma. Neither glass matrix dissolution nor precipitation on the surface was seen under an optical microscope. Little leaching of any element has been recognized by analyses using an electron microprobe analyzer. Secondary ion mass spectrometry analysis, however, indicates significant hydration which may dominantly be a permeation of molecular water.As an indicator of durability of glass against groundwater a normalized mass loss of Si (NLSi) has been evaluated for the volcanic glass based on free energy for hydration. The difference between estimated NLSi of the volcanic glass and that of a simulated waste glass is within one order so that the volcanic glass may be analogous to a waste glass with respect to durability to water. The argillaceous rock is analogous to the compacted bentonite with respect to physical properties such as dry-density, unconfined compression strength, porosity, and hydraulic conductivity. The ambient physical and chemical conditions surrounding the volcanic glass have been also investigated: temperature was in the range from 4 to 30°C due to the burial history of the volcanic glass. Over most of the past 1 Ma the volcanic glass has been in contact with groundwater originating from seawater. Thermodynamic calculations indicate (1) pH (=7.74–7.94) of the groundwater has mainly been controlled by dissolution of carbonate minerals, (2) the redox potential (Eh=−34–−73 mV) of the groundwater has dominantly been controlled by decomposition of organic materials to produce CH4(g), and (3) activity of aqueous silica of the groundwater was in equilibrium with SiO2 amorphous. Because of the equilibrium between aqueous silica and SiO2 amorphous, the volcanic glass did not dissolve during the burial.Vitrified nuclear waste sealed in compacted bentonite, therefore, will not dissolve significantly if buried in an environment as mentioned above.  相似文献   

3.
Modelling of radionuclide transport in fractured media is a primary task for safety evaluation of a deep nuclear waste repository. A performance assessment (PA) model has been derived from site characterization data with the aim of improving confidence for quantifying transport of sorbing radionuclides at a safety time scale of 106 y. The study was conducted on a 200?×?200?×?200 m semi-synthetic fractured block, providing a realistic system derived from the Äspö Hard Rock Laboratory (Sweden) dataset. The block includes 5,632 fractures ranging from 0.5 to 100 m in length and a heterogeneous matrix structure (fracture coating, gouge, mylonite, altered and non-altered diorite). The PA model integrates steady-state flow conditions and transport of released radionuclides during the safety time scale. An original simulation method was developed involving Eulerian flow and transport within fracture planes with a mixed hybrid finite element scheme and a semi-analytical source term to account for heterogeneous matrix diffusion. Total mass flux of radionuclides (conservative to strongly sorbing) was computed. A method to simplify the system was demonstrated, leading to a major path of 12 fractures. This is mainly due to the low connectivity of the fracture network. Matrix diffusion and sorption proved to have major impact on block retention properties for PA conditions.  相似文献   

4.
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   

5.
《Applied Geochemistry》1996,11(4):511-521
It is difficult to measure accurately the natural long-term corrosion rates of highly durable nuclear waste glasses. Care should be taken when using data from high temperature experiments to predict corrosion rates under ambient repository conditions as there are many factors (such as the precipitation of secondary compounds, the chemistry of the water in contact with the glass, or circulation of this water through the repository) that can influence the temperature dependence of aqueous reactions. In this study, some standard leach tests using pure water, in continuous flow and direct sampling autoclaves, were performed on a synthetic medieval glass. Archaeological glass samples of a similar composition and which had suffered several centuries of corrosion in damp soil had been the subject of previous studies. The corrosion of the archaeological samples in damp soil was well understood and the aim was to determine how well standard leach tests would predict the observed corrosion.The experimentally measured long-term corrosion rates were not simply dependent on temperature, therefore they could not be used to predict either the corrosion rates or products found on the archaeological samples. In continuous flow experiments this was largely because the release of some cations (e.g. Mg2+) was proportional to the flow rates used, and so the long-term corrosion was dependent on both flow rate and temperature. In the autoclave experiments, concentrations of dissolved ions climbed rapidly in the small water volume, leading to the precipitation of complex mineral phase assemblages. The experiments did not reach silica saturation, therefore the long-term rates measured were a function of both the temperature and the extent of reaction. The initial release rates of silica and of the network modifying cations showed an Arrhenius temperature dependence with an activation energy of about 78.5 kJmol−1. These results would have predicted the soil corrosion of the archaeological samples to within about 30%, i.e. the initial corrosion rate in pure water was similar to the long-term rate in damp soil. As an explanation of the experimental observations it is suggested that clay minerals in the soil consumed silica as the glass dissolved, maintaining under-saturated conditions and allowing corrosion at a rate similar to the initial rate in pure water.  相似文献   

6.
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7.
田芹  佟玲  宋淑玲  战楠  潘萌  邱静 《岩矿测试》2016,35(6):569-578
六溴环十二烷(HBCDs)是一种全球生产的添加型溴化阻燃剂,被广泛应用于隔热建筑材料阻燃剂、室内装潢、纺织品和电子产品中,不仅对生态环境造成污染,而且还会通过食物链的传递危害人类健康。研究生态系统中HBCDs异构体及对映体的环境行为与生物放大作用是进行环境风险评估和有效控制污染的生态学基础。基于此,本文从HBCDs的基本特性出发,阐述了HBCDs异构体及对映体在食物链中的选择性生物富集放大及转化行为,分析了发生选择性富集及转化的影响因素,这些因素包括生物体的生活环境、饮食习惯、所处食物链中营养级水平以及HBCDs选择性吸收、代谢和异构化等。已有的研究报道显示HBCDs异构体及对映体在生态系统中的富集、转化及生物放大行为不是单一的过程,是生物体和环境多因素综合的结果。今后应对HBCDs异构体及对映体在各种食物链(如淡水食物链和陆生食物链)中的选择性环境行为以及在食物链传递中发生选择性的主控因素等方面进行深入系统的研究,为全面评价其生态风险提供科学依据。  相似文献   

8.
Under the background of China as a big coal-hungry country lasting till 2050, deep mining becomes more and more significant. However, deep coal seams usually have a very complex geological structure like Karst collapse columns, and excavation is often accompanied with water-inrush accidents, restricting the development of the coal industry. In order to study on seepage problems on fractured rock accompanying with mass loss during excavation in coal mines with karst collapse columns, researchers studied on water-inrush mechanism in karst collapse columns directly, researched on seepage behavior of fractured rock with pressure as the basis of studying on water-inrush mechanism indirectly, studied the fluid flow change in fractured rock regarding the change of liquid flow type in fractured rock as seepage instability, and observed and studied the phenomenon of mass loss during seepage in succession. In the following research, (1) the cementation, lithology, and match rate of testing samples, which are the foundation of the simulation study, need to be determined in more detail; (2) migrated particles in fractured rock should be distributed which are from migration, corrosion, erosion, and abrasion; (3) multi-permeate agents in the fractured geological structure, their diffusion and convection, and the related chemical reactions should be involved; (4) more and more contemporary mathematical methods will be introduced to help us to study the complex dynamic system; and (5) experimental equipment needs to be designed and improved. What we did before, do now, and will do later is to penetrate the mysteries of seepage problems on fractured rock accompanying with mass loss during excavation in coal mines with karst collapse columns.  相似文献   

9.
Many hydrologic conceptual models in riparian areas assume that the alluvial deposits zone is hydraulically more active than the fractured bedrock below. Therefore, these models undervalue the possible contribution of deeper groundwater from the fractured bedrock system. A hydrochemical study, under various hydrological conditions, has been carried out in a small riparian zone of the Salburua wetland (Basque Country) in order to highlight the conceptual model. This wetland is included in a wide Quaternary aquifer, which has been declared a Nitrate Vulnerable Zone. The results of this study suggest that the fractured bedrock is at least as dynamic as the upper clayey deposits. The presence of more fractured zones, which act as hydraulic “windows”, allow the upwelling of deeper groundwater and, consequently, make the upper alluvial deposits and the fractured bedrock water systems to be cross-connected. Nevertheless, this upwelling is limited to some small areas in the riparian zone. As a result of this local interaction, several chemical reactions have been observed and the hydrochemical characteristics of shallow groundwater undergo seasonal variations. The study shows that a hydrologic conceptual model, which does not consider the hydraulic activity of the fractured bedrock, can be too simplistic. The presence of hydraulic windows could be considered throughout the entire Quaternary aquifer, knowledge of which could help the managers of the Vulnerable Zone and the wetland to take more effective measures for regulation and conservation.  相似文献   

10.
Multi-component mineral precipitation in porous, subsurface environments is challenging to simulate or engineer when in situ reactant mixing is controlled by diffusion. In contrast to well-mixed systems, the conditions that favor mineral precipitation in porous media are distributed along chemical gradients, which evolve spatially due to concurrent mineral precipitation and modification of solute transport in the media. The resulting physical and chemical characteristics of a mixing/precipitation zone are a consequence of coupling between transport and chemical processes, and the distinctive properties of individual chemical systems. We examined the spatial distribution of precipitates formed in “double diffusion” columns for two chemical systems, calcium carbonate and calcium phosphate. Polyacrylamide hydrogel was used as a low permeability, high porosity medium to maximize diffusive mixing and minimize pressure- and density-driven flow between reactant solutions. In the calcium phosphate system, multiple, visually dense and narrow bands of precipitates were observed that were reminiscent of previously reported Liesegang patterns. In the calcium carbonate system, wider precipitation zones characterized by more sparse distributions of precipitates and a more open channel structure were observed. In both cases, formation of precipitates inhibited, but did not necessarily eliminate, continued transport and mixing of the reactants. A reactive transport model with fully implicit coupling between diffusion, chemical speciation and precipitation kinetics, but where explicit details of nucleation processes were neglected, was able to qualitatively simulate properties of the precipitation zones. The results help to illustrate how changes in the physical properties of a precipitation zone depend on coupling between diffusion-controlled reactant mixing and chemistry-specific details of precipitation kinetics.  相似文献   

11.
Corrosion is the destructive reaction of metals with their environment. The environment associated with a waste container is an extremely complex one, creating many possibilities for corrosion of the waste container. The different basic types of corrosion are governed by different equations and reactions. Schematic drawings and photographs illustrate the mechanisms of corrosion and factors which influence the forms of corrosion are outlined. There are techniques for testing the susceptibility to certain types of corrosion, and some standard test procedures have been developed. Predictive models have been proposed for crevice corrosion, stress corrosion cracking and scale formation. Existing models and extrapolations are all subject to limits on their applicability.  相似文献   

12.
Here we present a long-term nonisothermal reactive transport model for the interactions of the corrosion products of a carbon-steel canister and the compacted bentonite of the engineered barrier of a high-level radioactive waste repository in granite. Canister corrosion causes an increase in the pH and the concentration of dissolved Fe2+ of the bentonite porewater. Iron precipitates as magnetite and siderite and sorbs via cation exchange and surface complexation on weak sites. Magnetite precipitation reduces significantly the porosity of the bentonite near the canister. The thickness of the zone of reduced porosity is 7 cm at t = 1 Ma. This thickness increases significantly when the dependence of the corrosion rate on the chemical conditions is considered and decreases 3 cm when smectite dissolution and analcime precipitation are taken into account. Model results are not significantly sensitive to the thermal transient and the effect of temperature on the corrosion rate. The conclusions of our simulations are consistent for the most part with those reported by others for engineered barrier systems at similar chemical conditions.  相似文献   

13.
The unsaturated fractured volcanic deposits at Yucca Mountain in Nevada, USA, have been intensively investigated as a possible repository site for storing high-level radioactive waste. Field studies at the site have revealed that there exist large variabilities in hydrological parameters over the spatial domain of the mountain. Systematic analyses of hydrological parameters using a site-scale three-dimensional unsaturated zone (UZ) flow model have been undertaken. The main objective of the sensitivity analyses was to evaluate the effects of uncertainties in hydrologic parameters on modeled UZ flow and contaminant transport results. Sensitivity analyses were carried out relative to fracture and matrix permeability and capillary strength (van Genuchten α) through variation of these parameter values by one standard deviation from the base-case values. The parameter variation resulted in eight parameter sets. Modeling results for the eight UZ flow sensitivity cases have been compared with field observed data and simulation results from the base-case model. The effects of parameter uncertainties on the flow fields were evaluated through comparison of results for flow and transport. In general, this study shows that uncertainties in matrix parameters cause larger uncertainty in simulated moisture flux than corresponding uncertainties in fracture properties for unsaturated flow through heterogeneous fractured rock.  相似文献   

14.
Fractured archaeological glass blocks altered 1800 years in seawater are investigated because of their morphological analogy with vitrified nuclear waste. They provide an opportunity for understanding glass alteration in variable confined media (cracks), by studying an actual ancient system in a known stable natural environment. Characterization of the crack network from two-dimensional trace maps (length, alteration thickness, orientation) allows us to determine the three-dimensional geometric parameters (crack density, fracture ratio) and the percentage of alteration, using stereological relations. This methodology could be applied to nuclear glass. From a representative archaeological glass block, we showed that the surface developed by the cracks is 86 ± 27 times greater than the geometric surface but the volumetric alteration is 12.2 ± 4.1%, which is only 12 times greater than the volumetric alteration of the block periphery (about 1 vol%). This unexpected low value is explained by the large variation of the alteration thicknesses in the different types of cracks in relation with their location in the block. The alteration thickness is usually smaller in the internal zone than in the border zone. The alteration layers resulted from three main mechanisms (interdiffusion, glass dissolution, and secondary phase precipitation) leading to two different alteration products (a sodium-depleted layer and mainly a Mg-smectite). Geometric parameters such as the glass surface area/solution volume ratio and transport parameters (renewal of the alteration solution) strongly affected the glass dissolution kinetics. The confined conditions and the diffusive transport of reactive species favor low alteration kinetics. The precipitation of secondary phases also results in sealing of the cracks. Consequently, although it is not known if subcritical crack growth occurred, internal cracks account for only a minor contribution to the overall alteration. These results improve our understanding of alteration in cracks for assessing the predominant physical and chemical parameters that must be considered in long-term nuclear glass modeling.  相似文献   

15.
Vitreous materials are quite routinely found in natural settings. Most of them are aluminosilicates, which often occur in large deposits. Considering the geological formations in which naturally occurring vitreous aluminosilicates are found, they have generally remained stable for more than 1 Ma on the earth's surface, even in different geological and climatic environments. These non-crystalline solids played a very important role in the development of ancient human civilizations, long before the introduction of metallic tools. Today, however, the properties of natural glasses are of interest to mankind for completely different reasons. For example, industrial glasses are used today for encapsulating toxic wastes, especially radioactive waste, which remains active for centuries or more, in order to prevent the unwanted transfer of harmful materials to the environment. The chemical compositions of industrially produced glasses are in large part different from the compositions of natural glasses. Little is quantitatively known about the stability of industrial glasses over very long periods of time (>10,000 years). However, the physical and chemical stability of natural aluminosilicate glasses is known to extend over very long periods of time.The advancement of technological design to prevent or at least minimize the melt down of toxic waste during the encapsulation process is currently a major challenge, using glasses of natural chemical composition. Brecciated glass, which is found frequently in natural settings, provides a special clue to the possibility of producing vitreous solids by sintering glass fragments without melting the cullets. It is essential to prevent melting of the cullets because the melt has the potential of chemically reacting with the toxic waste.This paper summarizes the geological, chemical, and physical facts concerning naturally produced glasses, and seeks to establish a recognized database for further research in the domain of understanding the glass-forming processes that occur in nature. Furthermore, the authors hope to stimulate research into the utilization of natural resources that to solve the problem of storing of toxic waste safely.Major and trace element data have been collected over the past 100 years. These data constitute a sufficient basis for the chemical characterization of natural glasses. More information about the major elements is not required, in order to understand the chemical properties of these materials. On the other hand, large gaps in compositional data exist where other related components are concerned: e.g., in the case of “water-species”, with its different forms of bonding in silicates or oxygen (oxygen fugacity), CO2-, sulphur - or hydrocarbons (methane)-, hydrogen-, chlorine-and fluorine-species. All these components have a significant impact on the properties of glasses, even when present only in minor quantities. Glass textures and crystal morphologies reflect the processes of nucleation and crystal growth in a glass-forming matrix during the cooling and reheating cycles which are currently not thoroughly understood. In nature, the processes that led to the formation of vitreous materials are very different from those used in the production of industrial glasses. The different genetic conditions under which glass formation occurs permit differentiation between magmatic and metamorphic vitreous solids. Sedimentary and biogenetic processes also contribute to the formation of non-crystalline solids.  相似文献   

16.
Reprocessing of spent nuclear fuel (SNF) for recovery of fissionable elements is a precondition of long-term development of nuclear energetics. Solution of this problem is hindered by the production of a great amount of liquid waste; 99% of its volume is low- and intermediate-level radioactive waste (LILW). The volume of high-level radioactive waste (HLW), which is characterized by high heat release, does not exceed a fraction of a percent. Solubility of glasses at an elevated temperature makes them unfit for immobilization of HLW, the insulation of which is ensured only by mineral-like matrices. At the same time, glasses are a perfect matrix for LILW, which are distinguished by low heat release. The solubility of borosilicate glass at a low temperature is so low that even a glass with relatively low resistance enables them to retain safety of under-ground LILW depositories without additional engineering barriers. The optimal technology of liquid confinement is their concentration and immobilization in borosilicate glasses, which are disposed in shallow-seated geological repositories. The vitrification of 1 m3 liquid LILW with a salt concentration of ～300 kg/m3 leaves behind only 0.2 m3 waste, that is, 4–6 times less than by bitumen impregnation and 10 times less than by cementation. Environmental and economic advantages of LILW vitrification result from (1) low solubility of the vitrified LILW in natural water; (2) significant reduction of LILW volume; (3) possibility to dispose the vitrified waste without additional engineering barriers under shallow conditions and in diverse geological media; (4) the strength of glass makes its transportation and storage possible; and finally (5) reliable longterm safety of repositories. When the composition of the glass matrix for LILW is being chosen, attention should be paid to the factors that ensure high technological and economic efficiency of vitrification. The study of vitrified LILW from the Kursk nuclear power plant with high-power channel reactors (HPCR; equivalent Russian acronym, RBMK) and the Kalinin nuclear power plant with pressurized water reactors (PWR; equivalent Russian acronym VVER) after their 14-yr storage in the shallow-seated repository at the MosNPO Radon testing ground has confirmed the safety of repositories ensured by confinement properties of borosilicate matrix. The most efficient vitrification technology is based on cold crucible induction melting. If the content of a chemical element in waste exceeds its solubility in glass, a crystalline phase is formed in the course of vitrification, so that the glass ceramics become a matrix for such waste. Vitrified waste with high Fe; Na and Al; Na, Fe, and Al; Na and B is characterized. The composition of frit and its proportion to waste depends on waste composition. This procedure requires careful laboratory testing.  相似文献   

17.
A pollen profile obtained from lake sediments at Lunkaransar, Rajasthan, in northwest India was used along with a pollen-climate calibration function to estimate past precipitation. Between 10,500 and 3500 yr B.P., the estimated precipitation was about 500 mm/yr, or about 200 mm/yr above the modern value. A model was used for the energy and hydrologic budget of a lake basin and lake at Sambhar (located 240 km SE of Lunkaransar) to calculate that a 200 mm/yr increase in rainfall above the modern amount would have raised the lake level about 20 m above the modern level. Topographic charts and satellite imagery provided some evidence in support of an enlarged paleolake of that elevation, but field exploration would be required to confirm the size and date of a former lake. After about 3500 yr B.P., the Lunkaransar profile indicated a desiccated lake bed; because no pollen was preserved, the pollen-climate calibration function was of no use for estimating the amount of the precipitation decline. A reduction of precipitation of about 200 mm/yr below the modern amount was estimated from the energy and hydrologic budget for paleolake Sambhar by assuming that the lake was one-tenth of its present size during the dry interval.  相似文献   

18.
A two-dimensional boundary integral method to analyse the flow of contaminant in fractured media having a two- or three-dimensional orthogonal fracture network is presented. The method assumes that the fractures provide the paths of least resistance for transport of contaminants while the matrix, because of its low permeability, acts as ‘storage blocks’ into which the contaminant diffuses. Laplace transform is used to eliminate the time variable in the governing equation in order to facilitate the formulation of a boundary integral equation in the Laplace transform space. Conventional boundary element techniques are applied to solve for the contaminant concentrations at specified locations in the spatial domain. The concentration in the time domain is then obtained by using an efficient inversion technique developed by Talbot. The method is able to analyse the behaviour of waste repositories which have diminishing concentration due to the mass transport of the contaminant into the surrounding fractured media.  相似文献   

19.
Coupled hydro-mechanical (HM) processes are significant in geological engineering such as oil and gas extraction, geothermal energy, nuclear waste disposal and for the safety assessment of dam foundations and rock slopes, where the geological media usually consist of fractured rock masses. In this study, we developed a model for the analysis of coupled hydro-mechanical processes in porous rock containing dominant fractures, by using the numerical manifold method (NMM). In the current model, the fractures are regarded as different material domains from surrounding rock, i.e., finite-thickness fracture zones as porous media. Compared with the rock matrix, these fractured porous media are characterized with nonlinear behavior of hydraulic and mechanical properties, involving not only direct (poroelastic) coupling but also indirect (property change) coupling. By combining the potential energy associated with mechanical responses, fluid flow and solid–fluid interactions, a new formulation for direct HM coupling in porous media is established. For indirect coupling associated with fracture opening/closure, we developed a new approach implicitly considering the nonlinear properties by directly assembling the corresponding strain energy. Compared with traditional methods with approximation of the nonlinear constitutive equations, this new formulation achieves a more accurate representation of the nonlinear behavior. We implemented the new model for coupled HM analysis in NMM, which has fixed mathematical grid and accurate integration, and developed a new computer code. We tested the code for direct coupling on two classical poroelastic problems with coarse mesh and compared the results with the analytical solutions, achieving excellent agreement, respectively. Finally, we tested for indirect coupling on models with a single dominant fracture and obtained reasonable results. The current poroelastic NNM model with a continuous finite-thickness fracture zone will be further developed considering thin fractures in a discontinuous approach for a comprehensive model for HM analysis in fractured porous rock masses.  相似文献   

20.
In this study, we have investigated and clarified the processes occurring during the alteration of SON68 glass – the reference nuclear glass for the waste arising from reprocessing of spent fuel from light water reactors – at 50 °C in Callovo-Oxfordian clay groundwater in presence of magnetite. Magnetite is known to be one of the iron corrosion products expected to be present in the vicinity of glass in geological disposal conditions. The effects of the amount of magnetite relative to the glass surface and the transport of aqueous species during glass alteration were studied. A first series of experiments was focused on the effect of various magnetite amounts by mixing and altering glass and magnetite powders. In a second series of experiments, magnetite was separated from the glass by a diffusive barrier in order to slow down the transport of aqueous species. Glass alteration kinetics were analyzed and solids were characterized by a multiscale approach using Raman Spectroscopy, Scanning and Transmission Electron Microscopy, Energy-Dispersive X-ray and Scanning Transmission X-ray Microscopy coupled with Fe L2,3-edge and C K-edge NEXAFS.It appears that glass alteration increases with the amount of magnetite and that the transport of aqueous species is a key parameter. Several processes have been identified such as (i) the silica sorption on the magnetite surface, (ii) the precipitation of Fe-silicates in the vicinity of the glass (iii) the precipitation of SiO2 on the magnetite surface, (iv) the incorporation of Fe within the alteration layer. Process (iv) was not frequently observed, suggesting local variations in geochemical conditions. Moreover, this process is strongly influenced by the transport of aqueous species as indicated by the morphology and composition of the alteration layers. Indeed, when glass and magnetite are homogeneously mixed, the glass alteration layer consists of a gel enriched in Fe having the same Fe(II)/Fe(III) ratio as in magnetite. When both materials are separated by a diffusive barrier, the glass alteration layer consists of a porous gel (not enriched in iron) in presence of a mixture of Fe-silicates with Fe having the same valence as in magnetite, rare-earth precipitates and phyllosilicates. These results suggest that Fe incorporation within the alteration layer changes depending on the distance and the time required for dissolved Fe originating from the magnetite to reach the glass.  相似文献   

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