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1.
Several designs proposed for high-level nuclear waste (HLW) repositories include steel waste canisters surrounded by montmorillonite clay. This work investigates montmorillonite stability in the presence of native Fe, magnetite and aqueous solutions under hydrothermal conditions. Two series of experiments were conducted. In the first, mixtures of Na-montmorillonite, magnetite, native Fe, calcite, and NaCl solutions were reacted at 250 °C, Psat for between 93 and 114 days. In the second series, the starting mixtures included Na-montmorillonite, native Fe and solutions of FeCl2 which were reacted at temperatures of 80, 150, and 250 °C, Psat, for 90-92 days. Experiments were analysed using XRD, FT-IR, TEM, ICP-AES, and ICP-MS. In the first series of experiments, native Fe oxidised to produce magnetite and the starting montmorillonite material was transformed to Fe-rich smectite only when the Fe was added predominantly as Fe metal rather than Fe oxide (magnetite). The Fe-rich smectite was initially Fe(II)-rich, which oxidised to produce an Fe(III)-rich form on exposure to air. The expansion of this material on ethylene glycol solvation was much reduced compared to the montmorillonite starting material. TEM imaging shows that partial loss of tetrahedral sheets occurred during transformation of the montmorillonite, resulting in adjacent layers becoming H-bonded with a 7 Å repeat. The reduced swelling property of the Fe-smectite product may be due predominantly to the structural disruption of smectite layers and the formation of H-bonds. Solute activities corresponded to the approximate stability field calculated for hypothetical Fe(II)-saponite. In the second series of experiments, significant smectite alteration was only observed at 250 °C and the product contained a small proportion of a 7 Å repeat structure, observable by XRD. In these experiments, solute activities coincide with berthierine. The experiments indicate that although bentonite is still a desirable choice of backfill material for HLW repositories, some loss of expandability may result if montmorillonite is altered to Fe-rich smectite at the interface between steel canisters and bentonite.  相似文献   

2.
高放废物地质处置研究中的矿物学问题   总被引：2，自引：0，他引：2  
在高放废物地质处置研究中的一些矿物学问题应引起矿物学家的注意 。高放废物地 质处置库的缓冲/回填材料是选择以钠质蒙脱石为主要成分的钠基膨润土,还是以钙质蒙脱 石为主的钙基膨润土?怎样选择对99Tc、129I有较好吸附能力的硒汞矿、脆 硫锑铅矿和辉锑矿的替代物来作缓冲/回填材料中的添加剂,以能阻滞99Tc和129 I的迁移?沸石对某些放射性核素的吸附特征也需进一步研究。  相似文献   

3.
我国高放废物处置库缓冲／回填材料压实膨胀特性研究   总被引：11，自引：0，他引：11  
本文研究了我国高放废物地质处置库缓冲／回填材料－内蒙古高庙子膨润土的压实、膨胀力和膨胀变形特性。实验结果表明，膨润土样品的压实密度与压制压力和蒙脱石含量有关，膨胀力与样品压实密度和蒙脱石含量有关，样品在荷载作用下膨胀变形明显减小。  相似文献   

4.
The detection of phyllosilicates and sulfates on Mars has revealed a complex aqueous history which suggests distinct geochemical environments separated temporally and spatially. Recent observations by MRO CRISM in Mawrth Vallis have shown that phyllosilicate deposits exhibit a specific stratigraphy, which remains incompletely understood. Moreover, MER Spirit has evidenced association between phyllosilicates, amorphous silica and sulfates. We investigated the hypothesis that these parageneses resulted from the acidic weathering of older phyllosilicate deposits. We exposed nontronite (Fe-rich smectite), montmorillonite (Al-rich smectite) and kaolinite to H2SO4 solutions at pH 0, 2 and 4, and at a temperature of 60 °C. After the acid treatment, a combination of mineralogical techniques was used to assess the degree of alteration of the three phyllosilicate minerals. XRF, XRD and ESEM measurements show that nontronite was the most unstable when acid leached, followed by montmorillonite and then kaolinite. Progressive acidic leaching of nontronite leads to alteration of the phyllosilicate to amorphous silica, along with Fe-sulfate and anatase, and the formation of an acidic Al,Fe-rich solution. Alteration of montmorillonite resulted in the formation of Fe-, Al-, Ca- and Mg-sulfates, and a Al-rich leaching solution. Comparatively, leaching of kaolinite resulted in the formation of Al-sulfates and a Al-rich solution as well, with only slight alteration of the primary mineralogical features. The effects of acid leaching of the phyllosilicates were also observed in NIR reflectance spectra, allowing a comparison with CRISM spectra from Mawrth Vallis. Based on our results, we propose a new model where acid leaching of mixed phyllosilicate deposits leads to kaolinite overlaying montmorillonite, which in turn caps Fe,Mg-smectites. Leaching of cations and subsequent evaporation leads to sulfate deposits, as supported by geochemical modeling, while amorphous silica remains as a residue. Depending on the intensity (pH) and length of exposure of acidic leaching, our model can explain the stratigraphic distribution of phyllosilicates, and the association of sulfates, silica and smectites.  相似文献   

5.

Buffer/backfill material is an important engineering barrier in a deep geological repository of high-level radioactive waste (HLW). Its thermo-hydro-mechanical (THM) performance is very important for the safe and stable operation of the HLW repository system. Natural graphite powder mixed with sodium bentonite forms a buffer/backfill material that can dissipate heat quickly and provide strong isolation. In this paper, the THM characteristics of bentonite–sand–graphite–polypropylene fiber (BSGF) mixtures, used as a buffer/backfill material, were studied through a series of laboratory tests. The influence of graphite and polypropylene fiber contents on thermal conductivity, swelling pressure, hydraulic conductivity, and strength properties of BSGF mixtures with different sand contents was analyzed. Experimental results indicated that the graphite content, the maximum graphite mesh number, and the initial dry density of bentonite–graphite mixtures influenced the thermal conductivity of bentonite–graphite mixtures. The addition of polypropylene fiber was found to enhance the shear strength and inhibit cracking without significantly affecting the expansivity, permeability, and thermal conductivity of the BSGF mixtures. This study provides a new buffer/backfill material that can improve the stability, functionality, and thermal efficiency of the HLW repository.

  相似文献   

6.
In the context of the deep waste disposal, we have investigated the respective stabilities of two iron-bearing clay minerals: berthierine ISGS from Illinois [USA; (Al0.975FeIII0.182FeII1.422Mg0.157Li0.035Mn0.002)(Si1.332Al0.668)O5(OH)4] and chlorite CCa-2 from Flagstaff Hill, California [USA; (Si2.633Al1.367)(Al1.116FeIII0.215Mg2.952FeII1.712Mn0.012Ca0.011)O10(OH)8]. For berthierine, the complete thermodynamic dataset was determined at 1 bar and from 2 to 310 K, using calorimetric methods. The standard enthalpies of formation were obtained by solution-reaction calorimetry at 298.15 K, and the heat capacities were measured by heat-pulse calorimetry. For chlorite, the standard enthalpy of formation is measured by solution-reaction calorimetry at 298.15 K. This is completing the entropy and heat capacity obtained previously by Gailhanou et al. (Geochim Cosmochim Acta 73:4738–4749, 2009) between 2 and 520 K, by using low-temperature adiabatic calorimetry and differential scanning calorimetry. For both minerals, the standard entropies and the Gibbs free energies of formation at 298.15 K were then calculated. An assessment of the measured properties could be carried out with respect to literature data. Eventually, the thermodynamic dataset allowed realizing theoretical calculations concerning the berthierine to chlorite transition. The latter showed that, from a thermodynamic viewpoint, the main factor controlling this transition is probably the composition of the berthierine and chlorite minerals and the nature of the secondary minerals rather than temperature.  相似文献   

7.
Cement-bentonite interactions will occur in deep geological repositories for high level radioactive waste. We performed laboratory experiments in order to constrain some previous geochemical and mineralogical uncertainties in the formation of secondary minerals in the high pH reaction of FEBEX bentonite at moderate temperatures.The reactivity of a Mg-homoionic FEBEX bentonite was studied at 25, 60 and 90 °C in batch reactors using two solutions representative of short and long time evolution stages of cement degradation. These solutions were periodically renewed in order to maintain a constant pH regime for a period of almost 2 years.Chabazite and merlinoite were observed to be the main zeolites that formed at 60 °C, while merlinoite was the dominant zeolite formed at 90 °C with the hyperalkaline (K-Na-OH) solution. The alkaline experiments (Ca-OH solution) showed minor reactivity and negligible mineralogical alteration, but the overall results suggest that the reaction tends to equilibrium conditions between C-S-H and montmorillonite at high temperature and metastable conditions at low temperature. The montmorillonite dissolution rates were calculated for all experiments, showing good agreement with previous calculations.  相似文献   

8.
盐溶液法测定非饱和膨润土的水分特征曲线   总被引：3，自引：0，他引：3  
对于高放废物的最终处置，深地质处置被国内外公认为最合适的方法，而膨润土也被认为是高放废物处置库缓冲回填材料的良好基质。鉴于膨润土各项性质研究的重要性。本文介绍了利用盐溶液法进行非饱和膨润土水分特征曲线的测定工作，发现盐溶液法适合测定吸力极高的非饱和土，是一种值得推广的方法。  相似文献   

9.
Clay minerals are ubiquitous on epigeosphere, especially in soils and sediments where microbes thrive. The clay-microbe interactions are common in these geological media and greatly contribute to accelerating the mineral transformation process, e.g. the illitization of nontronite (a Fe-rich smectite) catalyzed by microbes under anoxic atmosphere in 2 weeks. However, few has considered montmorillonite, a Fe-poor smectite more typical in natural environments than nontronite. This study therefore focuses on the interaction between montmorillonite and bacteria under conditions relevant to those in natural soils and sediments.  相似文献   

10.
Smectite clay has been proposed for embedding canisters with highly radioactive waste in deep repositories because of its isolating capacity. Montmorillonite-rich bentonite is a premier buffer candidate for many national organizations that are responsible for disposal of such waste. Experience from the use of drilling mud at large depths indicates that other smectite clay minerals are more stable chemically and saponite is one of them. The physical properties of smectitic mixed-layer minerals like Friedland clay are known to be less sensitive to high salt contents and such clay may also be a buffer candidate. Montmorillonite-rich MX-80 clay, Greek saponite with a minor amount of palygorskite, and Friedland clay were investigated in hydrothermal tests with dense samples confined in oedometers with 95 °C temperature at one end, which was made of copper, and 35 °C at the other, for 8 weeks. A 1 % CaCl2 solution was circulated through a filter at the cold end. At the end of the tests, the samples were sliced into three parts, which were tested with respect to expandability, hydraulic conductivity, and chemical composition. The tests showed that while the saponite was hardly changed at all and did not take up any copper, MX-80 underwent substantial changes in physical performance and adsorbed significant amounts of copper. The Friedland clay sample was intermediate in both respects.  相似文献   

11.
Greenish veins occurring in brecciated bentonite were found in the Kawasaki bentonite deposit of the Zao region in Miyagi Prefecture, Japan. Their occurrence possibly indicates the interaction of bentonite with Fe-rich hydrothermal solutions. In order to prove the hypothesis and understand the long-term mineralogical and petrographic evolution of bentonite during such interactions, the greenish veins and the surrounding altered bentonite were analyzed using X-ray fluorescence (XRF), scanning electron microscopy (SEM), X-ray diffraction (XRD), electron probe micro-analysis (EPMA), scanning transmission electron microscopy with energy dispersed spectroscopy (STEM-EDS) and micro X-ray absorption near-edge structure (XANES). The greenish veins resulting from hydrothermal solution are composed of mixed-layer minerals consisting of smectite and glauconite (glaucony), pyrite and opal. The occurrences indicate that glaucony and pyrite formed almost simultaneously from hydrothermal solution prior to opal precipitation. The mineral assemblages of the greenish veins and their surroundings indicate that the hydrothermal activity had most likely taken place at a temperature of less than 100 °C and that the pH and Eh conditions of the reacted solution were neutral to alkaline pH and reducing. The unaltered bentonite is composed mainly of Al smectite and opal. These minerals coexist as a mixture within the resolution level of the microprobe analyses. On the other hand, the bentonite in contact with the greenish veins consists of discrete opal grains and dioctahedral Al smectite containing Fe and was altered mineralogically and petrographically by the hydrothermal activity. Both the clay minerals and the opal were formed by dissolution and subsequent precipitation from the interaction of the original bentonite with the hydrothermal solution.  相似文献   

12.
Chemico-mineralogical attributes of authigenic clays associated with the altered volcanic tuffs that occur in the Palaeoproterozoic Porcellanite Formation contain evidences of hydrothermal alteration and diagenetic processes in a marine environment. Previous sedimentological and geochemical studies on Porcellanite Formation were restricted to the Chopan area, but, the details related to provenance, nature and source of volcanism archived in these clays have not been ascertained. In order to understand these aspects, present study on these authigenic clays were carried out. Clay minerals represent dominance of illite with subordinate amount of montmorillonite. Moreover, low abundance of kaolinite is also noticed. The illite fibers and plates associated with the kaolinite indicate illitization. The kaolinite to illite transformation is favoured by incorporation of K+ ions, derived from the K-feldspar dissolution and its overgrowth. Major oxide contents of these clays and their ratios when plotted over diagrams marked with standard illite, kaolinite, smectite and chlorite compositional fields show clustering within or close to the illite field. Thermodynamic components calculated for these clays when plotted over AR23+AlSi3O10(OH)2 − R23+Si4O10(OH)2 − AR2+R3+Si4O10(OH)2 ternary diagram, data plots lie within the illite, mixed layer I/S and smectite fields. Binary major oxide data plots between bulk rock and authigenic clay compositions showed felsic affinity. Montmorillonite and illite predominated in the eastern and western marginal areas of the Vindhyan Basin, respectively. However, former resulted from the hydrothermal alteration of volcanic glass associated with the ferruginous breccia and altered tuffs and remnants of the volcanic vents, whereas, later is associated with the tuffaceous beds. Owing to the adsorption, Ba, Rb and Sr is enriched in clays comparing to the bulk rock composition. Low (< 15 ppm) Sc values suggested major contribution from the felsic component. Also, low Rb/Sr and Th/U values revealed moderate insitu weathering. The dominance of K-feldspar alteration and insitu weathering is also evident from clustering of clay data plots in the A-CN-K ternary diagram. Pronounced negative Eu anomaly together with higher LREE/HREE values associated with these clay minerals implied proximity to source and their possible derivation from the silicified felsic tuffs available in the provenance.  相似文献   

13.
Recent exploration work in South Morocco revealed the occurrence of several carbonatite bodies, including the Paleoproterozoic Gleibat Lafhouda magnesiocarbonatite and its associated iron oxide mineralization, recognized here as iron-oxide-apatite (IOA) deposit type. The Gleibat Lafhouda intrusion is hosted by Archean gneiss and schist and not visibly associated with alkaline rocks. Metasomatized micaceous rocks occur locally at the margins of the carbonatite outcrop and were identified as glimmerite fenite type. Rare earth element (REE) and Nb mineralization is mainly linked to the associated IOA mineralization and is represented by monazite-(Ce) and columbite-(Fe) as major ore minerals. The IOA mineralization mainly consists of magnetite and hematite that usually contain large apatite crystals, quartz and some dolomite. Monazite-(Ce) is closely associated with fluorapatite and occurs as inclusions within the altered parts of apatite and along cracks or as separate phases near apatite. Monazite shows no zonation patterns and very low Th contents (<0.4 wt%), which would be beneficial for commercial extraction of the REE and which indicates monazite formation from apatite as a result of hydrothermal volatile-rich fluids. Similar monazite-apatite mineralization and chemistry also occurs at depth within the carbonatite, although the outcropping carbonatite is barren, suggesting an irregular REE ore distribution within the carbonatite body. The barren carbonatite contains some tiny unidentified secondary Nb-Ta-U phases, synchysite and monazite. Niobium mineralization is commonly represented by anhedral minerals of columbite-(Fe) which occur closely associated with magnetite-hematite and host up to 78 wt% Nb2O5, 7 wt% Ta2O5 and 1.6 wt% Sc2O3. This association may suggest that columbite-(Fe) precipitated by an interaction of Nb-rich fluids with pre-existing Fe-rich minerals or as pseudomorphs after pre-existing Nb minerals like pyrochlore. Our results most strongly suggest that the studied mineralization is economically important and warrants both, further research and exploration with the ultimate goal of mineral extraction.  相似文献   

14.
Simplified evaluation for swelling characteristics of bentonites   总被引：9，自引：0，他引：9  
Hideo Komine   《Engineering Geology》2004,71(3-4):265-279
Bentonite is currently planned to be used as buffer and backfill materials for repositories of high-level nuclear waste because these materials must have the swelling characteristics to seal the waste. In the design for buffer and backfill materials, we must choose the adequate bentonite among many kinds of bentonite in the world. The database of the swelling characteristics of various bentonites and its evaluation will be available when we will select the adequate bentonite. For this purpose, this study performed the laboratory tests on the swelling pressure and swelling deformation of four kinds of bentonite produced in Japan and the United States. These bentonites have different physicochemical properties. This study investigated the characteristics of swelling pressure and swelling deformation from the viewpoint of the physicochemical properties of each bentonite. Furthermore, this study also proposed the simplified evaluation of swelling characteristics of various bentonites on the basis of microscopic analysis.  相似文献   

15.
Nuclear waste from thermal plants poses a lasting risk to the biosphere because of its long radioactive life. The planned definitive storage place for it is in deeply buried repositories. Such repositories would need to be both impermeable to water, and plastic during deformation, in order to avoid the formation of cracks that may allow water in. One of the clay minerals, smectite, has these two properties and is an ideal candidate as a sealing material or even host rock for nuclear waste repositories. The chemical stability of smectite in the repository environment is sufficient to maintain good sealing properties during the active life of the relevant radionuclides.  相似文献   

16.
Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe2+–Fe3+ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe2+/Fe3+ ratios to the reduction potential (Eh).  相似文献   

17.
缓冲材料作为高放废物深地质处置库中一道重要的人工屏障,与高放废物容器和处置库围岩直接接触,在高放废物衰变热、辐射作用和地下水等影响下产生复杂的热-水-力-化学耦合作用,为了验证缓冲材料是否能长期有效地发挥其屏障材料的作用,核工业北京地质研究院利用高庙子钠基膨润土组装并运行了模拟中国高放废物地质处置室 尺寸的大型缓冲材料膨润土试验台架（China-Mock-Up）。建立了缓冲材料试验台架的安装和试验方法,依据实测数据和理论分析,揭示了热-水-力-化学耦合作用条件下膨润土中的相对湿度是在加热器的热效应和外部供水的湿效应共同作用下发生变化的,压实膨润土中应力的变化主要是由于膨润土遇水膨胀和加热器的热效应引起的,试验验证了模拟高放废物地质处置室内加热器（废物罐）运行初期的位移过程,为缓冲材料和高放废物地质处置库的设计提供了重要的工程参数和理论依据。  相似文献   

18.
Experimental batch and miscible-flow cultures were studied in order to determine the mechanistic pathways of microbial Fe(III) respiration in ferruginous smectite clay, NAu-1. The primary purpose was to resolve if alteration of smectite and release of Fe precedes microbial respiration. Alteration of NAu-1, represented by the morphological and mineralogical changes, occurred regardless of the extent of microbial Fe(III) reduction in all of our experimental systems, including those that contained heat-killed bacteria and those in which O2, rather than Fe(III), was the primary terminal electron acceptor. The solid alteration products observed under transmission electron microscopy included poorly crystalline smectite with diffuse electron diffraction signals, discrete grains of Fe-free amorphous aluminosilicate with increased Al/Si ratio, Fe-rich grains, and amorphous Si globules in the immediate vicinity of bacterial cells and extracellular polymeric substances. In reducing systems, Fe was also found as siderite. The small amount of Fe partitioned to the aqueous phase was primarily in the form of dissolved Fe(III) species even in the systems in which Fe(III) was the primary terminal electron acceptor for microbial respiration. From these observations, we conclude that microbial respiration of Fe(III) in our laboratory systems proceeded through the following: (1) alteration of NAu-1 and concurrent release of Fe(III) from the octahedral sheets of NAu-1; and (2) subsequent microbial respiration of Fe(III).  相似文献   

19.
There is convincing evidence from field data that smectite clay undergoes conversion primarily to illite and chlorite if it is fully water-saturated and heated. The conversion may take place through mixed-layer formation with increasing illite/smectite ratio at higher temperatures and pressures. This process requires dehydration of the interlamellar space, for which either an external pressure or drying are needed. An alternative mechanism that takes place without dehydration, is dissolution of smectite and neoformation of illite. Both processes imply reorganization of the smectite crystal lattice for which the activation energy is fairly high, meaning that the conversion is negligible at temperatures lower than about 60°C. At elevated temperatures the conversion rate is controlled by the access to potassium for either mechanism.

An ongoing detailed investigation of this subject has led to a tentative model for the smectite-to-illite conversion in natural sediments and in canister-embedding clay in high-level radioactive waste (HLW) repositories.  相似文献   


20.
Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients (Kd) were determined in two media: water and 0.02 mol L−1 Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The Kd values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg−1) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of Kd values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.  相似文献   

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