首页 | 本学科首页   官方微博 | 高级检索  
相似文献
 共查询到20条相似文献，搜索用时 31 毫秒
1.
A new variety of matrices based on synthetic phases whose structure is close to that of murataite (a natural mineral) is proposed for immobilization of nuclear wastes. Murataite is Na, Ca, REE, Zn, and Nb titanate with a structure derived from the fluorite lattice. This very rare mineral was found in alkali pegmatites from Colorado in the United States and the Baikal region in Russia. The synthetic murataite-like phases contain manganese instead of zinc, as well as actinides and zirconium instead of sodium, calcium, and niobium. Varieties with threefold, as in the mineral, and five-, seven-, and eightfold repetition of the lattice relative to the fluorite cell have been established. Correspondingly, the structural varieties M3, M5, M7, and M8 are recognized among the synthetic murataites. A decrease in the contents of actinides, rare earth elements, and zirconium occurs in the series M7-M5-M8-M3, along with enrichment in Ti, Al, Fe, and Ga. Murataite-based ceramics are characterized by high chemical and radiation stability. The rate of U, Th, and Pu leaching with water at 90°C in static and dynamic tests is 10?6–10?5 g/m2 per day. These values are lower than the leaching rate of other actinide confinement matrices, for example, zirconolite-or pyrochlore-based. Murataite is close to other titanates in its radiation resistance. At 25°C, amorphization of its lattice is provided by a radiation dose of 2 × 1018 α decays/g, or 0.2 displacements/atom. Murataite-based matrices are synthesized within a few hours by cold compacting combined with sintering at 1300°C or by melting at 1500–1600°C and subsequent crystallization. The melting technology, including induction smelters with a cold crucible, makes it possible to produce samples with zonal murataite grains. The inner zone of such grains is composed of structural variety M5 or M7; the intermediate zone, of M8; and the outer zone, of M3. The contents of actinides, zirconium, and rare earth elements reach a maximum in the inner zone and drop to a minimum in the outer zone, while the amounts of nonradioactive elements—Ti, Al, Fe, and Ga—vary conversely. The U, Th, and Pu contents in the inner and outer zones differ by three to five times. Such a distribution precludes removal of actinides by interaction of the matrix with solution after its underground disposal. Individual actinides (Np, Pu, Am); the actinide-zirconium-rare earth fraction of high-level radioactive wastes (HLW); Am-Ga residues of weapons plutonium reprocessing with its conversion into U-Pu mixed oxide (MOX) fuel; and other sorts of HLW enriched in actinides, REE, and products of corrosion (Mn, Fe, Al, Zr) can be incorporated into a murataite-based matrix. As much as 350 kg of HLW components can be included in 1 t of such a ceramic. An actinide matrix that is composed of titanates with a pyrochlore structure is its nearest analogue. The advantage of murataite in comparison with pyrochlore consists in its universal character; i.e., a murataite-based matrix can be used for utilization of a wider range of actinide-bearing highly radioactive wastes.  相似文献   

2.
The reprocessing of spent nuclear fuel (SNF) is accompanied by the formation of liquid high-level radioactive waste (HLW). To increase the safety of handling HLW, it is proposed to extract actinide isotopes (An) and REE from them. These elements may be incorporated into crystalline matrices, e.g., based on ferrites with garnet structure, and then disposed in a geologic repository. The actinide-REE fraction is characterized by a complex composition. In addition to major components (An and REE), Al, Si, Na, and Sn occur therein in small amounts (a few wt %). Possible incorporation of the admixtures into ferrite garnets, as well as their effect on the phase composition of matrices and Th, Ce, Gd, and La contents were studied. It was shown that admixtures enter into garnet by means of isomorphic replacement. The properties of samples change only when admixtures are added in amounts exceeding their concentrations in HLW. The ability of ferrite garnets to accumulate significant amounts of An, REE, and admixture elements makes them suitable for use as matrices in immobilizing actinide-REE HLW of complex composition.  相似文献   

3.
Crystallization of borosilicate glasses, used now for solidification of liquid nuclear high-level wastes (HLW), is accompanied by the formation of silicates with the apatite-type structure and high contents of actinides and REE. The stability of these silicates determines the safety of immobilization of radionuclides. As a result of radioactive decay, the crystalline phases of actinides become amorphous with time and their solubility in aqueous solutions increases. One of the ways to assess the radiation stability of compounds is the study of their natural analogues that contain radioactive elements. Minerals of the britholite group are the natural analogues of synthetic rare earth silicates and actinides with the apatite-type structure. Seven britholites of different ages and with different ThO2 + UO2 contents have been studied. The stages of partial damage and complete destruction of sample structures under the effect of radioactive decay were distinguished. The radiation stability of natural britholites surpasses that of their synthetic analogues. The annealing of metamict samples recovers the primary apatite-type structure without formation of any other phases. With an increase in annealing duration from 1 to 5 h, the mineral structure is recovered at a lower (by 200°C) temperature (down to 550–600°C). The temperature conditions in underground storages and the substantially longer occurrence of HLW therein will prevent crystalline matrices with the apatite-type structure from amorphization and thus ensure the retention of their stability.  相似文献   

4.
Extraction of the actinide-REE fraction and its subsequent incorporation into sparingly soluble crystalline phases (confinement matrices) is assumed in processing of spent nuclear fuel from high-level radioactive wastes (HLW). The chemical stability in the process of interaction with subsurface water governs the capability of a matrix phase to keep radionuclides from getting into the biosphere. In static experiments at 90 and 150°C, the chemical stability of ferrite garnets was investigated for three compositions with Th4+, Ce4+ and Gd3+ + serving as simulator components of the actinide fraction of HLW. Experiments were carried out in distilled water (pH 6.5), 0.01 M HCl solution (pH 2), and 0.01 M NaOH solution (pH 12). The behavior of ferrigarnet matrices depends on the acidity of the solution. In neutral and alkaline media, Th, Ce, and Gd are virtually not transferred into the liquid phase. Acid leaching promotes intense dissolution of garnet matrices. In this case, the leaching rate of Gd and Th from ceramics into the liquid phase is two orders of magnitude lower than the leaching rate of Ce because the Ce-doped phases contain less stable (relative to garnet) Ce-rich perovskite. Amorphization of the ferrigarnet structure due to 244Cm isotope decay leads to an increase in the leaching rate of Cm by no more than five times. In terms of radiation and chemical stability, ferrite garnets are not inferior to zirconolites and titanate pyrochlores. The experimental results suggest that garnet matrices can reliably immobilize actinides in subsurface repositories.  相似文献   

5.
核废物处置安全评价的地质类比研究   总被引：3，自引：0，他引：3  
闵茂中 《地质论评》1994,40(2):150-156
本文简要论述了利用天然地质类似物（或类比体），类比评价核废物处置系统的安全性能。地质类比研究是安全评价核废物处置系统的重要方法之一，也是地质学科的新研究领域。目前已有的地质类比研究对象主要有火山玻璃，陨石玻璃，粘土矿物，铁陨石，铜矿床，铀矿床，含含Ｔｈ和ＲＥＥ的铁矿床，天然核反应堆（一种特殊的铀矿床）和火成岩接触带等。最后对我国今后从事同类研究提出了若干建议。  相似文献   

6.
Doklady Earth Sciences - The durability of matrices for the rare-earth–actinide fraction of high-level radioactive waste (HLW) composed of Nd2ZrTiO7 (cubic pyrochlore-type structure) or...  相似文献   

7.
《Applied Geochemistry》2004,19(6):899-916
A 7 step sequential extraction procedure has been conducted on a podzolic soil profile from the Vosges Mountains in order to determine the ability of several elements to be released to the environment. Very little Si, K and Al were extractable (<10% of the total soil concentration) but larger proportions (> 10% of the total soil concentration) of Ca, P, metals (Fe, Pb), REE and actinides (Th, U) could be leached. For each element, preferential binding sites can be recognized. High recovery of P and Ca in the acid soluble fraction (AS) suggests that phosphate minerals are highly involved in this step of the extraction. Organic matter appears to control the adsorption of Ca, Fe, Th, U and REE, even at depths in the soil profile where organic matter content is particularly low (0.5%). Weak acid leaching experiments (with HCl and acetic acid 0.001 N) were also performed in order to characterize the origin of the insoluble material in this soil profile. The leachable REE distributions indicate that a large part of the labile REE in the surface horizon has an atmospheric origin whereas at greater depth phosphate mineral (apatite) alteration is the main factor controlling REE release in the leachate. The study further suggests that adsorbed material holding actinides and REE are not strictly the same. So, caution should be taken when using REE as analogues for actinides in soils systems.  相似文献   

8.
Zirconolite, its Ce-, Nd-, and Y-analogs, and laachite, another member of the zirconolite group, are typomorphic minerals of the fenitized xenoliths in nepheline syenite and foidolite of the Khibiny–Lovozero Complex, Kola Peninsula, Russia. All these minerals are formed at the late stage of fenitization as products of ilmentie alteration under the effect of Zr-bearing fluids. The diversity of these minerals is caused by the chemical substitutions of Na and Ca for REE, Th, and U compensated by substitution of Ti and Zr for Nb, Fe and Ta, as well as by the redistribution of REE between varieties enriched in Ti (HREE) or Nb (LREE). The results obtained can be used in the synthesis of Synroc-type titanate ceramics assigned for the immobilization of actinides.  相似文献   

9.
谭光贵 《湖南地质》1996,15(4):229-233
湘南主要稀土矿区的岩、矿石和稀土矿物的放射性特征表明，矿区放射性强度的高低与稀土总量无关，而与矿石的铀、钍含量密切相关；主要矿区的放射性对其开发与产品都没有影响，但长期接触对人体有一定危害。因此，开采时必须加强防护，防止放射性的长期照射，并选用无放射性的清洁饮用水，以保护人体健康。  相似文献   

10.
The mobility of the rare-earth elements (REE) is relevant to nuclear waste management in that REE are produced during radioactive decay in high-level waste and they are good chemical analogues for some of the trivalent actinides (e.g., Am3+ and Cm3+). Car☐ylic acids are present naturally in many geologic fluids and also have been disposed of along with radionuclides; such complexing agents may increase the mobility of the REE (actinides) and need to be considered in geochemical models of the transport of these metals into the far-field environment. In this study, available stability constants for the formation of REE complexes with the organic ligands acetate, adipate, benzoate, citrate, ETDA, formate, fumarate, glutarate, glycolate, -hydroxyisobutyrate, isobutyrate, lactate, maleate, malonate, -mercaptoacetate, oxalate, m-phthalate, o-phthalate, propionate, salicylate and succinate have been critically evaluated. Those stability constants considered most reliable were, where necessary, corrected to 25°C using published enthalpy data and, where possible, corrected to infinite dilution using a model based on the Pitzer equations. These data provide the basis for future geochemical modelling of the behavior of the REE in nuclear waste disposal sites. Some simple geochemical calculations presented in this paper suggest that monodentate ligands such as acetate are unlikely to contribute significantly to REE (actinide) mobility in most nuclear waste disposal environments. However, ligands capable of chelating in a multi-dentate manner, e.g., oxalate, malonate, succinate, EDTA, etc., may increase the mobility of trivalent lanthanides and actinides significantly, even though their concentrations are lower than monodentate ligands in most natural environments. However, the effectiveness of any of these organic ligands depends on the concentrations of competing ions, such as Ca2+, Mg2+, etc., being low relative to the total ligand concentration.  相似文献   

11.
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   

12.
1INTRODUCTION THELATEPRECAMBRIANGRANITOIDSOFTHEARABONU BIANSHIELDINEGYPTWEREEXPOSEDBYEARLYTOMIDDLE TERTIARYUPLIFTANDENSUINGEROSIONDURINGTHEREDSEA RIFTINGEVENT(GREENBERG,1981).THEREAREANUMBER OFEFFECTIVEANDRELATIVELYSUCCESSFULSCHEMESFORTHE CLASSIFICATIONOF…  相似文献   

13.
The convective transfer of radionuclides by subsurface water from a geological repository of solidified high-level radioactive wastes (HLW) is considered. The repository is a cluster of wells of large diameter with HLW disposed of in the lower portions of the wells. The safe distance between wells as a function of rock properties and parameters of well loading with wastes has been estimated from mathematical modeling. A maximum permissible concentration of radionuclides in subsurface water near the ground surface above the repository is regarded as a necessary condition of safety. The estimates obtained show that well repositories allow for a higher density of solid HLW disposal than shaft storage facilities. Advantages and disadvantages of both types of storage facilities are considered in order to estimate the prospects for their use for underground disposal of solid HLW.  相似文献   

14.
凡人类从事于与核材料有关的许多生产、生活活动均可能产生不同活度的放射性废物。高放废物由于具有放射性水平高、发热量大、核素寿命长等特点,其安全处置倍受全球科学家和广大公众所重视。目前深地质处置被国际上公认为处置高放废物的最有效可行的方法。借鉴已有研究成果,我国采用多重工程屏障系统(包括废物固化体、废物罐及其外包装和缓冲/回填材料)和适宜的地质围岩地质体共同作用来确保高放废物与生物圈的安全隔离。参照国际上该领域的研究成果,结合我国处置概念,本文就高放废物地质处置中的工程材料(废物固化体、废物罐、外包装、缓冲材料、回填材料),以及其材料选择、设计要求和研究重点等进行了总结。  相似文献   

15.
BEA  F. 《Journal of Petrology》1996,37(3):521-552
A systematic study with laser ablation—ICP-MS, scanningelectron microscopy and electron microprobe revealed that 70–95wt% of REE (except Eu), Y, Th and U in granite rocks and crustalprotoliths reside within REEYThU-rich accessories whose nature,composition and associations change with the rock aluminosity.The accessory assemblage of peraluminous granites, migmatitesand high-grade rocks is composed of monazite, xenotime (in low-Cavarieties), apatite, zircon, Thorthosilicate, uraninite andbetafite-pyrochlore. Metaluminous granites have allanite, sphene,apatite, zircon, monazite and Thorthosilicaie. Peralkaline graniteshave aeschinite, fergusonite, samarskite, bastnaesite, fluocerite,allanite, sphene, zircon, monazite, xenotime and Th-orthosilicate.Granulite-grade garnets are enriched in Nd and Sm by no lessthan one order of magnitude with respect to amphibolite-gradegarnets. Granulitegrade feldspars are also enriched in LREEwith respect to amphibolite-grade feldspars. Accessories causenon-Henrian behaviour of REE, Y, Th and U during melt—solidpartitioning. Because elevated fractions of monazite, xenotimeand zircon in common migmatites are included within major minerals,their behaviour during anatexis is controlled by that of theirhost. Settling curves calculated for a convecting magma showthat accessories are too small to settle appreciably, beingseparated from the melt as inclusions within larger minerals.Biotite has the greatest tendency to include accessories, therebyindirectly controlling the geochemistry of REE, Y, Th and U.We conclude that REE, Y, Th and U are unsuitable for petrogeneticalmodelling of granitoids through equilibrium-based trace-elementfractionation equations. KEY WORDS: accessory minerals; geochemical modelling; granitoids; REE, Y, Th, U  相似文献   

16.
This paper reports a geochemical and mineralogical study on carbonatites from the Guli massif, which hosts rare-metal mineralization. The principal carriers of radioactive elements in the carbonatites are pyrochlore-group minerals, zirconolite, and thorianite, which are described here. They are characterized by elevated concentrations (wt %) of radioactive elements: up to 17.89 UO2 and 20.01 ThO2 in pyrochlore, up to 6.49 UO2 and 94.29 ThO2 in thorianite, and up to 6.74 ThO2 in zirconolite. The pyrochlore-group minerals, zirconolite, and thorianite from the early calcite carbonatites occur in intimate association with Ti-Zr oxides calzirtite, perovskite, and baddeleyite. Significant radioactive element fractionation in early-stage derivatives results in the depletion of the residual magmatic products in these elements. The dolomite carbonatites are reported to contain only trace amounts of pyrochlore-group minerals. It was shown that the distribution of U, Th, Nb, and Ta in the calcite and dolomite carbonatites is correlated with the evolutionary trends of pyrochlore composition. Typical schemes of isomorphic substitution are proposed for pyrochlore-group minerals and zirconolite. The pyrochlore-group minerals show an apparent evolutionary trend from U-rich towards more Th- and Ta-rich varieties, and Ba-Sr cation-deficient varieties originate during the latest stage of the evolution. The pyrochlore-group minerals, zirconolite, and thorianite may also accumulate in placers, together with gold. Because of the relative ease of extraction of the accessory minerals, the carbonatites of the Guli massif can be considered as commercial sources of radioactive raw materials.  相似文献   

17.
由于自然伽马能谱测井(NGS)的放射性元素U、Th、K的含量与粘土矿物有着密切的关系,所以可利用NGS定性或定量确定油气储层粘土矿物含量。阐述了自然伽马能谱测井资料在确定粘土矿物含量中的地质依据,建立了研究地层粘土矿物含量的计算模型。由研究油田的NGS测井资料计算并对比了粘土矿物的含量,最终得到很好的效果。  相似文献   

18.
Ion microprobe data for minerals from the eclogites of the Atbashi Range (South Tianshan) constrain the distribution of trace (Rb, Sr, Ba, Cr, V, Zr, Hf, Nb, Ta, U, Th, and Y) and rare-earth elements (REE) in zoned garnets and mineral inclusions in them. This study showed that garnets from the Atbashi eclogites are the main hosts for heavy REE; epidotes are important hosts for REE, Y, Sr, Th, and U; and omphacites are depleted in almost all trace elements compared with the bulk-rock compositions. Garnet, as well as epidote and omphacite inclusions exhibit systematic rimward depletion in a number of trace elements, which is related to the depletion of the rock matrix in these elements during crystallization. Deviations from this trend, including the enrichment of garnet rims in HREE and strong variations in the REE contents of garnets and mineral inclusions, can be explained by metamorphic reactions involving the destabilization of REE-bearing minerals. Our data suggest that the mobility of trace elements under eclogites-facies conditions is mainly controlled by the stability of certain minerals.  相似文献   

19.
Doklady Earth Sciences - The thermal fields for a borehole repository of the Cs–Sr and REE–actinide fractions of radioactive waste are calculated based on the waste content, the size of...  相似文献   

20.
Complex oxides of the pyrochlore (space groups Fd3m, [8]A2 [6]B2O7) and garnet (Ia3d, [8]A3 [6]B2 [4]T3O12) structures (“A” = Ca2+, Ln3+/4+, An3+/4+; “B” = (Ti, Sn, Hf, and Zr)4+ in pyrochlore, and Al3+, Ga3+, and Fe3+ in garnet alone; “T” = (Al3+, Ga3+, and Fe3+) are promising matrices for actinide-bearing wastes. In order to identify optimal compositions of these phases, their isomorphic capacity with respect to REE, actinides, and other components of wastes was examined. The long-term behavior of the matrix at a repository was predicted based on data obtained on the behavior of pyrochlores and garnets under ion irradiation and 244Cm decay and on the determined leaching rates of REE from the matrices because of their interaction with aqueous solutions, including that after amorphization. In order to propose efficient synthesis techniques, samples prepared with the use of various methods were studied. The possibility of incorporating long-lived decay products of 99Tc into the crystalline matrices was analyzed.  相似文献   

设为首页 | 免责声明 | 关于勤云 | 加入收藏

Copyright©北京勤云科技发展有限公司  京ICP备09084417号