粤北下庄铀矿田中铀酰矿物的成分特征——对核废料处置库中UO2氧化行为的启示

下庄铀矿为一花岗岩型铀矿，矿田地处湿热气候条件下，沥青铀矿普遍产于破碎带中，这种特定的产出环境致使该区沥青铀矿经受了强烈的风化，形成种类繁多、数量丰富的铀酰矿物；而我国高放废物地质处置库拟建在花岗岩体中。因此，下庄铀矿田是开展核废料氧化的天然类比研究的理想地区，并对我国的高放废物地质处置库的安全性评价有重要的指导作用。下庄铀矿田的铀酰矿物组合为铀酰氢氧化物、铀酰硅酸盐和铀酰磷酸盐，包括柱铀矿、黄钙铀矿、calciouranoite、红铀矿、富硅铀酰相、硅钙铀矿、钙铀云母和盈江铀矿等。根据它们的空间分布特征可划分成两个风化系列，即硅酸盐风化系列和磷酸盐风化系列，其共生次序分别为：沥青铀矿→铀酰氢氧化物（氧化物）→富硅铀酰相→硅钙铀矿和沥青铀矿→铀酰氢氧化物（氧化物）→钙铀云母→盈江铀矿。在该矿田中，铀酰氢氧化物是亚稳定相矿物，常常被铀酰硅酸盐或磷酸盐取代，因此，铀酰氢氧化物仅出现在少数样品中，而铀酰硅酸盐和铀酰磷酸盐矿物则非常普遍。矿田中的铀酰矿物在化学成分上以富钙为其显著特征，由于核废料地质处置库近场地下水中的Ca^2＋含量应该明显比下庄矿田地下水中的高，因此，我们预测含Ca的铀酰硅酸盐和铀酰磷酸盐矿物等热力学上的稳定物相很可能是地质处置系统中最主要的铀酰矿物，处置库内放射性核素的迁移主要是由这些矿物控制的。     

模拟含铀废液中沥青铀矿形成机理探讨

在利用沥青铀矿结晶法处理含铀废液的20组实验中发现,由于实验条件与溶液含铀浓度的不同,除直接可以形成沥青铀矿外,还形成了其他终极产物及中间过渡产物。对反应过程的观察以及对产物X射线衍射、红外光谱及其能谱分析结果的研究表明,在酸性条件下,较高的温度与较高的铀浓度有利于直接形成沥青铀矿,否则会先形成水合氢氧化铀酰、UO2和UO3的混合物、UO3等中间产物,再进一步形成沥青铀矿,或者反应止步于单质S、UO2和UO3的混合物。     

广西花山铀矿床氧化带中铀酰矿物特征、成因及其勘查指示意义

本文分析了广西花山铀矿床氧化带中铀酰矿物的类型、组合及赋存特征,探讨铀酰矿物的成因机制及其对深部铀矿体勘查的指示意义。研究发现,花山铀矿床氧化带中铀酰矿物的类型非常复杂,长冲、白石脚和糙米坪等三个矿点出现不同的铀酰矿物组合。长冲矿点发育准钙铀云母、钙铀云母和硅钙铀矿等铀酰磷酸盐和铀酰硅酸盐组合,铀酰矿物的阳离子组分以富Ca为特点;白石脚矿点出现硅铅铀矿和斜磷铅铀矿等铀酰硅酸盐组合,铀酰矿物的阳离子组分以富Pb为特点;糙米坪矿点出现翠砷铜铀矿、铜铀云母和脂状铅铀矿等铀酰磷酸盐、铀酰砷酸盐和铀酰氢氧化物组合,铀酰矿物的阳离子组分以富Cu和As等为特点。花山铀矿床中的铀酰矿物是原生铀矿物(推断为沥青铀矿)在氧化环境下发生次生沉淀作用而形成的,三个矿点铀酰矿物组合的差异归因于原生铀矿体元素地球化场、地下水中络阴离子类型和地下水介质pH环境等多种因素的耦合。研究认为,铀矿床氧化带中的铀酰矿物对于指导深部盲矿勘查具有一定的指示意义。在花山地区,铀酰矿物沿断裂带出现大规模的垂向分布,它的发育位置大致记录了原生铀矿体的产状特征,而铀酰矿物的含量和类型则有助于提供原生铀矿石品位和硫化物含量等重要的成矿信息。本研究预测,在花山矿区内的糙米坪和白石脚矿点仍然存在发现氧化型铀矿体的良好潜力。     

砂岩型铀矿床中铀矿物的形成机理

本文通过对砂岩型铀矿床中铀在不同地球化学环境中的行为、存在形式及铀矿物种类的分析，论述了主要工业铀矿物——沥青铀矿的形成机理：(1)铀是变价元素，在氧化环境中活化迁移，在还原环境中还原沉淀；(2)来自于氧化环境的[UO2(CO3)3]^4-、[UO2(CO3)2]^2-在氧化还原过渡带与有机质、硫化物及低价铁等还原剂发生反应，形成铀的简单氧化物——沥青铀矿；(3)有机质、粘土矿物等吸附UO2^2 ，加快了其被还原的速度，有利于铀的富集。因此认为：有机质还原UO2^2 形成H2S和H2S还原UO2^2 的作用是沥青铀矿形成的主要原因，这一反应在中性和弱碱性碳酸盐溶液中广泛和普遍存在。H2S等还原剂的存在是环境Eh值下降的主要原因，从而使水中的UO2^2 在氧化还原过渡带处于过饱和状态，加速了铀的吸附和沉淀。     

天然金属铀的首次发现

正铀广泛分布于地球的各种地质体中,由于其化学性质活泼,通常以+3、+4、+5、+6价态的化合物状态存在,其中+4和+6价铀化合物稳定。四价态铀通常以晶质铀矿(或沥青铀矿)(UO2)形成于岩浆、热液、沉积和变质作用产物中,而六价态通常以铀酰离子(UO2+2)化合物溶于水体中或在沉积、蒸发和氧化的条件下形成硫酸盐、碳酸     

铀矿床作为高放废物处置库天然类似物的国内外研究进展

铀矿床具有目前国际上开发的高放废物深地质处置概念的相似特征，对其开展天然类比研究，是认识核素在地质环境中迁移行为的一种有效方法。本文阐述了高放废物深地质处置库天然类似物的一般概念及天然类比研究拟解决的科学问题。重点介绍了30年来国内外在天然类比研究中取得的主要成果、认识以及国内外研究进展。     

宁安盆地501矿点铀矿化特征

宁安盆地501矿点是1960年代末期提交的小型砂岩型铀矿。该矿点主要产于砂砾岩、砂岩中,以产次生铀酰矿物为主;近年来的研究表明,它是一种特殊的基底古河谷型砂岩铀矿,其形成后遭受了强烈的后生氧化改造,次生铀酰矿物是铀矿床或铀矿体的地表氧化带产物。运用地浸砂岩型铀矿成矿理论,对501矿点地质特征、铀矿化特征进行了论述,认为铀矿化赋存于辫状河沉积体系中,与原始沉积灰色层、潜水氧化带等关系密切。     

我国产出的铀酰砷酸盐矿物及其环境矿物学意义

对我国产出的铀酰砷酸盐矿物的矿物学特征、形成环境和环境矿物学意义进行了较系统的综合论述。铀酰砷酸盐矿物是主要产出于铀矿床氧化带中比较特征的黄绿色表生矿物，是寻找原生铀矿床(体)的重要矿物学标志，化学组成主要是[AsO4]^3-和[UO2]^2 ，其中As和U均是对环境造成极大危害的有毒或放射性有害元素。As、U的地球化学性质十分活跃，在不同的酸、碱和氧化还原介质环境中的分解、迁移能力均很强，在矿床氧化带中的分解、迁移扩散会对矿区周围及其下游地区造成较大范围的严重环境污染。而在弱酸性至中性介质条件下，[AsO4]^3-和[UO2]^2 结合并与各种金属阳离子化合可形成相对稳定的铀酰砷酸盐矿物，由此可在一定程度上减少U、AS的迁移扩散及其对环境的危害。     

低煤级煤与UO22+的吸附络合及亲煤型铀矿成矿过程

针对中国亲煤(煤系)砂岩型铀矿床成矿过程,以不同氧化程度的低煤级煤为研究对象,采用分光光度法研究煤对铀酰离子的吸附络合作用.结果表明,煤对铀酰离子(UO22+)的吸附作用受煤氧化程度、煤种、溶液pH值、环境温度和铀溶液初始浓度等因素影响.脱附实验和红外光谱分析进一步证明,煤中活性官能团与铀酰离子发生了明显的化学吸附/络合作用.基于上述结果,提出了亲煤型砂岩铀矿的成矿过程,为揭示煤与铀矿共伴生关系提供了基础数据.     

赣南6722铀矿床钛铀矿—晶质铀矿—铀石—沥青铀矿显微共生组合的厘定及成因意义

通过235U诱发裂变径迹及电子探针测试综合研究,在6722铀矿床的含矿隐爆角砾岩胶结物中首次发现钛铀矿—晶质铀矿—铀石—沥青铀矿显微共生组合。这样一种在1 cm2(光薄片)范围内分布,而且不存在任何脉状相互穿插现象的钛铀矿—晶质铀矿—铀石—沥青铀矿显微共生组合表明其形成于同一成矿物理化学体系中。根据UO2—TiO 2—H2O体系稳定场,确定6722铀矿床中钛铀矿—晶质铀矿—铀石—沥青铀矿显微共生组合形成温度范围为250~350℃,属中—高温热液成因。     

Alteration of uraninite from the Nopal I deposit,Pen˜a Blanca District,Chihuahua, Mexico,compared to degradation of spent nuclear fuel in the proposed U.S. high-level nuclear waste repository at Yucca Mountain,Nevada

At the Nopal I uranium deposit, primary uraninite (nominally UO_2+x) has altered almost completely to a suite of secondary uranyl minerals. The deposit is located in a Basin and Range horst composed of welded silicic tuff; uranium mineralization presently occurs in a chemically oxidizing and hydrologically unsaturated zone of the structural block. These characteristics are similar to those of the proposed U.S. high-level nuclear waste (HLW) repository at Yucca Mountain, Nevada. Petrographic analyses indicate that residual Nopal I uraninite is fine grained (5–10 μm) and has a low trace element content (average about 3 wt%). These characteristics compare well with spent nuclear fuel. The oxidation and formation of secondary minerals from the uraninite have occurred in an environment dominated by components common in host rocks of the Nopal I system (e.g. Si, Ca, K, Na and H₂O) and also common to Yucca Mountain. In contrast, secondary phases in most other uranium deposits form from elements largely absent from spent fuel and from the Yucca Mountain environment (e.g. Pb, P and V). The oxidation of Nopal I uraninite and the sequence of alteration products, their intergrowths and morphologies are remarkably similar to those observed in reported corrosion experiments using spent fuel and unirradiated UO₂ under conditions intended to approximate those anticipated for the proposed Yucca Mountain repository. The end products of these reported laboratory experiments and the natural alteration of Nopal I uraninite are dominated by uranophane [nominally Ca(UO₂)₂Si₂O₇·6H₂O] with lesser amounts of soddyite [nominally (UO₂)₂SiO₄·2H₂O] and other uranyl minerals. These similarities in reaction product occurrence developed despite the differences in time and physical—chemical environment between Yucca Mountain-approximate laboratory experiments and Yucca Mountain-approximate uraninite alteration at Nopal I, suggesting that the results may reasonably represent phases likely to form during long-term alteration of spent fuel in a Yucca Mountain repository. From this analogy, it may be concluded that the likely compositional ranges of dominant spent fuel alteration phases in the Yucca Mountain environment may be relatively limited and may be insensitive to small variations in system conditions.     

Uranium Behavior in the Process of Primary Pitchblende Ores Alteration by the Post‐ore Hydrothermal Solutions: An Application to Assessment of Uranium Migration from Underground Spent Nuclear Fuel Repositories

It has been shown that the main uranium ore mineral, pitchblende (uranium dioxide), is a natural analog of synthetic uraninite (also uranium dioxide), which constitutes 96% of spent nuclear fuel (SNF). Geochronological studies of the U‐Pb isotope systems in unaltered pitchblende from the orebodies reveal that these systems remained completely closed over the entire period (approximately 135 Ma) since the formation of the deposits. The bulk of the primary uranium ores within the Streltsovskoye ore field was influenced to various degrees by post‐ore hydrothermal solutions that led to pitchblende spherulites being replaced by pseudomorphs of an amorphous phase with a U‐Si composition; this phase also re‐precipitated in veinlets proximal to the pitchblende pseudomorphs. A technique specially developed by the authors was used to carry out quantitative counts of the abundance of uranium minerals by calculating the uranium mass balance in one of the orebodies subjected to hydrothermal alteration. The calculations reveal minimal uranium loss from the orebody. Uranium liberated in the process of the pseudomorphic replacement of pitchblende was immediately fixed, in situ, in the newly formed coffinite‐like amorphous U‐Si phase as a result of the development of an efficient geochemical barrier that prevented the long‐distance migration of uranium. In assessing the long‐term safety of underground SNF repositories, the results of the present study give us confidence that SNF uraninite, in terms of the preservation of its integrity as a mineral phase, provides for the reliable long‐term isolation of uranium, transuranium elements, and fission products that are “sealed” in the uraninite matrix. In the case of the mineral transformation of the uraninite matrix by hydrothermal solutions, the liberated uranium would be efficiently immobilized by the newly formed amorphous U‐Si phase.     

Fate of trace elements during alteration of uraninite in a hydrothermal vein-type U-deposit from Marshall Pass, Colorado, USA

Alteration of uraninite from a hydrothermal vein-type U-deposit in Marshall Pass, Colorado, has been examined by electron microprobe analysis in order to investigate the release and migration of trace elements W, As, Mo, Zr, Pb, Ba, Ce, Y, Ca, Ti, P, Th, Fe, Si, Al, during alteration, under both reducing and oxidizing conditions. The release of trace elements from uraninite is used to establish constraints on the release of fission product elements from the UO₂ in spent nuclear fuels. Uraninite occurs with two different textures: (1) colloform uraninite and (2) fine-grained uraninite. The colloform uraninite contains 1.04-1.75 wt% of WO₃, 0.16-1.70 wt% of As₂O₃, 0.06-0.88 wt% of MoO₃; whereas, the fine-grained uraninite retains 2.25-4.93 wt% of WO₃, up to 5.76 wt% of MoO₃, and 0.26-0.60 wt% of As₂O₃. The near constant concentration of incompatible W in the colloform uraninite suggests W-incorporation into the uraninite structure or homogeneous distribution of W-rich nano-domains. Incorporation of W and Mo into the uraninite and subsequent precipitation of uranyl phases bearing these elements are critically important to understanding the release and migration of Cs during the corrosion of spent nuclear fuel, as there is a strong affinity of Cs with W and Mo. Zoning in the colloform texture is attributed to variation in the amount of impurities in uraninite. For unaltered zones, the calculated amount of oxygen ranges from 2.08 to 2.32 [apfu, (atom per formula unit)] and defines the stoichiometry as UO_2+x and U₄O₉; whereas, for the altered zones of the colloform texture, the oxygen content is 2.37-2.48 [apfu], which is probably due to the inclusion of secondary uranyl phases, mainly schoepite. The supergene alteration resulted in precipitation of secondary uranyl minerals at the expense of uraninite. Four stages of colloform uraninite alteration are proposed: (i) formation of an oxidized layer at the rim, (ii) corrosion of the oxidized layer, (iii) precipitation of U⁶⁺-phases with well-defined cleavage, and (iv) fracture of the uraninite surface along the cleavage planes of the U⁶⁺-phases.     

含铀副矿物的热液蚀变：来自华南鹿井矿田碎裂蚀变岩型铀矿床的矿物学研究

花岗岩型铀矿中铀的来源问题，长期以来是铀矿床学研究的热点问题之一。大多数学者认为其成矿物质主要来源于花岗岩本身的含铀副矿物，然而对于含铀副矿物热液蚀变行为研究较少。鹿井铀矿田位于诸广山复式岩体的中部，是华南最主要花岗岩型铀矿田之一，碎裂蚀变岩型铀矿化在该矿田内占主导地位。小山铀矿床位于鹿井矿田中部，是近些年新发现的碎裂蚀变岩型矿床。本文以钻孔ZK1- 1为研究对象，对热液蚀变带开展了精细矿物学研究。研究表明：蚀变带中发育有晶质铀矿、铀石—钍石、独居石、磷钇矿、锆石、磷灰石、金红石等含铀副矿物。晶质铀矿、铀石—钍石中铀含量高，热液蚀变条件不稳定，铀容易释放；独居石蚀变为直氟碳钙铈矿和磷钇矿蚀变为次生磷灰石过程中容易释放出铀；锆石因结构稳定，铀难以释放；磷灰石、金红石中铀含量较低，供铀能力差。综合分析认为花岗岩中晶质铀矿、铀石—钍石是主要铀源矿物，独居石、磷钇矿为次要铀源矿物。     

Behavior of uranium under conditions of interaction of rocks and ores with subsurface water

The behavior of uranium during interaction of subsurface water with crystalline rocks and uranium ores is considered in connection with the problem of safe underground insulation of spent nuclear fuel (SNF). Since subsurface water interacts with crystalline rocks formed at a high temperature, the mineral composition of these rocks and uranium species therein are thermodynamically unstable. Therefore, reactions directed toward the establishment of equilibrium proceed in the water-rock system. At great depths that are characterized by hindered water exchange, where subsurface water acquires near-neutral and reducing properties, the interaction is extremely sluggish and is expressed in the formation of micro- and nanoparticles of secondary minerals. Under such conditions, the slow diffusion redistribution of uranium with enrichment in absorbed forms relative to all other uranium species is realized as well. The products of secondary alteration of Fe- and Ti-bearing minerals serve as the main sorbents of uranium. The rate of alteration of minerals and conversion of uranium species into absorbed forms is slow, and the results of these processes are insignificant, so that the rocks and uranium species therein may be regarded as unaltered. Under reducing conditions, subsurface water is always saturated with uranium. Whether water interacts with rock or uranium ore, the equilibrium uranium concentration in water is only ≤10^?8 mol/l. Uraninite ore under such conditions always remains stable irrespective of its age. The stability conditions of uranium ore are quite suitable for safe insulation of SNF, which consists of 95% uraninite (UO₂) and is a confinement matrix for all other radionuclides. The disposal of SNF in massifs of crystalline rocks at depths below 500 m, where reducing conditions are predominant, is a reliable guarantee of high SNF stability. Under oxidizing conditions of the upper hydrodynamic zone, the rate of interaction of rocks with subsurface water increases by orders of magnitude and subsurface water is commonly undersaturated with uranium. Uranium absorbed by secondary minerals, particularly by iron hydroxides and leucoxene, is its single stable species under oxidizing conditions. The impact of oxygen-bearing water leads to destruction of uranium ore. This process is realized simultaneously at different hypsometric levels even if the permeability of the medium is variable in both the lateral and vertical directions. As a result, intervals containing uranyl minerals and relics of primary uranium ore are combined in ore-bearing zones with intervals of completely dissolved uranium minerals. A wide halo of elevated uranium contents caused by sorption is always retained at the location of uranium ore entirely destroyed by weathering. Uranium ore commonly finds itself in the aeration zone due to technogenic subsidence of the groundwater table caused by open-pit mining or pumping out of water from underground mines. The capillary and film waters that interact with rocks and ores in this zone are supplemented by free water filtering along fractures when rain falls or snow is thawing. The interaction of uranium ore with capillary water results in oxidation of uraninite, accompanied by loosening of the mineral surface, formation of microfractures, and an increase in solubility with enrichment of capillary water in uranium up to 10^?4 mol/l. Secondary U(VI) minerals, first of all, uranyl hydroxides and silicates, replace uraninite, and uranium undergoes local diffusion redistribution with its sorption by secondary minerals of host rocks. The influx of free water facilitates the complete dissolution of primary and secondary uranium minerals, the removal of uranium at the sites of groundwater discharge, and its redeposition under reducing conditions at a greater depth. It is evident that the conditions of the upper hydrodynamic zone and the aeration zone are unfit for long-term insulation of SNF and high-level wastes because, after the failure of containers, the leakage of radionuclides into the environment becomes inevitable.     

纳米比亚欢乐谷地区白岗岩型铀矿矿物特征研究

本文通过系统的岩矿鉴定和电子探针分析,对纳米比亚欢乐谷地区白岗岩型铀矿的矿物特征进行了详细的研究.该地区铀的赋存形式以独立铀矿物为主,少量以类质同像形式存在于钍矿物中.铀矿物的主要种类有:晶质铀矿、钍铀矿、铀石、铀钍石、钛铀矿、沥青铀矿、硅钙铀矿和钒钾铀矿等,其中,晶质铀矿、钍铀矿和钛铀矿等原生铀矿物约占69％,而反应边状铀石、铀钍石、沥青铀矿、钒钾铀矿和硅钙铀矿等次生铀矿物约占31％.由此可见,该区铀矿化主要表现为原始岩浆的分异作用与后期热液改造作用的相互叠加,其热液改造程度不大,仅使铀发生内部再分配.     

μ-XRF技术在黄龙铺钼(铀)矿床铀矿物学研究中的应用

东秦岭碳酸岩型钼成矿带是全球最大的钼成矿带。该带内的黄龙铺矿床是中国最早发现的碳酸岩型钼矿床之一。最近的野外地质调查发现,部分钼矿石具有较高的放射性异常,但其放射性元素的赋存形式和矿物学特征尚不明确。本文借助聚毛细管微束X射线荧光光谱分析(μ-XRF)分析速度快、原位无损、高灵敏度的分析优势,快速查明铀矿物的空间位置,再结合扫描电镜分析(SEM)和X射线能谱分析(EDS),确定铀矿物的种类及其次生变化。研究表明:黄龙铺矿床高放射性矿石中主要的铀矿物为钛铀矿、铌钛铀矿和晶质铀矿,它们与方解石、长石、黄铁矿、辉钼矿和黄铜矿呈共生关系。矿石中铀矿物后期均遭受氧化性流体改造,发生了明显的蚀变,钛铀矿蚀变之后转变为含Nb的钛铁氧化物,铌钛铀矿和晶质铀矿蚀变后矿物内部形成大量空洞,流体来源可能为大气降水。背散射电子(BSE)图像上灰度差异明显,暗示着矿物中元素分布的不均一性。     

Geochemical fixation of rare earth elements into secondary minerals in sandstones beneath a natural fission reactor at Bangombé, Gabon

To study geochemical processes for migration and fixation of fissiogenic rare earth elements (REE) in association with uranium dissolution, in situ isotopic analyses using an ion microprobe were performed on U- and REE-bearing secondary minerals, such as coffinite, françoisite, uraniferous goethite, and uraninite found in a sandstone layer 30 to 110 cm beneath a natural fission reactor at Bangombé, Gabon. Phosphate minerals such as phosphatian coffinite and françoisite with depleted ²³⁵U (²³⁵U/²³⁸U = 0.00609 to 0.00638) contained large amount of fissiogenic light REE, while micro-sized uraninite grains in a solid bitumen aggregate have normal U isotopic values (²³⁵U/²³⁸U = 0.00725) and small amount of fissiogenic REE components. The proportions of fissiogenic and non-fissiogenic REE components in four samples from the core of BAX03 vary in depth ranging from 30 cm to 130 cm beneath the reactor, which suggests mixing between fissiogenic isotopes from the reactor and non-fissiogenic isotopes from original minerals in the sandstone. Significant chemical fractionation was observed between Ce and the other REE in the secondary minerals, which shows evidence of an oxidizing atmosphere during their formation. Pb-isotopic analyses of individual minerals do not directly provide chronological information because of the disturbance of U-Pb decay system due to recent geologic alteration. However, systematic Pb-isotopic results from all of the minerals reveal the mobilization of fissiogenic isotopes, Pb and U from the reactor in association with dolerite dyke intrusion ∼0.798 Ga ago and the formation of the secondary minerals by mixing event between 2.05 Ga-old original minerals and reactor materials due to recent alteration.     

电子探针技术研究粤北龙华山岩体中独居石蚀变晕圈的结构与成分特征

独居石是华南产铀花岗岩中常见的含铀副矿物.龙华山岩体是粤北诸广山复式岩体中一个重要的产铀花岗岩,该岩体的独居石具有蚀变晕圈现象.但是,该岩体中独居石蚀变晕圈的结构和成分特征以及对铀成矿的指示意义尚未开展研究.本文利用电子探针(EPMA)对龙华山岩体的独居石蚀变晕圈开展结构和成分研究.测试结果表明:独居石蚀变晕圈是从内到...