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.     

A possible origin of uranium deposits in granites in special reference to the formation of SL deposit

The tectonic destruction and hydrothermal alteration of the H granite massif resulted in the formation of the green alteration zone. During this process, infiltrating hydrothermal solutions would resorb uraninite in the rocks, leading to the mobilization and thus migration of uranium into fissures and grain interstices, or being adsorbed on clay minerals. As a result, the medium and space were provided for later mineralization. In the Cretaceous period, the upper part of the green alteration zone underwent strong oxidation, followed by the resorption and then the transformation of metallicsulfides into limonite and hydrogeothite. And uranium present both in uraninite and in fissures was further mobilized and concentrated to form uranium ore deposits of economic importance in the redox boundary between the green zone and the purple zone.     

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。     

Origin of uranium and rare earth minerals in bone detritus from rare metal deposits

In order to ascertain the forms in which uranium is present in ores of the Melovoe rare metal sedimentary deposit of uranium and rare earth minerals (South Mangyshlak), we investigated a series of typical ore samples that were collected earlier; both the uranium content and the total content of rare earth metals in them lay within 0.1–0.3%. The study was carried out by analytical electron microscopy using transmission electron microscopy and scanning electron microscopy, electron microdiffraction, and microprobing. It was ascertained that both uranium and rare earth elements are present in ore mostly associated with biogenic phosphate in the form of natural minerals, such as uraninite, ningyoite, coffinite, autenite, and churchite. Iron hydroxides and graphitized organic matter are present in some samples. It is assumed that the co-occurrence of uranium and rare earth elements, which is nontypical for the sedimentary process, resulted from secondary epigenetic processes and alternation of reducing and oxidizing environmental conditions.     

广东大亚湾西北部新发现铀矿点及找矿远景讨论

2003年在广东大亚湾西北部新发现了一处火山岩型铀矿点,经刻槽取样分析,铀矿石品位高达0.459%。该处铀矿物成份主要是沥青铀矿和次生铀矿物,前者 UO_2最高为94%,Al_2O_3<1%,P_2O_5含量变化大,按照 P_2O_5含量可分两组,其一变化于2.23%～2.57%,另一组变化于17.96%～19.95%;次生铀矿物含 UO_3大约为60%左右,Al_2O_3在1.6%～3.0%之间,P_2O_5变化于10%～15%。对含矿岩石及围岩进行了岩石学和地球化学研究,结果表明,出露的岩石主要为流纹质岩石,与著名的相山矿田的岩石类型相似。岩石具有高的 LREE/HREE 值,Eu 负异常并不普遍。从主、微量元素及稀土元素特征来看,含矿岩石及围岩差别不大,总特征与一般的钙碱性火山岩相似。新发现的铀矿化带范围虽然不大,但含矿岩石铀品位高,所处构造环境与相山铀矿田的某些矿床有一定的相似性,是值得注意和进一步工作的地区。     

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。     

新疆伊犁盆地砂岩型铀矿床层间氧化带中粘土矿物特征及与铀矿化关系研究

新疆伊犁盆地砂岩型铀矿床,由于规模大、成矿环境和成矿条件好,在同类型矿床中具有良好的代表性,研究矿床的成矿作用对今后找矿勘查以及开采具有重要理论意义。本文在区域赋铀层位沉积环境研究基础上,以赋矿围岩为研究主体,对伊犁盆地典型铀矿床沉积序列和矿床的控矿层位开展研究,通过对赋矿沉积层位中粘土质对铀矿成矿的控制作用及与铀矿的空间联系和成因分析,开展系统的铀矿床学、能谱测试、显微结构、扫描电镜、地球化学、氢氧同位素等研究,特别是开展了富矿砂体中粘土矿物的种类、成分、结构、同位素、成因等的研究,对粘土质矿物对铀矿成矿的控制作用进行了系统研究。通过研究粘土矿物在伊犁盆地蒙其古尔砂岩型铀矿床成矿过程中的作用及与铀矿的空间联系和成因分析表明:粘土矿物在层间氧化带中分布较为广泛,在主要矿体的氧化还原过渡带中,尤其是部分具有强烈粘土蚀变的砂岩层中铀含量较其他层位要高,反映出粘土矿物与铀成矿是有成因关联的。通过系统的扫描电镜、能谱测试研究,从微观证明粘土矿物与铀成矿有相关关系;粘土矿物的存在导致在近地表含氧含铀水在经过砂岩孔隙时被具有较强吸附能力和巨大表面自由能的粘土矿物所吸附,形成了铀含量较高的片状,团块状的粘土矿物,其在铀成矿作用中起到了吸附和界面的作用,有利于赋矿空间的形成及定位。结合沉积作用、构造活动和后期流体成矿作用等因素,分析了成矿机制和成矿作用,赋矿层位中的粘土矿物、其它成矿条件如岩性(赋矿层和矿源层)、构造(对铀矿化的动力和对地下水径流及铀矿体)等共同控制了铀成矿作用。     

云南牟定戌街地区铀矿化特征及成因探讨

云南牟定戌街1101铀矿区位于扬子地台西南缘,康滇地轴中南段,是我国西南地区产于元古界变质岩中的铀矿之一。通过对矿化区岩石及矿石的岩石学、矿物学、地球化学及年代学特征进行研究,分析了铀矿的形成条件,揭示了铀成矿规律。研究发现:①牟定戌街地区铀矿化赋存于斜长角闪岩、角闪斜长片麻岩和二云母石英片岩等变质混合岩中,主要铀矿物为晶质铀矿、钛铀矿及次生铀矿,含铀矿物有榍石、锆石,硫化物丰富,围岩蚀变主要为硅化、赤铁矿化、碱交代等;②牟定1101铀矿化地区混合岩化岩石的地球化学特征表现为高钾钙碱性-钙碱性系列岩石;③研究区混合岩形成于1 056 Ma左右,铀矿形成于845 Ma左右,为新元古代产物;④牟定1101地区铀成矿受构造、岩性控制,与混合岩化作用、构造热液活动及碱交代作用关系密切,属热液成因铀矿。     

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.     

东秦岭丹凤地区伟晶岩型铀矿矿化特征与成矿模式

伟晶岩型铀矿是北秦岭成矿带东段重要的铀矿类型,本文介绍了该类型铀矿的矿体特征、矿石特征、副矿物特征和年代学特征.铀矿体产于淡色含榴花岗岩体内外接触带伟晶岩脉中,围绕花岗岩体产出,形态复杂,随伟晶岩脉的形态而变化,呈似脉状、透镜状和不规则状,晶质铀矿为最主要的工业矿物.通过LA-ICP-MS锆石U-Pb定年获得含铀伟晶岩年龄为404.3±1.4 Ma,略晚于淡色含榴花岗岩体年龄,矿岩时差小,显示了岩浆成矿的特征.综合分析表明早泥盆世丹凤地区进入后碰撞构造环境,秦岭岩群发生部分熔融形成富铝含榴花岗质岩浆,随着岩浆结晶分异演化的不断进行,铀元素以U4+形式与O2-结合形成晶质铀矿,在岩体内外接触带黑云母富集部位沉淀成矿.三叠纪后接受长期隆升剥蚀,侵入岩呈岩株出露地表,围绕岩株外带产出的含铀伟晶岩脉,表现为光石沟式铀矿床.随着隆升剥蚀作用的进一步加剧,侵入岩顶部相遭受剥蚀之后以岩基出露地表,在岩体的内接触带不规则形态的含铀伟晶岩出露地表,表现为陈家庄式铀矿床.依据成矿模式,预测伟晶岩型铀矿成矿远景区2片,分别为大毛沟地区和纸房沟地区.      

电子探针测年方法应用于粤北长江岩体的铀矿物年龄研究

晶质铀矿被认为是花岗岩型铀矿成矿的主要矿源提供者,在评价岩体的含矿性和确定成岩成矿年龄方面有重要意义。长江岩体属于诸广山复式岩体的一部分,是粤北地区重要的产铀花岗岩体,本文利用电子探针对该岩体中的铀矿物进行研究。结果表明:长江岩体中的铀矿物多以充填或被黄铁矿包围的形式存在,或者分布于石英、黑云母、绿泥石等矿物中;铀矿物类型主要有晶质铀矿、沥青铀矿、铀石、铀钍石四种。晶质铀矿/沥青油矿的化学年龄值可分为三组:~155 Ma、~106 Ma和~74 Ma。第一组年龄代表岩体的形成时代,后两组年龄代表铀矿的多期次成矿作用年龄。铀矿物从成岩后到~106 Ma,成分没有发生明显变化,直到~74 Ma后才发生明显的U元素活化、迁移。因此,可以推测长江岩体地区主要的铀矿成矿期应发生在~74 Ma及之后。     

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 coupling of uranium and phosphorous in soils overlying an unmined uranium deposit: Coles Hill, Virginia

The mineralogy and geochemistry of soils developed over the unmined Coles Hill uranium deposit (Virginia) were studied to determine how phosphorous influences the speciation of uranium in oxidizing soil/saprolite systems typical of the eastern US. Results from this study have implications for both uranium remediation (e.g. in situ stabilization) and uranium resource exploration (e.g. near-surface geochemical sampling). The primary uranium ore (coffinite and uraninite hosted in quartzo-feldspathic gneiss) weathers to saprolites containing the same uranium concentration as the underlying ore (approximately 1000 mg U/kg saprolites). In these water saturated (below water table) saprolites the uranium is retained as uranyl phosphates of the meta-autunite group (mainly meta-uranocircite). Above the water table the soils overlying the deposit contain approximately 200 mg uranium per kg soil (20 times higher than uranium concentrations in similar soils formed from unmineralized rocks adjacent to the deposit). In these unsaturated zone soils uranium is retained by two processes: (1) incorporation into barium–strontium–calcium aluminum phosphate minerals of the crandallite group (mainly gorceixite), and (2) sorption of uranium with phosphorous onto iron oxides that coat the surfaces of other soil minerals.Thermodynamic calculations suggest that the meta-autunite group minerals present in the saprolites below the water table are not stable in the unsaturated zone soils overlying the deposit due to the drop in soil pH from  6.0 down to  4.5. Mineralogical observations suggest that, once exposed to the unsaturated environment, the meta-autunite group minerals react to form U(VI)-bearing aluminum phosphates and U(VI) surface complexes or nano-precipitates associated with ferric oxides. These results therefore indicate that models predicting U(VI) speciation in phosphate amended soils must simultaneously account for variations in pH, ion activities (aluminum appears to be particularly important) and surface complexation with iron oxide mineral surfaces.     

Genetic model of uranium mineralization in the Permo-Triassic sedimentary rocks of the Stara Planina eastern Serbia

One deposit and four occurrences of uranium minerals in the Permo-Triassic sedimentary rocks of the Stara Planina in eastern Serbia were ascertained using data from years of multidisciplinary geological research. The minerals are the fissure-filling type, and were assigned to the exogenic mineralization group, being mostly epigene in nature. Relevant geological information was used to derive a genetic model of uranium mineralization in the Permo-Triassic sedimentary rocks of the Stara Planina. The model explains the formation of Permo-Triassic rocks and three stages of the complex process of U mineralization. The genetic model treats: (1) the primary sources of the uranium; (2) the mobility of uranium; and (3) accessory metals from the parent rocks to their deposition in host rocks and the postmineral change in ore bodies. A geochemical barrier zone was identified in the sedimentary rocks that contained uranium mineral ore. This geochemical barrier area included crescent-shaped, flat-lens, or vein-like ore bodies. The U-containing mineral described is comparable with those from the relatively common fissure-filling uranium minerals found around the world.     

电子探针化学测年在攀枝花大田晶质铀矿中的应用及其意义

晶质铀矿和沥青铀矿是热液铀矿床的主要工业铀矿物,在研究热液铀矿床成因及成矿规律方面具有重要的意义。攀枝花大田地区是我国混合岩型热液铀矿分布区,已发现粗粒特富铀矿滚石(铀含量10%)及较富基岩矿石(铀含量为0.1%~2%),主要铀矿物为晶质铀矿,对两种晶质铀矿成分及形成时代的研究对该区混合岩型热液铀矿成矿规律研究具有重要的价值。本文通过对大田地区滚石中的晶质铀矿和基岩矿石中的晶质铀矿进行矿物学及电子探针分析,研究了晶质铀矿的成分及形成时代。结果表明:(1)大田地区滚石和基岩矿石中的晶质铀矿除铅之外化学成分较为相似,两类矿石晶质铀矿中UO_2含量为77.36%~84.04%,ThO_2含量为0.98%~5.59%,PbO含量为1.79%~8.8%,其中滚石晶质铀矿中的铅含量低于基岩晶质铀矿,钍含量高于基岩晶质铀矿;(2)电子探针化学定年结果表明,基岩矿石晶质铀矿的形成时代为774.9~785.5 Ma,滚石晶质铀矿的形成时代为783.7 Ma,与传统同位素测年结果(775~777.6 Ma)非常一致,一方面说明滚石晶质铀矿和基岩晶质铀矿为同一时代的产物,另一方面说明电子探针原位测年方法是可靠的;(3)在后期的热液蚀变中,晶质铀矿先后发生了硅化、碳酸盐化及赤铁矿化,蚀变发生的时间分别为730.6Ma、699.8 Ma和664.0 Ma。此结论对研究攀枝花大田地区热液铀矿成矿时代及成矿作用过程提供了依据。     

康滇地轴巨粒晶质铀矿的发现及其地质意义

康滇地轴米易海塔地区富晶质铀矿石英脉产于晚元古代受混合岩化作用影响的五马箐组黑云斜长片岩中,受韧-脆性断裂构造裂隙带控制。晶质铀矿呈黑色,半金属光泽;晶形完好,以立方体与八面体聚形及菱形十二面体为主,少量呈立方体;粒径大多0.5cm左右,最大可达1cm以上。共生矿物组合为石英-晶质铀矿-榍石-辉钼矿组合。研究认为,晶质铀矿形成于温度压力较高及深度较大的地质环境,是高温偏酸性流体在温度缓慢下降的强还原条件下结晶而成的。康滇地轴具有形成高强度铀矿化的地质背景和成矿条件,在康滇地轴混合岩地区最有前景的铀矿类型应为受韧-脆性构造控制的中高温热液脉型矿化。     

Mineral chemical study of U-bearing minerals from the Dominion Reefs,South Africa

The Neo-Archean Dominion Reefs (~3.06 Ga) are thin meta-conglomerate layers with concentrations of U- and Th-bearing heavy minerals higher than in the overlying Witwatersrand Reefs. Ore samples from Uranium One Africa’s Rietkuil and Dominion exploration areas near Klerksdorp, South Africa, were investigated for their mineral paragenesis, texture and mineral chemical composition. The ore and heavy mineral assemblages consist of uraninite, other uraniferous minerals, Fe sulphides, Ni–Co sulfarsenides, garnet, pyrite, pyrrhotite, monazite, zircon, chromite, magnetite and minor gold. Sub-rounded uraninite grains occur associated with the primary detrital heavy mineral paragenesis. U–Ti, U–Th minerals, pitchblende (colloform uraninite) and coffinite are of secondary, re-mobilised origin as evidenced by crystal shape and texture. Most of the uranium mineralisation is represented by detrital uraninite with up to 70.2 wt.% UO₂ and up to 9.3 wt.% ThO₂. Re-crystallised phases such as secondary pitchblende (without Th), coffinite, U–Ti and U–Th phases are related to hydrothermal overprint during low-grade metamorphism and are of minor abundance.     

含矿自流盆地的放射性环境地质和地浸法开采铀矿床

层间 渗入型铀矿床不同的现代水文地质环境对采用地浸方法采矿过程中保护环境不受污染的程度不同。根据水文地质特征 ,特别是水动力指标可将铀矿床分为有利的、不利的和非常不利的 3类 :有利的铀矿床指矿区的水流从矿带两侧分别从氧化带和原生灰色岩石带以斜交形式向矿带方向流动 ,并沿矿带走向方向相互作用。这样的水文地质条件下工艺溶液不可能流到矿带范围以外 ,故环境将不受污染。完全不利的水文地质条件是指水流垂直穿透矿带从氧化带向原生灰色岩石带流动 ,它们能将有毒元素和重金属带到矿带以外的相邻地区。不利的水文地质条件是指同时具有上述两种特征的铀矿床。实践证明 ,水文地质条件有利于地浸方法开采和有关工艺流程时 ,开采工作对现场造成的污染要比天然放射性污染低。     

砂岩型铀矿中铀矿物U-Pb年代学研究现状及研究方向

该文基于中国地质调查局天津地质调查中心研究团队近年来的研究工作及对相关文献的综合研究,对砂岩型铀矿中一些重要铀矿物如沥青铀矿(晶质铀矿)、铀石、钛铀矿等的微区原位成因矿物学和U-Pb年代学研究现状进行了深入分析,提出新的研究方向,即通过采用二次离子质谱法、激光剥蚀多接收器电感耦合等离子体质谱法与电子探针化学分析法和同位素稀释热电离质谱法相结合的方式,综合研究砂岩型铀矿中沥青铀矿(晶质铀矿)、铀石、钛铀矿等铀矿物和金红石、磷灰石等含铀矿物的微区原位成因矿物学和U-Pb年代学,探索砂岩型铀矿中矿石矿物的U-Pb同位素测年新方法,获取更精确的砂岩型铀矿成岩成矿的年代学信息。这对于全面准确地认识砂岩型铀矿床的生成和演化历史,建立砂岩型铀矿床的成矿新理论具有十分重要的科学意义。铀矿物测年新方法在砂岩型铀矿床的地质勘探中也有广阔的应用前景。