Chemical and Sr isotopic characterization of North America uranium ores: Nuclear forensic applications

This study reports major, minor, and trace element data and Sr isotope ratios for 11 uranium ore (uraninite, UO_2+x) samples and one processed uranium ore concentrate (UOC) from various U.S. deposits. The uraninite investigated represent ores formed via different modes of mineralization (e.g., high- and low-temperature) and within various geological contexts, which include magmatic pegmatites, metamorphic rocks, sandstone-hosted, and roll front deposits. In situ trace element data obtained by laser ablation-ICP-MS and bulk sample Sr isotopic ratios for uraninite samples investigated here indicate distinct signatures that are highly dependent on the mode of mineralization and host rock geology. Relative to their high-temperature counterparts, low-temperature uranium ores record high U/Th ratios (>1000), low total rare earth element (REE) abundances (<1 wt%), high contents (>300 ppm) of first row transition metals (Sc, Ti, V, Cr, Mn, Co, Ni), and radiogenic ⁸⁷Sr/⁸⁶Sr ratios (>0.7200). Comparison of chondrite normalized REE patterns between uraninite and corresponding processed UOC from the same locality indicates identical patterns at different absolute concentrations. This result ultimately confirms the importance of establishing geochemical signatures of raw, uranium ore materials for attribution purposes in the forensic analysis of intercepted nuclear materials.     

鄂尔多斯盆地东胜砂岩型铀矿微量和稀土元素地球化学特征

鄂尔多斯盆地东胜砂岩型铀矿的微量和稀土元素能为铀矿勘查提供地球化学标志。以东胜铀矿层位侏罗系及其中铀矿化为对象,针对砂岩型铀矿石、铀矿化砂岩和围岩几类地质体进行元素地球化学对比研究。东胜砂岩型铀矿微量元素地球化学特征表明,Pb、Mo与U关系极为密切,它们在铀矿石中最富集,铀矿化砂岩中次富集,砂质和泥质围岩中不富集;Pb和Mo可以作为东胜铀矿床矿化的指示元素,Pb、U和Mo蛛网图上构成的"W"式样可作为东胜地区砂岩铀矿化的指示模型。铀矿石、铀矿化砂岩、砂岩以及泥岩表现出相似的REE地球化学特征和配分模式,推断其具有统一的物源、沉积环境和构造背景。部分铀矿石明显富集HREE,显然在沉积成岩后期经历了(热液)改造作用。东胜铀矿化经历了沉积成岩和热液改造作用两个成矿阶段。     

相山铀矿田成矿流体特征:来自微量、稀土元素地球化学证据

相山铀矿田的成矿流体性质和来源存在争议,为进一步探讨相山铀矿田成矿流体的性质和来源,本文对相山铀矿田西部的居隆庵铀矿床和北部的沙洲铀矿床中的新鲜围岩、蚀变围岩及矿石的微量、稀土元素含量及其变化进行了研究。结果显示:在含较多热液成因萤石的居隆庵铀矿床中,从新鲜围岩到蚀变围岩到矿石,Zr、Hf含量先降低再升高;而在含少量热液萤石的沙洲铀矿床中,新鲜围岩、蚀变围岩和矿石的Zr、Hf含量基本一致。鉴于富F流体易汲取岩石中的Zr、Hf,因此,这两个矿床中不同类型样品Zr、Hf含量的不同变化趋势,可能与居隆庵铀矿床的成矿流体富F、而沙洲铀矿床的成矿流体相对贫F有关。这两个铀矿床中矿石的稀土配分曲线与其各自的新鲜及蚀变围岩的稀土配分曲线形态相似但又存在差异,说明每个矿床的新鲜围岩、蚀变围岩和矿石之间的稀土元素既具有继承性、又受到不同性质的流体的影响。居隆庵铀矿床中矿石显示Eu负异常,可能主要是继承了围岩的Eu负异常;沙洲铀矿床中矿石Eu显示弱负异常至弱正异常的特征,可能与围岩中斜长石因热液蚀变作用而释放出的Eu的进入流体有关。基于新鲜围岩、蚀变围岩及矿石的U和REE研究,推断居隆庵铀矿床成矿流体中U和REE均以F的络合物形式迁移;但沙洲铀矿床中铀矿石品位较低,可能是与流体中相对贫F有关。     

北秦岭丹凤地区产铀花岗岩稀土元素地球化学特征

针对北秦岭丹凤地区产铀花岗岩的区域地层、赋矿围岩、蚀变岩和铀矿石进行稀土元素地球化学研究,结果表明:各类样品具有大体类似的LREE富集及Eu负异常的稀土配分模式,表明它们之间稀土元素特征具有继承性;赋矿黑云母二长花岗岩与区域地层(丹凤岩群变质基性火山岩)稀土元素特征指示,二者均形成于岛弧环境;蚀变花岗岩和铀矿石主要继承了赋矿花岗岩的特征。各类样品Y/Ho值变化范围狭窄,为25.09~33.46,显示它们具有共同的源区。铀矿石具有最高的w_B(∑HREE),且与铀矿石的品位存在正相关关系,暗示HREE与铀的迁移具有同步性。     

The oxygen isotopic composition of uranium minerals: A review

Uranium ore is an essential material in the preparation of nuclear fuel for civilian as well as military uses. Uranium is first extracted from uranium-bearing minerals using a variety of reagents, and is precipitated from solutions as yellow cake prior to isotope enrichment processes. The disintegration of the former Eastern Bloc in the 1990s and frequent unrest in the Middle East have underscored the need for better characterizing source uranium ores for forensic and attribution purposes.The world's major deposits of U occur in several distinctly different geological environments. Fourteen principal types of U deposits and rocks with elevated uranium contents are recognized with more than 40 subtypes. Combining our own analysis and literature data, we have amassed over 250 oxygen isotope data from 13 major U-producing countries, which vary widely from − 32 to + 11‰. However, interpreting the oxygen isotopic composition of uraninite in terms of the composition of the fluid from which it precipitated, or interacted with, requires knowledge of the fractionation factor and temperature of interactions, which are not always available. Since each deposit type occurs within a unique geologic setting and is generally formed from chemically distinct fluids, the chemical compositions of the uranium ores are also distinct: uranium deposits that form in igneous rocks have higher trace element compositions relative to sandstone-hosted deposits. Our data shows that one of the most useful techniques for distinguishing between uranium ore is to use a combination of δ¹⁸O values and rare-earth elements (e.g., La/Yb ratios). These methods may allow investigators to trace uranium ore back to the source.     

Geochemical signatures of uranium oxides in the Lufilian belt: From unconformity-related to syn-metamorphic uranium deposits during the Pan-African orogenic cycle

The Pan-African Lufilian belt (Zambia and Democratic Republic of Congo) is known for its world-class copper and cobalt deposits. In addition, the Lufilian Copperbelt hosts several uranium occurrences concentrated within deformed siliciclastic rocks of the basal Neoproterozoic Katanga Supergroup. We report LA-ICPMS and EMP analyses of the rare earth element (REE) and yttrium (Y) abundances (designated as the REY signatures) of uranium oxides from two uranium mineralizing events of the Lufilian belt previously dated at 652 ± 8 Ma and 530 ± 6 Ma by the U–Pb method on uraninite. Uranium oxides dated at ca. 650 Ma from the External fold-and-thrust belt are characterized by (i) bell shape REE patterns centered on middle REE (MREE), (ii) positive europium (Eu) anomalies and (iii) relatively low Y contents. In contrast, uranium oxides dated at ca. 530 Ma from the Domes region are characterized by (i) REE patterns but with a less pronounced light REE (LREE) fractionation, (ii) negative Eu anomalies and (iii) higher Y contents. Moreover, the External fold-and-thrust belt also contains uranium mineralization dated at ca. 530 Ma having the same characteristics as the ca. 530 Ma uranium oxides from the Domes region (a moderately fractionated REE pattern and a negative Eu anomaly).As REY signatures are known to reflect mineralizing processes, the distinct geochemical signatures of the two uranium oxide generations (ca. 650 Ma and ca. 530 Ma) provide meaningful information about the uranium cycle during the Pan-African orogeny. Compared to the REY signatures of the known worldwide uranium deposit types, the REY signature of uranium oxides dated at ca. 650 Ma of the External fold-and-thrust belt is similar to the REE patterns from unconformity-related U deposits (Athabasca in Canada and Kombolgie in Australia). Uranium oxides of the Domes region and some of the External fold-and-thrust belt display similar characteristics to syn-metamorphic U deposit (Mistamisk in Canada). Accordingly, we propose that the two stages of uranium oxide crystallizations within the Lufilian belt, at ca. 650 and ca. 530 Ma, occurred under distinct physico-chemical conditions. The first stage, at ca. 650 Ma, may be related to late diagenesis hydrothermal processes, at the basement/cover interface, with the circulation of highly saline basinal brines linked to evaporites of the Roan Group. This Pan-African unconformity-related uranium deposit is the youngest of this type described to date. The second stage may be connected to metamorphic fluid circulations, at about 530 Ma, during the Lufilian orogeny in the Domes region and also in the External fold-and-thrust belt.     

江西邹家山铀矿床成矿特征及物质来源

邹家山矿床是一个典型的热液脉型铀矿床,产于江西中部相山火山—侵入杂岩体的西部。受邹家山—石洞断裂带及其派生的一系列张性—张扭性裂隙群(带)控制,脉状、透镜状矿体成群成带,围岩蚀变包括早期的以钠长石化为特征的碱交代和晚期的以水云母化、萤石化为特征的酸蚀变。从早期到晚期含矿热液的酸度逐渐降低、1δ8O逐渐变小的演化特征与典型的岩浆热液矿床类似。U、Th密切共生,沥青铀矿、矿石的稀土配分模式与碎斑熔岩和花岗斑岩近一致,反映了其成矿物质与碎斑熔岩和花岗斑岩一样,都来源于深部的岩浆体系,具有相同的来源。     

Happy Jack Uraninite: A New Reference Material for High Spatial Resolution Analysis of U‐Rich Matrices

There is currently a lack of well‐characterised matrix‐matched reference materials (RMs) for forensic analysis of U‐rich materials at high spatial resolution. This study reports a detailed characterisation of uraninite (nominally UO_2+x) from the Happy Jack Mine (UT, USA). The Happy Jack uraninite can be used as a RM for the determination of rare earth element (REE) mass fractions in nuclear materials, which provide critical information for source attribution purposes. This investigation includes powder X‐ray diffraction (pXRD) data, as well as major, minor and trace element abundances determined using a variety of micro‐analytical techniques. The chemical signature of the uraninite was investigated at the macro (cm)‐scale with micro‐X‐ray fluorescence (µXRF) mapping and at high spatial resolution (tens of micrometre scale) using electron probe microanalysis (EPMA) and laser ablation‐inductively coupled plasma‐mass spectrometry (LA‐ICP‐MS) analyses. Based on EPMA results, the uraninite is characterised by homogeneous UO₂ and CaO contents of 91.57 ± 1.49% m/m (2s uncertainty) and 2.70 ± 0.38% m/m (2s), respectively. Therefore, CaO abundances were used as the internal standard when conducting LA‐ICP‐MS analyses. Overall, the major element and REE compositions are homogeneous at both the centimetre and micrometre scales, allowing this material to be used as a RM for high spatial resolution analysis of U‐rich samples.     

幔源铀成矿作用的地球化学证据——以下庄小水“交点型”铀矿床为例

文章以小水铀矿床为例,探讨了下庄矿田"交点型"铀矿成矿物质来源。研究表明:(1)小水"交点型"铀矿床矿石主要由沥青铀矿、方解石和萤石等矿物组成,方解石产于矿脉两壁,萤石和沥青铀矿沉淀于矿脉中间部位;(2)沥青铀矿年龄为71.8~75.2 Ma,与围岩基性脉岩(120~100Ma)之间存在较大的矿岩时差;(3)萤石中流体包裹体的δD为-124.44‰~-97.08‰,δ18OSMON为7.40‰~11.02‰,具有幔源同位素组成特征;(4)在微量元素地球化学特征上,矿石与辉绿岩表现出相似性,与下庄花岗岩则具有明显的差异。笔者认为,下庄矿田小水"交点型"铀矿床成矿流体中的矿化剂来自地幔,铀源可能直接来自与辉绿岩具有相似源区性质的富集地幔;推测铀的沉淀成矿与富含CO2、F、H2S、U等组分的超临界态成矿流体在临界点附近发生沸腾作用相关。     

相山铀矿田邹家山矿床碱交代型矿石地球化学特征及其成矿意义

邹家山铀矿床碱交代蚀变广泛发育,与铀成矿作用关系极为密切。笔者通过野外宏观地质调查和室内岩相学、电子探针分析、常量及微量元素化学分析等方法,初步查明该矿床碱交代型矿石的矿物交代蚀变顺序为钠交代、钾交代、硅质交代。碱性成矿热液先是富Na,而后富K,且两者成分相似,但富K热液更利于铀成矿。与正常碎斑熔岩相比,碱交代型矿石SiO2含量减少,K2O或Na2O、Al2O3、Fe2O3、MgO、P2O5、CaO和U、Th、Zr、Hf、Sm、Ti及REE含量明显增高。与钾交代型矿石相比,钠交代型矿石Rb和REE含量较少,稀土分异强。碱交代作用有利于副矿物蚀变并释放铀,有利于对地层中铀的萃取,有利于铀的稳定迁移。     

Alteration geochemistry of the Nopal I uranium deposit (Sierra Peña Blanca,Mexico), a natural analogue for a radioactive waste repository in volcanic tuffs

Natural analogues provide an approach to characterize and test the long‐term modelling of a repository performance. This article presents geochemical information about the alteration conditions of the Nopal I uranium deposit, Mexico, an analogue for the proposed Yucca Mountain radioactive waste repository. Mineralization and hydrothermal alteration of volcanic tuffs are contemporaneous, according to petrographic observations. Trace element geochemistry (U, Th, REE) provides evidence for local mobilization of uranium under oxidizing conditions and further precipitation under reducing conditions. O‐ and H‐isotope geochemistry of kaolinite, smectite, opal and calcite suggests that argillic alteration proceeded at shallow depth with meteoric water at 25–75 °C, a low‐temperature context, unusual for volcanic‐hosted uranium deposits. This temperature range is compatible with some post‐closure evolution models of the proposed Yucca Mountain repository.     

REE地球化学在砂岩型铀成矿研究中的应用--以川北砂岩型铀矿床为例

本文在系统的取样分析基础上,总结了川北砂岩型铀矿床的稀土元素地球化学特征,分析研究了围岩、矿石、方解石脉和铀矿物的稀土元素组成、关系,讨论了岩、矿石沉积和成岩过程的稀土元素变化规律,与国内外典型的火山岩型和变质岩型热液成因铀矿床进行了对比,认为川北砂岩型铀矿具有热液（水）改造成矿作用的稀土元素地球化学特征,铀矿化经历了沉积成岩和热液改造富集两个阶段,为砂岩型铀矿成矿研究提供了新的思路。     

桂北沙子江铀矿床稀土元素地球化学特征

针对沙子江矿床的区域地层、赋矿围岩、成矿各阶段方解石及铀矿石进行稀土元素地球化学研究发现:各类样品具大体类似的LREE富集及Eu负异常的稀土配分模式,表明它们之间稀土元素特征具有继承性,赋矿花岗岩与区域地层稀土元素特征指示两者具有共同的陆壳沉积物源区;方解石及矿石中稀土元素主要继承了赋矿花岗岩的特征。成矿各阶段方解石Y/Ho值范围狭窄,在28.86~38.22之间,显示它们具共同的源区,且从成矿早阶段经主成矿阶段到成矿晚阶段,Eu负异常趋于强烈,δEu均值由0.34→0.26→0.25,表明成矿流体向相对还原环境演化。铀矿石具最高的稀土元素总量(ΣREE=259.88×10-6~869.31×10-6),且与铀矿石的品位存在正相关关系,暗示稀土元素与铀的迁移具同步性。铀矿石(以原生铀矿物为主)中Ce负异常的形成可能与铀源岩中分散的U(Ⅳ)被活化为在成矿流体中易迁移的U(Ⅵ)的氧化过程相伴;而铀黑的Ce正异常则是由表生作用过程所导致。     

大新铀矿床稀土元素地球化学特征及成矿机理

通过对大新铀矿床各构造地球化学带的稀土元素特征参数、球粒陨石标准化配分曲线以及分层聚类谱系的分析,笔者对该矿床铀源和成矿机理进行了探讨。研究表明,大新矿床的铀主要来自于寒武纪地层,泥盆纪地层虽然有一定的预富集作用,但以作为有利的储矿空间为主。成矿过程为地下水在燕山早期和晚期构造运动产生的构造热和岩体加热下形成地下热水,并在构造驱动下沿着沟通寒武系和泥盆系的F2主断层向上运移,萃取寒武系中的活性铀,在F2正断层的次级断层F13、F23、F33等控制的富含有机质、黄铁矿的还原环境中沉淀富集,形成铀矿床。     

REE and Trace Element Geochemistry of Yinachang Fe-Cu-REE Deposit, Yunnan Province, China

1IntroductionThebehaviorsoftherare earthelements (REE)duringmagmatism ,metamorphismandmeta somationareofgreatgeologicalinterestbecauseoftheirapplicationsingeochronologyandgeochemi caltracing (e .g .reviewsbyFaure ,1 986;LipinandMckay ,1 989) .Becauseoftheirsimilargeo chemicalbehaviorsandlowsolubilitiesinwater,theREEshaveprovedthemselvestobeapowerfultoolforthecharacterizationofprovenanceswhenappliedtosedimentaryrocks (McDanieletal.,1 994) .Althoughtheirbehaviorsunderhydrothermalconditionsar…     

REE geochemical characteristics of the No. 302 uranium deposit in northern Guangdong, South China

The No. 302 uranium deposit, located in Guangdong Province, is a typical granite-type uranium ore deposit REE geochemical characteristics of the wall rocks, pitchblende, altered rocks, calcite and fluorite from this deposit have been systematically studied in this paper. The result showed that the alkali-metasomatic granites and other altered rocks have the same REE distribution patterns as Indosinian granites. It is indicated that the hydrothermal ore-forming solution had altered the Indosinian granites, and ore-forming materials may directly originate from the Indosinian granites. Calcite and fluorite of different stages are the products derived from the same source but different stages. The evolution and degassing of the mineralizing solution might induce LREE enrichment to varying degree. Mantle fluid and a large volume of mineralizer may be the crucial factors controlling uranium mineralization, and the hydrothermal solution with mineralizer played an important role in U transport and concentration. Meanwhile, the degassing of CO2 might promote U and REE precipitation.     

Bayan Obo Controversy: Carbonatites versus Iron Oxide‐Cu‐Au‐(REE‐U)

The Bayan Obo Fe‐REE‐Nb deposit is the world’s largest rare earth element (REE) resource and its genesis has been the subject of much debate for many years. The most popular are the carbonatite‐related and hydrothermal Fe oxide‐Cu‐Au‐(REE‐U) genetic models. Comparisons of geologic setting, lithology, mineral assemblages, metal associations, geochemistry (particularly REE and light REE/heavy REE ratios), fluid chemistry and isotopics indicate that the Bayan Obo deposit shares features of both types, which are classified differently; that is, the carbonatites model is host‐rock based, while the Fe oxide‐Cu‐Au‐(REE‐U) model is essentially mineral assemblage and metal association based. A speculative classification scheme is tentatively put forward to link the two models, but many questions remain for further studies.     

铀成矿作用、核废物地球化学处置与吸附作用的关系

在不同类型的工业铀矿床的矿石中,吸附状态的铀占了很大的比重,铁钛氢氧化物、硅胶、粘土、有机质等是常见的主要吸附剂。本文利用朗缪尔等温式、弗仑德里奇等温式、D-R等温式,讨论了粘土矿物(主要是高岭土、蒙脱石)对溶液中铀的吸附作用,对吸附作用在铀成矿作用、核废物处置中的意义作了详细的讨论,认为吸附作用是一种重要的成矿作用。     

豫西嵩县上庄坪铅锌银矿床地球化学特征及地质意义

上庄坪铅锌银矿床是新一轮国土资源大调查中在北秦岭二郎坪群发现的硫化物矿床。笔者通过对矿床矿石、容矿同岩、重晶石岩的微量、稀土元素地球化学特征分析和地质特征研究,探讨成矿构造环境、成矿物质来源及矿床成因问题。研究表明.矿石和容矿围岩稀土元素球粒陨石标准化组成模式均为右倾型.矿石与围岩在Cu-Pb-Zn判别图解中投点区域一致.矿石Zn/(Zn Pb)与冲绳海槽和上向黑矿矿石特征相似、与TAG和EPR13°N区硫化物存在差异.矿石具较高As、Sb和Pb与低Cu、Cd和Se元素特征.认为该矿床成矿元素来源于壳幔混合、但以壳源为主的围岩变(石英)角斑岩和变细碧岩。矿石稀土元素、微量元素地球化学特征、矿床地质特征及与热水沉积重晶石岩和硅质岩的紧密共生关系说明,上庄坪矿床是弧后盆地构造环境海底热液喷流成岩成矿作用的产物。重晶石岩、硅质岩、矿床纵向和横向分带是寻找和勘探该类矿床的重要标志和依据。     

In Situ Quantitative Measurement of Rare Earth Elements in Uranium Oxides by Laser Ablation‐Inductively Coupled Plasma‐Mass Spectrometry

Advances in the quantification of rare earth elements (REE) at the micrometric scale in uranium oxides by laser ablation‐inductively coupled plasma‐mass spectrometry are described. The determination of the best analytical conditions was tested using a uranium oxide (Mistamisk) the concentrations of REE in which were previously estimated by other techniques. Comparison between the use of U or Pb as an internal standard clearly showed a diameter‐dependent fractionation effect related to Pb at small crater diameters (16 and 24 μm), which was not found for U. The quantification of REE contents in uranium oxide samples using both matrix‐matched (uranium oxide) and non‐matrix‐matched (NIST SRM 610 certified glass) external calibrators displayed no significant difference, demonstrating a limited matrix effect for REE determination by LA‐ICP‐MS. Moreover, no major interferences on REEs were detected. The proposed methodology (NIST SRM 610 as external calibrator and U as internal standard) was applied to samples from uranium deposits from around the world. The results showed that LA‐ICP‐MS is a suitable analytical technique to determine REE down to the μg g^?1 level in uranium oxides at the micrometre scale and that this technique can provide significant insights into uranium metallogeny.