Kaolinite as an in situ dosimeter for past radionuclide migration at the Earth's surface

The origin of 3 types of point defects (A-, A′- and B-centers) in kaolinite, due to natural irradiation and detected by electron paramagnetic resonance spectroscopy (EPR), has been demonstrated by artificial irradiation. The potential use of tracing the dynamics of the transfer of radionuclides through A-centers (i.e. the most stable centers) was qualitatively tested on different low-temperature alteration systems, some associated with U-concentrations. This paper proposes a quantitative approach to the reconstruction of the past migration of radionuclides by dosimetry of A-centers. With this aim in mind, the efficiency of α- and γ-radiations to produce A-centers was determined by experimental irradiation. Parameters extracted from A-center growth curves, together with their relationship with a parameter describing the degree of order of kaolinite, permitted (i) a definition to be made of the dose range in which a given kaolinite could be used as a dosimeter and (ii) the quantitative derivation of U-concentration from the cumulative dose (paleodose) of kaolinites. This was achieved by a formalism that accounted for the contribution of natural radiosources to the production of A-centers. The formalism was applied to the Nopal I U-deposit (Chihuhua, Mexico), considered as a natural analogue of a high level nuclear waste repository. Irrespective of the scenario considered, in terms of kaolinite age and of degree of isotopic disequilibrium in the system, A-center dosimetry permitted the determination of past occurrences of U which were several orders of magnitude higher than the present-day measured U-concentrations. Furthermore, this approach also provided evidence for several previous episodes of U-migration. EPR spectroscopy is thus a unique tool for the quantitative, indirect assessment of past radionuclide migration in the geosphere and kaolinite is a reliable in-situ dosimeter.     

Near-field high temperature transport: evidence from the genesis of the Osamu Utsumi uranium mine, Poços de Caldas alkaline complex, Brazil

The chemical, isotopic and mineralogical alteration which occurred during primary uranium ore deposition at the breccia pipe-hosted Osamu Utsumi mine, Poços de Caldas, Brazil was studied as a natural analogue for near field radionuclide migration. Chemical and isotopic alteration models were combined with finite difference models of the convective cooling of caldera intrusives. The modeling indicates that the intense chemical, isotopic, and mineralogical alteration of the Osamu Utsumi breccia pipe requires the circulation of > 10⁵ kg/cm² of boiling hydrothermal fluid > 200°C through each square centimeter cross-section of the pipe. This circulation could be driven by heat from a 6 km diameter intrusive extending to 10 km depth. Even with this large amount of circulation concentrated in the permeable breccia pipe, uranium solubilities must be orders of magnitude greater than indicated in the most recent experiments (and more in line with previous estimates) to produce the primary uranium mineralization at the Osamu Utsumi mine.The same models applied to a hypothetical high temperature waste repository show that heat from radioactive decay will produce a hydrothermal circulation system remarkably similar to that studied at the natural analogue site at Poços de Caldas. The depth of fluid convection induced by the hypothetical repository would be 5 to 10 km, the maximum temperature would be 300°C, the lifetime of the high temperature phase would be a few thousand years, and boiling would occur and cause most of the alteration within the hypothetical waste repository. This physical analysis emphasizes the importance of permeability on a 10 × 10 × 10 km scale in controlling the potential amount of circulation through the hypothetical repository.Application of the chemical models successfully used to interpret mineralization and alteration at the Poços de Caldas Osamu Utsumi mine to the hypothetical waste repository shows that even in a worst case scenario (waste implaced in a permeable host rock with no measures taken to inhibit flow though the repository) the amount of hydrothermal alteration in the hypothetical repository will be 0.1% of that in the breccia pipe at Osamu Utsumi. Assuming no barriers to uranium mobility, uranium precipitation above the hypothetical repository would be 0.04 ppm (rather than 40 ppm), hydrothermal alteration 0.03 wt% (rather than 30 wt%), etc.Our analysis indicates that modeled mineralogical alteration is sensitive to the thermodynamic data base used. Prediction of mineralogical alteration (which may be necessary to predict the migration of radionuclides other than uranium, for example) probably cannot be based directly on even very carefully collected laboratory thermodynamic data. Mineralogical complexities of the system, as well as data base uncertainties will require calibration of the thermodynamic framework against mineralogical alteration observed in the laboratory or field.     

Radiation-induced paramagnetic defects in natural kaolinites: Alpha dosimetry with ion beam irradiation

Three types of paramagnetic radiation-induced defects (RID), namely A, A′ (Si-O^?-centers) and B (Al-O^?-Al center), had been identified in natural kaolinites by means of electron paramagnetic resonance spectroscopy. The A-center, stable at the scale of geological periods, was thought to be of particular relevance to quantify past transits of radionuclides in the geosphere. Alpha radiation being likely the main source of RID in kaolinite, the objective of this paper is to define the role of α-particles on the creation of RID and to test the use of A-centers for an α-dosimetry. Three kaolinites with different crystalline order and containing other clays as impurities were irradiated with He⁺ ion beams. The radiation dose range (0–750 MGy) was consistent with natural radioactivity in environments from the Earth's surface. Irradiation drastically enhanced the original signals due to RID. An important increase of concentration of the unstable B-center, partly due to unrealistic dose rate provided by accelerator ion beam, was observed from the lower doses. The most stable defects remained of the Atype all along experimental irradiations. The contribution of ancillary phyllosilicates to EPR spectra was negligible. The concentration of the three types of RID was related to radiation doses up to 30 MGy. Dosimetry growth curves for the A-centers exhibited variable efficiencies and saturation levels that were related to the structural order and the chemical purity of the kaolinites: the more ordered and purer the kaolinite, the higher the efficiency and the lower the saturation plateau. Moreover, these results are of geochemical significance: dosimetry based on A-centers could be directly used to quantify past migrations of radioelements in the geosphere, by determination of the naturally-cumulated doses (paleodose) of kaolinites.     

豆乍山地区产铀与非产铀岩体黑云母成分及赋存副矿物特征

豆乍山岩体和香草坪岩体成岩时代相近,空间关系密切,为苗儿山中段豆乍山地区产铀与非产铀岩体。文章选择豆乍山和香草坪新鲜花岗岩中黑云母为研究对象,结合诸广、贵东地区产铀与非产铀岩体中黑云母的电子探针数据开展综合分析,并在此基础上进行了黑云母中包裹副矿物种类的对比研究。结果表明:产铀岩体黑云母基本以铁叶云母为主,非产铀岩体黑云母为铁质黑云母,且前者具有相对富铝、铁、锰,贫镁、钛特征;产铀豆乍山岩体黑云母中副矿物为锆石-磷钇矿-独居石-钛铁矿-金红石-方钍石-晶质铀矿,非产铀香草坪岩体黑云母中副矿物为锆石-磷灰石-褐帘石-独居石,缺少钍石和晶质铀矿。不同亚种黑云母具有不同的成岩成矿环境,与各矿化类型往往具有直接对应关系,铁叶云母的出现有可能可以作为产铀与非产铀岩体(铀成矿潜力)的间接判别标志,对于后期找矿具有较大指导意义。     

Deterioration mechanisms of tuffs in Midas monument

Slightly weathered white and pink tuffs of the Midas monument have deterioration problems. In this study, depths and characteristics of the weathering zones developed within the tuffs are investigated through optical microscopy, X-ray diffractometry (XRD), chemical analyses, scanning electron microscopy (SEM) and some index parameters. Accelerated weathering tests including wetting–drying, freezing–thawing and salt crystallization are performed, and durability assessment methods are used to predict the durabilities of the tuffs. The findings are compared with field observations. By examining quantitative weathering indices and comparing them with thin section studies, it is found that thin section analyses of the crystals, LoI, and WPI are good indicators to quantify the depth of weathering for the tuffs. However, thin section studies have limited value for fine-grained tuffaceous matrix. The chemical weathering of the tuffs produces weathered zones that are 4.5-cm thick within the white tuff and 2.5-cm thick within the pink tuff. Physical weathering causes scaling of outer layers of the tuffs and fracturing of feldspars along their cleavage planes. However, variations of the index properties of the tuffs due to weathering are not so significant to quantify the weathering depths in the tuffs. Among the accelerated weathering tests, salt crystallization is found to be the most destructive environmental condition. Pigeon droppings rich in NO₃¹⁻ are found to be the main source of soluble salt at the Midas monument. The salt transported up by capillary rise due to surface water causes spalling of the tuffs in the capillary zone. Surface water and salt of any kind in the close vicinity of the monument should be totally eliminated for the purpose of conservation. Field observations and the durability equations reveal that the white tuff is less durable than the pink tuff. Wet-to-dry strength ratio yields a better stone durability assessment among various durability methods used in this study.     

324铀矿床近地表矿体中长寿命铀系核素和类比微量元素迁移特征

对一近地表铀矿体中某些铀系长寿命核素的放射性平衡状态和１４种微量元素迁移特征研究得出，自该铀矿床６３Ｍａ前生成至今，仅近１Ｍａ来，当上覆花岗岩遭剥蚀使矿体近地表时，矿石中天然放射性核和微量元素才因水－岩反应沿围岩破碎带，裂隙发生迁移；裂隙两侧岩石受水－岩反应影响的范围较小，裂隙面的化学组分以溶失为主，裂隙两侧粘土化花岗岩中则以核素、元素的扩散和吸附为主，最后阐述了本研究结果对高放废物处置库安全评价     

Formation and evolution of lateritic profiles in the middle Amazon basin: Insights from radiation-induced defects in kaolinite

The content of radiation-induced defects (RIDs) in kaolinite samples originating from lateritic soils and continental detritic sediments of the middle Amazon Basin (Brazil) is investigated using electron paramagnetic resonance. The paleodose registered by kaolinites ranges from 80 to 900 kGy. Present-day dose rates of radiation, determined from the whole-rock U and Th content, range between 4000 and 40,000 mGy/ka. In most samples, U and Th concentrations are correlated, suggesting that U has not been remobilized by lateritization. This observation is consistent with the fact that ∼80% of the total U content is incorporated in resistant minerals, such as zircon and Ti oxides. The heterogeneous distribution of U, observed by induced fission tracks mapping, makes it possible to neglect the α-radiation contribution of the U decay chains in the dose-rate calculation. The interpretation of the measured content of RIDs in kaolinite is then performed using the calculated present-day dose rate and assuming equilibrium in the radioactive decay chains. For the sedimentary samples, the amount of RIDs is broadly correlated to the dose rate and provides apparent absolute ages older than 20 Ma. The RID contents in kaolinites from the lateritic soils provide apparent ages ranging from 10 to 6 Ma. The high RID content of these lateritic kaolinites shows that their chemical, isotopic, and crystallographic properties are not representative of present-day weathering conditions. Models assuming the “dynamical equilibrium” of kaolinites with local physical-chemical conditions prevailing in lateritic soils are thus questionable. Alternatively, our findings bring strong support for the use of the isotopic composition of kaolinites to decipher continental paleo-climates.     

Tectonodynamics of fluid-conducting structural elements and migration of radionuclides in massifs of crystalline rocks

The principal aspects of reconstruction of conditions and paths of fluid migration in massifs of crystalline rocks are considered. The spatiotemporal relationships between stress fields, brittle failure, and migration of radionuclides are discussed. The main attention is focused on the staged character of tectonic events, fluid circulation conditions, and the sequence of uranium mineral formation as determined with structural, geological, tectonophysical, petrophysical, petrographic, mineralogical and geochemical, microstructural, microthermometric, and radiographic methods. As is exemplified in uranium deposits and massifs of silicic igneous rocks, the comprehensive consideration of the tectonodynamics of fluid-conducting structural elements and radionuclide migration is necessary for providing insights into the localization and redistribution of uranium, the PT conditions of uranium ore formation, and the forecast for long-term safety of disposal of radioactive wastes in crystalline rocks.     

相山铀矿田巴泉隐爆角砾岩(筒)地质特征与铀成矿

巴泉铀矿床位于相山矿田的北部边缘,是典型的隐爆角砾岩(筒)型铀矿床。隐爆角砾岩(筒)是由与相山火山机构有密切联系的燕山晚期侵入于震旦系变质岩中的潜花岗斑岩岩枝发生隐爆作用而生成。矿床是多阶段岩浆活动、多次隐爆作用和多期铀成矿作用互为响应、连续发展地质过程的产物,是集岩浆岩体-角砾岩体-铀矿体为一体的综合地质单元。燕山晚期潜花岗斑岩浆和英安玢岩浆的侵入、隐爆作用形成的角砾岩(筒),以及断裂构造的频繁运动,对铀成矿乃至矿床的形态和规模起到重要的控制作用。隐爆角砾岩(筒)的形成具有脉动性、隐爆性,显示隐爆角砾岩岩性的复杂多变,矿化蚀变种类、组合和强弱变化具有规律性。铀矿体(化)主要赋存于隐爆角砾岩和震碎角砾岩中,矿化显现出中富边贫、上强下弱的特征。     

670铀矿床地质特征及其成因

本文提供了一个与火山侵入-隐爆角砾岩有直接成因联系的铀矿床实例。并从岩石学、岩石化学、同位素等方面介绍了成矿角砾岩的成岩特点及物质来源,阐述了与其有关的铀矿床的主要地质特征和矿床成因。     

Geochemical soil sampling for deeply-buried mineralized breccia pipes,northwestern Arizona

Thousands of solution-collapse breccia pipes crop out in the canyons and on the plateaus of northwestern Arizona; some host high-grade uranium deposits. The mineralized pipes are enriched in Ag, As, Ba, Co, Cu, Mo, Ni, Pb, Sb, Se, V and Zn. These breccia pipes formed as sedimentary strata collapsed into solution caverns within the underlying Mississippian Redwall Limestone. A typical pipe is approximately 100 m (300 ft) in diameter and extends upward from the Redwall Limestone as much as 1000 m (3000 ft).Unmineralized gypsum and limestone collapses rooted in the Lower Permian Kaibab Limestone or Toroweap Formation also occur throughout this area. Hence, development of geochemical tools that can distinguish these unmineralized collapse structures, as well as unmineralized breccia pipes, from mineralized breccia pipes could significantly reduce drilling costs for these orebodies commonly buried 300–360 m (1000–1200 ft) below the plateau surface.Design and interpretation of soil sampling surveys over breccia pipes are plagued with several complications. (1) The plateau-capping Kaibab Limestone and Moenkopi Formation are made up of diverse lithologies. Thus, because different breccia pipes are capped by different lithologies, each pipe needs to be treated as a separate geochemical survey with its own background samples. (2) Ascertaining true background is difficult because of uncertainties in locations of poorly-exposed collapse cones and ring fracture zones that surround the pipes.Soil geochemical surveys were completed on 50 collapse structures, three of which are known mineralized breccia pipes. Each collapse structure was treated as an independent geochemical survey. Geochemical data from each collapse feature were plotted on single-element geochemical maps and processed by multivariate factor analysis. To contrast the results between geochemical surveys (collapse structures), a means of quantifying the anomalousness of elements at each site was developed. This degree of anomalousness, named the “correlation value”, was used to rank collapse features by their potential to overlie a deeply-buried mineralized breccia pipe.Soil geochemical results from the three mineralized breccia pipes (the only three of the 50 that had previously been drilled) show that: (1) Soils above the SBF pipe contain significant enrichment of Ag, Al, As, Ba, Ga, K, La, Mo, Nd, Ni, Pb, Sc, Th, U and Zn, and depletion in Ca, Mg and Sr, in contrast to soils outside the topographic and structural rim; (2) Soils over the inner treeless zone of the Canyon pipe show Mo and Pb enrichment anf As and Ga depletion, in contrast to soils from the surrounding forest; and (3) The soil survey of the Mohawk Canyon pipe was a failure because of the rocky terrane and lack of a B soil horizon, or because the pipe plunges. At least 11 of the 47 other collapse structures studied contain anomalous soil enrichments similar to the SBF uranium ore-bearing pipe, and thus have good potential as exploration targets for uranium. One of these 11, #1102, does contain surface mineralized rock. These surveys suggest that soil geochemical sampling is a useful tool for the recognition of many collapse structures with underlying ore-bearing breccia pipes.     

Process of slip-surface development and formation of slip-surface clay in landslides in Tertiary volcanic rocks, Japan

Once landslide movement has been initiated, the sliding mass tends to move toward a more stable position. However, landslides that have occurred in some Tertiary volcanic rocks in Japan show recurrent movement. A possible reason for this behavior is that the mineral composition and properties of slip-surface materials results in better ‘lubrication’ along the slip surface as movement continues. In order to determine the causes, five landslides in Japanese Tertiary volcanics with different movement histories were studied. Based on geological investigation, the results presented in this paper were obtained by studying the development process and formation of slip surfaces and clays in landslides in these volcanics.

For rocks of similar types and mineralogies the clay content of slip-surface materials can be directly related to the displacement and history of slide movement. This study indicates that the type of slip surface ranges from: (1) striation type (showing only striations on bedrock without clay), to (2) brecciated type (clayey breccia), (3) mylonite type (clay with breccia), and to (4) clay type (clay without breccia). If the slip surface occurs in tuff or tuffaceous materials and is subjected to increasing slide movement, the smectite content in the slip-surface clay increases, while the silicate mineral content decreases. Furthermore, the smectite content is observed to increase within the same landslide from the head to the toe portion of the landslide (direction of groundwater flow). The groundwater along the slip surface (above the impervious zone) contains an increased concentration of Ca⁺⁺ ions. As the concentration of HCO₃⁻ ions exceeds 40 mg/l, an environment is created that promotes the formation of smectite. This process indicates that there is an active ion exchange within the groundwater near the slip surface that forms smectite. Thus, the formation of smectite in the slip surface requires the presence of tuff and a sufficient concentration of HCO₃⁻ ions in the groundwater.

The study results presented here indicate that frictional resistance decreases as clay content increases. The reason for repeated movement of Japanese landslides in Tertiary tuffs or tuffaceous rocks at or in the immediate vicinity of the slip surface is attributed to: (1) an increase in clay materials along the slip surface as the slide movement is repeated and (2) the presence of groundwater that promotes the formation of smectite. As is commonly known, smectite is one of the clay minerals that has lowest frictional resistance.     

与斑岩型铜矿有关的角砾岩(筒)

斑岩型铜矿床是重要的铜矿类型，在已探明的铜储量中斑岩型铜矿居首位。研究认为，在板块构造的敛合带上，斑岩铜矿发育地区，常见有角砾状地质体和角砾岩筒。这些角砾状地质体和角砾岩筒对矿化与謇集起着重要作用，是斑岩铜矿的重要找矿标志，有时其本身就是铜矿体。本文中从理论与野外工作相结合的角度，总结了与斑岩型铜矿床有关的角砾状地质体和角砾岩筒的类型及地质特征，通过具体实例介绍了与斑岩铜矿有关的角砾岩筒的找矿思路与方法，适宜野外工作的实际应用。     

十红滩砂岩型铀矿床成矿控制因素与成矿模式研究

通过对十红滩铀矿床地质特征的研究,认为该铀矿床为一典型的层间氧化带砂岩型铀矿,其形成主要受铀源、构造、目的层沉积体系、层间氧化带发育程度、地下水动力变异等因素控制。在总结这些控制因素的基础上,初步建立了十红滩铀矿床的成矿模式。     

Argillization processes at the El Berrocal analogue granitic system (Spain): mineralogy,isotopic study and implications for the performance assessment of radwaste geological disposal

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of the uranium–quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of formation and thus complete the geothermal history of the system. For this purpose, δ¹⁸O values were determined for pure mineral from the unaltered granite and quartz from the uranium–quartz vein, as well as for mixture samples from the hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the uranium–quartz vein. The isotopic signature of quartz from the uranium–quartz vein and the monophasic nature of its fluid inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range from −8.3‰ to −5.7‰ V-SMOV, its temperature of formation being around 85–120 °C. The δ¹⁸O values of pure sericite from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 °C to approximately 120 °C. Clays from fracture fillings and clayey walls of the uranium–quartz vein are usually mixtures, in different proportions, of illite, approximately formed between 70 and 125 °C; two generations of kaolinite formed at approximately 90–130 °C and at around 25 °C, respectively; smectite, formed at ≤25 °C; and occasionally palygorskite, formed either between 30 and 45 °C or 19 and 32 °C, depending on the fractionation equation used. These data suggest that sericite from the hydrothermally altered granite, quartz from the uranium–quartz vein, illite and the first generation of kaolinite from the fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under certain physicochemical conditions (T≈100 °C, pH≈8 and log [H₄SiO₄] between −4 and −3), illite and kaolinite can be paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to the sulphide-rich uranium–quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed from alkaline Si–Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes, drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).     

松辽盆地钱家店地区姚家组砂岩黏土矿物特征及其与铀矿化的关系

[研究目的]钱家店铀矿床位于松辽盆地西南部,含铀岩系为上白垩统姚家组.目的层中含有大量的黏土矿物,因此揭示姚家组砂岩黏土矿物特征,对铀的成矿作用探讨至关重要.[研究方法]本文通过系统的显微镜下鉴定、扫描电镜、X射线衍射等分析测试手段,对钱家店地区姚家组砂岩黏土矿物的镜下特征、成分及含量进行了系统的观察和研究.[研究结果...     

放射性核素在地下介质中迁移机理与模型研究

介绍了铀尾矿库的物理、化学概念模型和其中重金属、放射性核素迁移的一般过程 ;论述了沉淀作用、络合作用和胶体作用对放射性核素迁移的影响 ;重点讨论了描述吸附作用的离子交换模型和表面络合模型的建模机理 ;对定量模拟放射性核素迁移行为的 Kd模型、表面络合模型及“反应 -运移模型”的应用进行了评述。     

Quantification of weathering depths in slightly weathered tuffs

Slightly weathered white and pink tuffs of Midas monument have deterioration problems. In this study, depths of the weathering zones developed in the tuffs are investigated through optical microscopy, XRD, chemical analyses, SEM and some index parameters. By examining quantitative weathering indices and comparing them with thin section studies, it is found that thin section analyses of the phenocrysts, LoI and WPI are good indicators to quantify the depth of weathering for the tuffs. However, thin section studies have limited value for fine-grained tuffaceous matrix. The chemical weathering of the tuffs produces weathered zones that are 4.5 cm thick within the white tuff and 2.5 cm thick within the pink tuff. Physical weathering causes fracturing of feldspars along their cleavage planes. Variations of the index properties of the tuffs caused by weathering are not significant enough to quantify the weathering depths in the tuffs.