The Coles Hill Uranium Deposit, Virginia, USA: Geology, Geochemistry, Geochronology, and Genetic Model

The Coles Hill uranium deposit, with an indicated resource of about 130 Mlb of U3O8, is the largest unmined uranium deposit in the United States. The deposit is hosted in the Taconian (approx. 480–450 Ma) Martinsville igneous complex, which consists of the Ordovician Leatherwood Granite (granodiorite) and the Silurian Rich Acres Formation (diorite). The host rock was metamorphosed to orthogneiss during the Alleghanian orogeny (approx. 325–260 Ma), when it also underwent dextral strike-slip movement along the Brookneal shear zone. During the Triassic, extensional tectonics led to the development of the Dan River Basin that lies east of Coles Hill. The mineralized zone is hosted in brittle structures in the footwall of the Triassic Chatham fault that forms the western edge of the basin. Within brittle fracture zones, uranium silicate and uranium-bearing fluorapatite with traces of brannerite form veins and breccia-fill with chlorite, quartz, titanium oxide, pyrite, and calcite. Uranium silicates also coat and replace primary titanite, zircon, ilmenite, and sulfides. Sodium metasomatism preceded and accompanied uranium mineralization, pervasively altering host rock and forming albite from primary feldspar, depositing limpid albite rims on igneous feldspar, altering titanite to titanium oxide and calcite, and forming riebeckite. Various geothermometers indicate temperatures of less than ~200°C during mineralization. In situ U-Pb analyses of titanite, Ti-oxide, and apatite, along with Rb/Sr and U/Pb isotope systematics of whole-rock samples, resolve the timing of geologic processes affecting Coles Hill. The host Leatherwood Granite containing primary euhedral titanite is dated at 450 to 445 Ma, in agreement with previously obtained ages from zircon in the Martinsville igneous complex. A regional metamorphic event at 330 to 310 Ma formed anhedral titanite and some apatite, reequilibrated whole-rock Rb/Sr and U-Pb isotopes, and is interpreted to have coincided with movement along the Brookneal shear zone. During shearing and metamorphism, primary refractory uranium-bearing minerals including titanite, zircon, and uranothorite were recrystallized, and uranium was liberated and mixed locally with hematite, clay, and other fine-grained minerals. Uranium mineralization was accompanied by a metasomatic episode between 250 and 200 Ma that reset the Rb-Sr and U-Pb isotope systems and formed titanium oxide and apatite that are associated and, in places, intimately intergrown with uranium silicate dating mineralization. This event coincides with rifting that formed the Dan River Basin and was a precursor to the breakup of Pangea. The orientation of late-stage tectonic stylolites is compatible with their formation during Late Triassic to Early Jurassic basin inversion, postdating the main stage of uranium mineralization and effectively dating mineralization as Mesozoic. Based on the close spatial and temporal association of uranium with apatite, we propose that uranium was carried as a uranyl-phosphate complex. Uranium was locally reduced by coupled redox reactions with ferrous iron and sulfide minerals in the host rock, forming uranium silicates. The release of calcium during sodium metasomatic alteration of primary calcic feldspar and titanite in the host rock initiated successive reactions in which uranium and phosphate in mineralizing fluids combined with calcium to form U-enriched fluorapatite. Based on the deposit mineralogy, oxygen isotope geochemistry, and trace element characteristics of uranium silicate and gangue minerals, the primary mineralizing fluids likely included connate and/or meteoric water sourced from the adjacent Dan River Basin. High heat flow related to Mesozoic rifting may have driven these (P-Na-F-rich) fluids through local aquifers and into basin margin faults, transporting uranium from the basin or mobilizing uranium from previously formed U minerals in the Brookneal shear zone, or from U-enriched older basement rock.

Diagenesis of Palaeozoic-Mesozoic Tethys Ocean Carbonate succession- Oman Mountains

This paper studies the uppermost unit of Kharus Formation (Cambrian) and the Autochthonous Akhdar Group (Permian-Triassic), which unconformably covers the pre-Permian strata. The petrographic and geochemical as well as field observations indicate that the succession underwent different stages of dolomitization that produced rocks inheriting the original host rock textures and structures (fabric-preserving dolomitization) and rocks with complete obliteration of the pre-existing textures (fabric-destroying dolomitization). Dolomites that retain the original fabric of the limestone are indicators of the host rock mineralogy, i.e., whether it was made up of high Mg-calcite or aragonitic allochems and indicate early dolomitization. The top part of the Kharus Formation consists of pervasively dolomitized units, whereas dolomites belonging to the Autochthonous Akhdar Group display variable degrees of structural and textural preservation. The evidence suggests very early dolomitization in a relatively short time interval for the Permian-Triassic carbonates. The preserved depositional features in the Permian-Triassic carbonates indicate deposition in shallow marine environments with variable energy levels. Seven facies are inferred: stromatolites, mudstones, wackestones, intraformational breccias, grainstones, packstones and grain/packstones. Petrographic as well as field observations exclude evidence of evaporites within Palaeozoic-Mesozoic rocks. Five paragenetic phases are determined to explain the type of dolomitization and to indicate the type and severity of diagenesis that affected the Palaeozoic-Mesozoic Tethys Ocean carbonates from the Oman Mountains.

Sr-bearing phosphates of the apatite supergroup from the alkaline rocks of the Konder pluton, Khabarovsk Krai

The paper presents a mineralogical description of Sr-bearing phosphates of the apatite supergroup found in eudialyte-aegirine-albite rocks of the Konder pluton, Khabarovsk krai. The Sr-dominant phases are associated with minerals of the lamprophyllite group and titanite, whereas the Ca-dominant phases are associated with calciocatapleite and kainosite-(Y), which are the products of the decomposition of eudialyte. The phosphates probably formed during post-magmatic alteration of host rock in a following sequence: stronadelphite > fuorostrophite > Sr-rich fuorapatite (fuorocaphite) > Na-REE-fuorapatite. Their variable chemical composition indicates decreasing Sr, Ba and F contents and increasing Ca, Na, REE and (OH) contents during crystallization. The crystallization sequence could refect a decrease in alkalinity of the mineral-forming conditions. Keywords: stronadelphite, fuorostrophite, fuorocaphite, Sr-rich fuorapatite, fuorapatite, alkaline rocks, hydrothermal alterations, Konder pluton, alkaline-ultramafc complexes.

All post- Cambrian ichnospecies of Psammichnites Torell, 1870 belong to Olivellites Fenton and Fenton, 1937a

The ichnogenus Psammichnites herein restricted to Psammichnites gigas is based on comparison of morphology, feeding behaviour, contrast between the burrows and the host rock and possible producers. The record of siphonal activity as a “snorkel device” is discussed. The diagnosis of the ichnogenus Olivellites now is amended and includes all the records of Psammichnites in the post-Cambrian. Olivellites is now documented in successions other than the classical tidal flat deposits facies of the Carboniferous of the USA. We propose that the producer of Olivellites was an animal with capacity for displacement to different shallow infaunal levels for different feeding strategies. An interpretation of detritus feeding behavior with sediment displacement (pasichnia) is favoured here. The producer of Olivellites was likely to have been a bivalved mollusc that evolved after the Late Ordovician mass extinction. It was euryhaline and lived in a broad bathymetric range, and is recorded in temperate to glacially related successions. The material of Olivellites implexus from western Argentina is the youngest record of the ichnogegenus from Western Gondwana.

Geology and Geochemistry of Selected Gold Deposits in the Ailaoshan Metallogenic Belt, China: Origin of Ore-Forming Fluids

The formation of the Ailaoshan metallogenic belt was the result of: the Neoproterozoic super mantle plume, the Indosinian and South China blocks in the Late Triassic after the Paleo-Tethys Ocean closure, and Oligocene-Eocene continental-scale shearing related to the India-Eurasia collision. It is one of the most important Cenozoic gold ore province in the world. In this paper, the geological characteristics, isotopic geochemistry, and geochemical data of ore-forming fluids of four large-scale gold deposits in the Ailaoshan metallogenic belt (Mojiang Jinchang, Zhenyuan Laowangzhai, Yuanyang Daping, and Jinping Chang’an) are comprehensively compared. The features of host-rock alteration, metallogenetic periods and stages, geochronology, fluid inclusion, and C-H-O-S-Pb isotopes of gold deposits are summarized and analyzed. The gold mineralization in the Ailaoshan metallogenic belt occurred mostly in 50–30 Ma, belonging to the Himalayan period. The gold mineralization is closely related to silicification, argillation, carbonation, and pyritization due to the strong mineralization of hydrothermal fluid, the development of alteration products, and the inconspicuous spatial zonation of alteration types. The ore-forming fluid is mainly composed of mantle fluid (magmatic water) and metamorphic fluid (metamorphic water). The ore-forming materials of the Jinchang, Chang’an, and Laowangzhai gold deposits mainly originate the host-rock strata of the mining area, and the carbon is more likely to from marine carbonate. The carbon in the Daping gold deposit from the original magma formed by the partial melting of the mantle. Pb isotopes have characteristics of crustal origin, accompanied by mixing of mantle-derived materials and multisource sulfur mixing, and are strongly homogenized.

Garnet major-element composition as an indicator of host-rock type: a machine learning approach using the random forest classifier

The major-element chemical composition of garnet provides valuable petrogenetic information, particularly in metamorphic rocks. When facing detrital garnet, information about the bulk-rock composition and mineral paragenesis of the initial garnet-bearing host-rock is absent. This prevents the application of chemical thermo-barometric techniques and calls for quantitative empirical approaches. Here we present a garnet host-rock discrimination scheme that is based on a random forest machine-learning algorithm trained on a large dataset of 13,615 chemical analyses of garnet that covers a wide variety of garnet-bearing lithologies. Considering the out-of-bag error, the scheme correctly predicts the original garnet host-rock in (i) > 95% concerning the setting, that is either mantle, metamorphic, igneous, or metasomatic; (ii) > 84% concerning the metamorphic facies, that is either blueschist/greenschist, amphibolite, granulite, or eclogite/ultrahigh-pressure; and (iii) > 93% concerning the host-rock bulk composition, that is either intermediate–felsic/metasedimentary, mafic, ultramafic, alkaline, or calc–silicate. The wide coverage of potential host rocks, the detailed prediction classes, the high discrimination rates, and the successfully tested real-case applications demonstrate that the introduced scheme overcomes many issues related to previous schemes. This highlights the potential of transferring the applied discrimination strategy to the broad range of detrital minerals beyond garnet. For easy and quick usage, a freely accessible web app is provided that guides the user in five steps from garnet composition to prediction results including data visualization.

Cement as a component of the multi-barrier system: radionuclide retention in cementitious environments

Safety concepts regarding nuclear waste disposal in underground repositories generally rely on a combination of engineered and geological barriers, which minimize the potential release of radionuclides from the containment-providing rock zone or even their transport into the biosphere. Cementitious materials are used for conditioning of certain nuclear waste types, as components of waste containers and overpacks, as well as being constituents of structural materials at the interface between backfilling and host rock in some repository concepts. For instance, the preferred option for the disposal of high-level waste (HLW) in Belgium is based on the supercontainer design, which consists of a carbon steel overpack surrounded by a thick concrete buffer (Bel et al., 2006). In the event of formation water interacting with cementitious materials, pore water solutions characterized by (highly) alkaline pH conditions will form. These boundary conditions define the chemical response of the radionuclides, but also influence the behaviour of neighbouring components of the multi-barrier system, e.g. bentonitic or argillaceous backfilling and host rock. Hardened cement paste or Sorel cement are considered to be main sorbing materials present in the near field of repositories for low- and intermediate-level waste (L/ILW). Hence, interactions of radionuclides with cementitious materials represent a very important mechanism retarding their mobility and potential migration from the near field (Wieland, 2014; Ochs et al., 2016). While the quantitative description of the sorption processes (usually in terms of sorption coefficients, i.e. Kd values) is a key input in the safety analysis of nuclear waste repositories, detailed mechanistic analysis and understanding of sorption phenomena provide additional scientific arguments and important process understanding, and thus enhance both the quality of safety arguments and the overall confidence in the safety assessment process. Research at KIT-INE dedicated to the interaction of cementitious materials with radionuclides is conducted in the context of different repository concepts, including clay (low- and high-ionic strength conditions), crystalline rock or rock salt. Experimental and theoretical studies are performed within the framework of national (GRAZ, BMWi) and international (CEBAMA and EURAD-CORI, EU Horizon 2020 Programme) projects, extending to third-party projects with several waste management organizations in Europe, e.g. SKB (Sweden), ONDRAF-NIRAS (Belgium) or BGE (Germany). The combination of classical experimental (wet chemistry) methods, advanced spectroscopic techniques and theoretical calculations provides both an accurate quantitative evaluation and a fundamental understanding of the sorption processes. Examples of recent studies at KIT-INE on radionuclide behaviour in cementitious systems in the context of both L/ILW and HLW will be presented in this contribution to explain methodologies, scientific approaches and results. The present state of knowledge as well as main remaining uncertainties affecting the retention processes of radionuclides in cementitious environments under different conditions will be critically discussed, also in view of current international research activities and repository projects.

Mineral stability, brine development and rock-fluid reaction at repository-relevant temperatures (<i>T</i> < 200 °C) in the potential host rock rock salt

For a repository of heat generating radioactive waste, the thermal behaviour of the host rock and the impact of temperature increase on rock properties is of general importance. In the German Site Selection Act (2017), the maximum temperature of the container surface is preliminarily limited to 100 ∘C but this limit might change in the future based on scientific and technological findings. Rock salt, as one of the possible host rocks, consists predominantly of halite with varying amounts of accessory minerals (e.g., Hudec and Jackson, 2007); however, some lithological units within a salt deposit, e.g. potash seams, show a different mineralogical composition with high amounts of potash minerals. Most of them are not very stable regarding temperature resistance and stress, contain water in the crystal lattice, and therefore react sensitively to changes in the environment. The melting point of most evaporated minerals is higher than the expected temperatures in a repository but dehydration and partial melting might occur at relevant temperatures, depending on the confining pressure. For example, the temperature of dehydration of carnallite is ca. 80 ∘C at 0.1 MPa confining pressure but increases to ca. 145 ∘C at 10 MPa confining pressure (Kern and Franke, 1986). The melting point of carnallite increases from ca. 145∘C/8MPa to ca. 167∘C/24MPa, which corresponds to a depth of ca. 1000 m. Depending on the mineral paragenesis and composition of saline solutions, different minerals develop with increasing temperature. For instance, a salt rock with an initial composition of kieserite + kainite + carnallite + solution R (25 ∘C) reacts solely to kieserite and solution R, when the temperature increases to 78 ∘C. A rock with a composition of kieserite + carnallite + bischofite + solution Z (25 ∘C) reacts to kieserite + carnallite from 25 to 50 ∘C, from 50 to 73 ∘C only kieserite is stable, and at temperatures >73 ∘C kieserite and bischofite develop (Usdowski and Dietzel, 1998). For the construction of an underground repository, the mineralogical composition of the host rocks and fluids have to be evaluated carefully and play an important role for the site selection and design of the underground facility.

Radionuclide geochemistry: solubility and thermodynamics in an HLW repository

Deep geological disposal is the internationally favoured option to isolate high-level nuclear waste (HLW) from the biosphere and to minimise the potential radiological risk for future generations. Potentially contacting aqueous solutions such as groundwater may, however, lead to the corrosion of the solid casks containing the nuclear waste, and the formation of aqueous radionuclide systems in the near-field of the emplacement rooms. As dissolved species, radionuclides can in principle further migrate into the far-field and finally reach the biosphere on medium and long timescales. Like all chemical species, the radionuclides are subject to fundamental (geo)chemical laws. Relevant reactions that control retention and release, and hence, the migration behaviour and fate of radionuclides in a repository, are solubility equilibria, formation of soluble complexes, redox reactions, sorption on and incorporation into mineral surfaces, transport phenomena etc. These processes depend directly on the (geo)chemical boundary conditions, and, consequently, can differ greatly for various host rock systems such as clay rock, rock salt, and crystalline rock. Many of the radionuclides in HLW are heavy metals that are sparingly soluble under various repository-relevant conditions, e.g. actinides, lanthanides, transition metals, so that only partial dissolution (mobilisation) from the solid waste matrices is expected. This underlines the importance of evaluating the radionuclide solubility within a geochemically based safety assessment for repositories as it provides reliable upper-limit concentrations of the mobile, potentially migrating radionuclide fraction in the near-field. In this contribution, we discuss relevant aspects related to the topic radionuclide solubility and thermodynamics in a HLW repository. This includes a summary of recent laboratory studies on the solubility behaviour and speciation of key radionuclides in repository-relevant solutions, which are an important basis for obtaining (geo)chemical information and models, and the corresponding fundamental thermodynamic constants on aqueous radionuclide systems. National and international thermodynamic database projects, where quality-assured thermodynamic data (solubility products, complex formation constants, and ion-interaction parameters) are evaluated and compiled, e.g. the Nuclear Energy Agency Thermochemical Database (http://www.oecd-nea.org, last access: 1 November 2021) or the Thermodynamic Reference Database (http://www.thereda.de, last access: 1 November 2021), are highlighted and the main remaining uncertainties discussed. The experimental information and the quantitative thermodynamic data are applied within a generic case study to demonstrate the impact of different geochemical solution conditions representing different host rock systems considered as HLW repositories in Germany on the solubility and speciation of selected radionuclides.