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Thorium (Th) is a naturally occurring radioactive element found in the environment, and recent advancements have been made in identifying and characterizing Th-bearing nanoparticles (NPs). However, the main focus is still on synthesized Th-bearing NPs and knowledge about natural Th-bearing NPs remains limited. Here, high-resolution transmission electron microscopy (HRTEM) observations of thorite from the Huayangchuan uranium ore deposit in Shaanxi Province, Central China, have revealed the nanoscale mineral characteristics of thorite. In this study, thorite NPs ranging from 5–10 nm in size were identified within the uranium ore. A combination of transmission electron microscopy-energy dispersive spectroscopy (TEM-EDS) elemental mapping and corresponding HRTEM images alongside Selected Area Electron Diffraction (SAED) and Fast Fourier Transform (FFT) patterns revealed a complex nanoscale structure in the thorite NPs, consisting of both amorphous and crystalline nanodomains with abundant defects. These nanostructures are associated with a metamictization mechanism in micrometer-sized thorite. Our findings indicate that the metamictization process can generate numerous thorite nanoparticles. Given the high penetrability and mobility of these NPs, the metamictization of thorite poses new challenges for the long-term stability of radioactive substances and the storage containers for radioactive waste. Furthermore, considering the likelihood of environmental release and the chemical toxicity, radioactivity, and nanotoxicity of natural Th-bearing NPs, increased attention should be given to the presence of natural thorite NPs in the ore deposit. [Display omitted] • Thorite comprises both originally crystalline minerals and amorphous matrix interspersed with isolated thorite nanoparticles. • Th-bearing NPs could play a significant role in the migration and potential environmental distribution of thorium. • Natural Th-bearing NPs is crucial for addressing future environmental challenges. [ABSTRACT FROM AUTHOR]

This study investigated the feasibility of Raman spectroscopy as a rapid and nondestructive chemical analysis tool for assessing radiation-induced amorphization in aggregate-forming minerals. Metachert and sandstone concrete aggregates, rich in quartz and containing additional minerals, such as albite and microcline in the case of sandstone, were exposed to various neutron fluence levels (1.2, 2.2, 7.0, and 14.3 × 1019 n/cm², E ≥ 0.01 MeV) at ∼53.3°C. The Raman spectra of both the nonirradiated and irradiated samples were collected with a specific focus on quartz characterization. Concurrently, X-ray diffraction (XRD) refinement was employed to calculate the cell volume expansions of the studied mineral. The crystal lattice defects in α-quartz induced by neutron irradiation cause changes in the Raman band attributes (band position, full width at half maximum, and relative intensity), and are also responsible for the growth of defect bands. The behavior of the most intense vibrational bands can be used to estimate the change in the cell volume of irradiated α-quartz in different rocks. The data analysis presented in this study demonstrates a good correlation between the changes in the cell volume of quartz, as measured using XRD, and the Raman band attributes. This correlation enhances our understanding of structural alterations, emphasizing the potential of Raman spectroscopy as a reliable method for investigating the structural changes induced by the irradiation of minerals and highlighting its agreement with well-established XRD analyses. [ABSTRACT FROM AUTHOR]

Accessory minerals in granitic rocks are unlikely significant radionuclide contributions to groundwater due to their remarkable durability. However, accessory minerals incorporating U and Th may suffer structural damages due to the radioactivity and become highly susceptible to alteration. This study investigates geochemistry coupled with textural analysis of the U–Th bearing accessory minerals using a field emission scanning electron microscope and an electron probe micro-analyzer. Altered zircons with numerous open structures related to the radioactive decay show higher contents of U and Th and low analytical totals. Some thorites show high contents of U and non-formula elements due to the hydrothermal alteration in the metamicted thorite. The cerianite including U occurs as micro-veinlet in fracture with trace of Fe and Mn oxides, which indicates secondary phase formation from the decomposed accessory minerals in an oxidizing environment. Some accessory minerals with the high content of U and Th have been found in Mesozoic granite terrain in South Korea, where high concentration levels of radionuclide in groundwater were also reported. The leaching of U may be more likely when the accessory minerals are highly metamicted or altered as found in our samples. The altered zircon and thorite of the study area could be major carriers of radioelement in Mesozoic granitic aquifers where the occurrence of soluble U-minerals has not been reported. [Display omitted] • High radionuclides concentration in groundwater poses a threat to human health. • Accessary minerals can enrich groundwater with radionuclides in granite aquifers. • Altered zircons contain high U and Th levels with open structures. • Thorites show elevated U levels and non-formula elements due to alteration. • Metamicted and/or altered accessory minerals increase uranium leaching potential. [ABSTRACT FROM AUTHOR]

[Display omitted] • We identified W-rich zircons from the granite in the Hukeng deposit. • These W-rich zircons record the activity of W-rich ore-forming fluids. • W/Gd ratios of zircons can be used as an indicator to estimate mineralization potential. South China is endowed with copious hydrothermal tungsten ore deposits, which are generally suggested to be associated with highly fractionated granites. However, the mechanism of tungsten enrichment and mineralization during magmatic-hydrothermal processes is not clear. Here, we clearly identified W-rich zircons (up to several thousand ppm) from the granite in the Hukeng tungsten deposit in South China. W-rich zircons are generally dark in cathodoluminescence images with irregular cracks, cavities and blurry oscillatory zones. They also show high contents of U, Nb, REEs, and high W/Gd ratios, which are not possible to be produced only by magma differentiation. Raman spectra of zircons indicate that these W-rich zircons have experienced different degrees of metamictization. Thus, these W-rich zircons should be crystallized from the late magma and subsequently altered by W-rich magmatic-hydrothermal fluids. W-rich zircons record the activity of W-rich ore-forming fluids which were exsolved from the granitic magma. We suggested that the W/Gd ratios of > 0.2 of zircons can be used as an indicator to estimate the W mineralization potential of a granite. This study provides a new pathway for using zircon to record tungsten mineralization processes and to guide tungsten ore prospecting. [ABSTRACT FROM AUTHOR]

In situ U-Pb geochronology has been conducted using laser ablation inductively coupled mass spectrometry (LA-ICP-MS) on shocked and thermally metamorphosed apatite, titanite, and zircon grains from the Steen River impact structure, Canada. The dated relict mineral phases occur within impact melt-bearing breccias that underwent post-deposition sintering at 450 °C > T < 800 °C. Apatite yields a refined lower intercept age of 141 ± 4 Ma, which we interpret as the best estimate age for the Steen River impact event. Titanite was only partially reset; yielding a lower intercept age of 113 ± 41 Ma. Zircon yields a lower intercept impact age of 120 ± 14 Ma, which is considered a minimum best-estimate impact age. The most reset zircon analyses that control this lower intercept are complicated by combinations of common-Pb incorporation and recent Pb loss associated with granularized and radiation-damaged (metamict) domains. All three phases preserve Paleoproterozoic crystalline basement ages, with a single concordant 206Pb/238U age of 1914 ± 39 Ma from apatite, an upper intercept age of 1882 ± 11 Ma from zircon, and an upper intercept age of 1842 ± 9 Ma from titanite. For apatite, the degree of isotopic resetting is largely thermally controlled, with the extent of reset closely associated with textural setting (degree of grain armouring, melt proximity and sample temperature) and, to a lesser extent, by shock/thermally generated microstructures (i.e., planar fractures, micro-vesicles, and recrystallized domains). While titanite records an impact age that falls within error of apatite and zircon, the majority of grains experienced only partial isotopic resetting, which we attribute to incomplete Pb loss associated with rapid cooling and post-depositional sintering of the breccia matrix below the titanite closure temperature (∼800 °C). In zircon, ancient (impact) Pb loss was facilitated along defect-related, fast-diffusion pathways within pre-impact metamict domains, shock defects, and via recrystallization. These same domains were also subject to recent (post-impact) Pb loss and common Pb contamination, significantly compromising the reliability of zircon ages. The distribution of U-Pb ratios in apatite and titanite is unlike those obtained in crystalline targets, a feature we interpret to be characteristic of impact structures developed in mixed (sedimentary – crystalline) targets, such as Steen River. In this case, disaggregated melt systems create thermal regimes distinct from those derived from predominantly igneous/metamorphic targets. With an age of 141 ± 4 Ma, Steen River joins the Dellen (Sweden), Gosses Bluff (Australia), Mjølnir (Barents Sea), and Morokweng (South Africa) impact structures in being formed at, or close to, the Jurassic-Cretaceous boundary. [ABSTRACT FROM AUTHOR]

The zircon U-Pb system is one of the most robust geochronometers, but during an impact event individual crystals can be affected differently by the passage of the shock wave and impact generated heat. Unraveling the potentially complex thermal history recorded by zircon crystals that experienced variable levels of shock and heating, as well as additioanl pre- and post-impact thermal events, has been difficult using classical geochronological methods. The existing high-precision 40Ar/39Ar age constraints for the K-Pg Chicxulub event, and the previous U-Pb dating of the basement rocks from the impact site, make Chicxulub an ideal location to study impact-induced effects on the zircon U-Pb systematics and to evaluate potential 'memory effects' of pre-impact U-Pb signatures preserved within those individual zircon crystals. Recent IODP-ICDP drilling of the Chicxulub impact structure recovered 580 m of uplifted shocked granitoid and 130 m of melt and suevite, providing an unprecedented opportunity to study zircon crystals subjected to a range of shock pressures, thermal, and deformational histories. Zircon morphologies were classified using scanning electron microscopy (SEM) imaging and then samples were depth profiled using laser ablation inductively coupled plasma mass-spectrometry (LA-ICP-MS) to document the range of preserved age domains from rim-to-center within individual crystals. The results show U-Pb ages range from 66 to 472 Ma, which are consistent with both inherited Carboniferous and Late Paleozoic basement ages as well as Pb loss ages in response to the K-Pg impact event. While the bulk of the zircon grains preserve Paleozoic ages, high U (metamict) zones within fractured zircon crystals exhibited an age within uncertainty (66 ± 6.2 Ma) of the impact age (66.038 ± 0.049 Ma), indicating that inherited intragrain U-Pb kinetics and/or hydrothermal fluid flow may have controlled age resetting those zircon crystals rather than impact-induced shock and heating alone. Moreover, the calculated α-decay doses suggest that the zircon crystals experienced Stage 1 or early Stage 2 radiation damage accumulation. Therefore, we suggest that the lowered crystal annealing temperature in crystals that previoulsy experienced radiation damage make the zircon U-Pb clock either more susceptible to the relatively short heat pulse of the impact event, the moderate pressure and temperature conditions in the peak ring, and/or to hot-fluid flow in the long-lasting post impact hydrothermal system. • Shocked zircon crystals extracted from Chicxulub's peak ring rocks are analyzed via U-Pb LA-ICP-MS depth profiling. • U-Pb LA-ICP-MS depth profiling and the subsequent data export in 1 s increments allows to spatially resolve age trends. • Zircon U-Pb clock partially and possibly fully reset due to the impact event. • Younger U-Pb ages are preserved in fractured zircon with a high U [ppm] concent. or in zircon displaying granular textures. [ABSTRACT FROM AUTHOR]

Abstract The enriched basaltic (martian) shergottite Ksar Ghilane (KG) 002, discovered in 2010, is exceptionally rich in coexisting but discrete apatite and merrillite crystals. It has been selected to better constrain the formation conditions and post-crystallization processes, and thus the evolution of martian rocks based on Ca-phosphates. A petrological, chemical, chronological and microstructural approach using a series of high-spatial resolution techniques including Raman spectroscopy, electron microscopy (SEM, EPMA, CL-imaging) and secondary ion mass spectrometry (SIMS) analysis has been applied to a representative number of Ca-phosphate grains. Analytical results for apatite and merrillite reveal: (i) zoning in F, Cl, Br and I concentrations, (ii) elevated Cl concentrations in the range of ∼11,900–35,300 µg/g and halogen ratios, i.e., Cl/Br and Cl/I, as well as stable chlorine isotope composition, reported as δ37Cl values rel. to Standard Mean Ocean Chloride (SMOC, defined as 0‰) with a value of +0.67 ± 0.14‰ (1σ), distinguishing KG 002 phosphates from that of other enriched and depleted shergottites. The halogen and heavier δ37Cl record indicate a slightly higher degree of ∼3.5% assimilation of Cl-rich and isotopically heavier crustal reservoir on Mars when compared to other enriched shergottites. (iii) Structural investigations together with the chemical and petrological context of the grains confirm the occurrence of hydroxyl-poor merrillite, indicate weak if any alteration effects induced by metamictization, only minor structural modifications due to shock metamorphism, and absence of replacement reactions. Therefore, igneous crystallization of Ca-phosphates from a fractionated, hydrous and ferrous mantle source, rich in volatiles including the halogens and Na and lithophile rare earth-elements, and absence of interaction with crustal fluids/brines of the sample is deduced. (iv) The Pb isotopic composition of six apatite and three merrillite grains is highly unradiogenic and the 238U-206Pb record yields a phosphate crystallization time at 395 ± 240 Ma (2σ), which is similar to those of other enriched shergottites. [ABSTRACT FROM AUTHOR]

Broad variability in intrasample effective U concentration (eU) in zircon crystals is required to characterize zircon (U-Th)/He (zircon He) date-eU relationships that resolve thermal histories in ancient rocks. We describe a new protocol for selecting grains for zircon He thermochronometry that leverages visual crystal metamictization, a proxy for radiation damage accumulation, to generate a range in intrasample eU and zircon He date-eU/metamictization trends. Plane polarized light images, eU concentration, and zircon He data from 59 individual grains from six Proterozoic and three Archean North American granitoids reveal a progressive increase in crystal opacity and discoloration that correspond to increasing eU in each sample. Zircon eU ranges from 89 to 1885 ppm across the dataset and individual samples have eU variations of 538 ppm to 1579 ppm. Three Proterozoic samples yield distinct negative zircon He date-eU patterns with individual dates of ~908 to 20 Ma. Archean grains collectively define a negative date-eU trend from ~661 to 4 Ma. In contrast, three other Proterozoic samples yield uniform ~25 Ma zircon He dates over an 1800 ppm eU range, despite increasing eU with increasing metamictization. Simple thermal history models that account for coevolution of zircon radiation damage and He diffusion demonstrate visible metamictization and diffusivity are either coupled or decoupled depending on a sample's thermal history. Zircon He date-eU/metamictization pediments develop when variable but high eU grains with variable visual damage and closure temperature close with respect to He at the same time. Uniform dates with progressive increases in eU and visual damage, reflect decoupled He diffusion and visual damage, are associated with rapid cooling, and/or imply some forms of damage in zircon may not fully anneal. [ABSTRACT FROM AUTHOR]

The application of zircon and xenotime geochronometers requires knowledge of their potential and limitations related to possible disturbance of the age record. The alteration of the intergrown zircon and xenotime in pegmatite from the Góry Sowie Block (SW Poland) was studied using the electron microprobe analysis, X-ray WDS compositional mapping, micro-Raman analysis, and LA-ICP-MS U-Pb dating of zircon and xenotime, as well as the U-Th-total Pb dating of uraninite. These microanalytical techniques were applied to understand the formation mechanisms of the secondary textures related to post-magmatic processes in the zircon and xenotime intergrowth, and to constrain their timing. Textural and compositional features combined with U-Pb data indicate that the pegmatite-related crystallization of the zircon and xenotime intergrowth occurred ca. 2.09 Ga (2086 ± 35 Ma for zircon and 2093 ± 52 Ma for xenotime), followed by the re-equilibration of zircon and xenotime ca. 370 Ma (373 ± 18 Ma and 368 ± 6 Ma, respectively) during the formation of the younger pegmatite. The zircon and xenotime were most likely derived from Precambrian basement rocks and emplaced in the pegmatite as a restite. The zircon preserved textures related to diffusion-reaction processes that affected its high-U core (up to ca. 9.6 wt% UO 2 ), which underwent further metamictization and amorphization due to self-radiation damage. The zircon rim and xenotime were affected by coupled dissolution-reprecipitation processes that resulted in patchy zoning, age disturbance and sponge-like textures. Xenotime was also partially replaced by fluorapatite or hingganite-(Y) and Y-enriched allanite-(Ce). The termination of the low-temperature alteration was constrained by the U-Th-total Pb age of the uraninite inclusions that crystallized in zircon at 281 ± 2 Ma, which is consistent with the age of 278 ± 15 Ma obtained from the youngest cluster of U-Pb ages in the re-equilibrated high-U zircon domains. This study demonstrates the importance of the careful examination of compositional, microtextural and geochronological data obtained using microanalytical techniques to reconstruct the complex thermal histories recorded by accessory minerals. [ABSTRACT FROM AUTHOR]

Two baddeleyite megacrysts were evaluated as potential reference materials (RMs) for SIMS oxygen isotope analysis, and utilized to understand and calibrate instrumental mass fractionation (IMF). A baddeleyite crystal (S0045) from the Phalaborwa carbonatite, South Africa has a mean δ 18 O VSMOW  = +4.6 ± 0.3‰ (range 0.75‰) measured using laser fluorination gas source mass spectrometry (LF-GMS) and one (S0069) from the Mogok metamorphic belt, Myanmar has δ 18 O VSMOW  = +22.2 ± 0.4‰ (range 0.89‰). SIMS standardization utilizing these inherently heterogeneous RMs is possible by analyzing a number of crystal fragments and utilizing one of them lying at the median of the range. Metamictization, lattice orientation, and chemical composition do not appear to be significant (<0.5‰) variables in matrix matching of RMs and unknowns. Propagation of errors while utilizing the imperfect RMs results in 10 μm diameter spot uncertainties of about ±0.3‰ (2σ). SIMS oxygen isotope analysis of co-crystalline zircon and baddeleyite from the 2.2 Ga Duck Lake sill (DLS) in the Northwest Territories, Canada, yield predominant δ 18 O VSMOW modes of +6.0‰ and +3.2‰, respectively. This difference is consistent with preserving high-temperature isotopic equilibrium between zircon and baddeleyite. DLS baddeleyite δ 18 O data as a whole are negatively skewed (to 0.0‰), and interpreted to reflect low temperature, open-system behaviour. Zircon δ 18 O are less affected, but also show hints of the same influences of secondary alteration and oxygen isotope exchange. [ABSTRACT FROM AUTHOR]

A sample of plutonium tetrafluoride that was separated prior to 1966 at the Hanford Site in Washington State was analyzed at the Pacific Northwest National Laboratory (PNNL) in 2015 and 2016. The plutonium tetrafluoride, as received, was an unusual color and considering the age of the plutonium, there were questions about the condition of the material. These questions had to be answered in order to determine the suitability of the material for future use or long-term storage. Therefore, thermogravimetric/differential thermal analysis and X-ray diffraction evaluations were conducted to determine the plutonium's crystal structure, oxide content, and moisture content; these analyses reported that the plutonium was predominately amorphous and tetrafluoride, with an oxide content near ten percent. Freshly fluorinated plutonium tetrafluoride is known to be monoclinic. During the initial thermogravimetric/differential thermal analyses, it was discovered that an exothermic event occurred within the material near 414 °C. X-ray diffraction analyses were conducted on the annealed tetrafluoride. The X-ray diffraction analyses indicated that some degree of recrystallization occurred in conjunction with the 414 °C event. The following commentary describes the series of thermogravimetric/differential thermal and X-ray diffraction analyses that were conducted as part of this investigation at PNNL. [ABSTRACT FROM AUTHOR]

We present a microstructural and U Pb systematics study comparing pristine, thermally annealed (TA) and chemically abraded (CA) ~ 3500 Ma zircon from a quartz-dioritic gneiss, with the aim to improve pre-analytical workflows for more accurate and precise LA-ICP-MS U Pb dating of ancient zircon. Four zircon domains are identified: i) low- to medium-U concentric-oscillatory zoned cores, ii-iii) two porous high-U outer alteration domains, and iv) low-U narrow inward growing recrystallization rims. Raman spectroscopy on the pristine zircon reveals a positive correlation between increasing structural damage and U content. The porous high-U outer domains show a drastic increase in non-formula Ca above estimated amorphous fractions of ~ 0.8, which we ascribe to hydrothermal alteration of high-damage zircon characterized by percolating networks of amorphous areas. Upon treatment (TA, CA), hyper-spectral CL and Raman spectroscopy suggest structural recovery of point defects, but not full repair of high-damage amorphous areas. Calculated Raman radiation damage ages suggest that natural annealing affected all domains at ~ 500 Ma, consistent with negligible laser ablation matrix effects comparing pristine and treated cores. We show that reverse discordance in pristine and TA cores is not an analytical artifact. High-U alteration domains are normal discordant and were partially reset at ca. 3410 Ma. Upon CA, U Pb discordance and scatter are reduced in the cores, yielding intercepts of 3503 ± 14 Ma and 560 ± 550 Ma (MSWD = 1.0). The lower intercept matches the timing of Pb-loss recorded in the alteration domains and the Raman radiation damage age. We argue that short distance Pb redistribution within the cores, which led to reverse discordance, was controlled by U Pb systematics recording both the crystallization age and the timing of Pb redistribution. Some excess Pb was redistributed from the partially re-set alteration domains into the cores, leading to mixed U Pb systematics and further reverse discordance. Removal of the latter excess Pb upon CA suggests that radiogenic Pb from the alteration domains accumulated within distinct damage sites accessible for CA leaching. We conclude that standardization of pre-analytical treatment is not recommended; we propose to investigate the structural state of unknown specimen by means of Raman spectroscopy, in combination with commonly applied CL imaging. During LA-ICP-MS analyses, co-measurement of non-formula and selected trace elements is deemed highly valuable in detecting ablations for use in reliable U Pb age determination. [ABSTRACT FROM AUTHOR]

Zircon (U–Th)/He (ZHe) data were acquired for 23 Proterozoic basement samples from an E–W transect through the Colorado Front Range to evaluate whether metamict zircons yield sensible (U–Th)/He data patterns and useful thermal history information. The 112 ZHe dates vary from 147 to 7 Ma, define positive and negative date–eU correlations, and are younger than titanite (U–Th)/He dates that range from 976 to 614 Ma. At moderate to high alpha dose of 10 18 – 10 19 α / g , zircons from the range core yield Laramide ( 52.5 ± 9.6 Ma) dates, whereas those within ∼15 km of the range front yield Miocene ( 21.6 ± 7.7 Ma) results. The He dates for the high alpha dose zircons are reproducible within each sample suite despite their visibly metamict character. The ∼20 Ma range front ZHe dates are younger than apatite (U–Th)/He (AHe) dates ( 66.5 ± 9.6 Ma) and published apatite fission-track data (65–45 Ma) for the same and nearby samples. Thermal history simulations can reproduce the first-order range front date–eU patterns and ZHe–AHe date inversion, but the high-damage zircons are more He retentive than predicted by the zircon damage He kinetic model. The ∼20 Ma ZHe dates may be explained by reheating from hydrothermal fluids along range front faults. The results demonstrate the promise of using He data for high-damage zircons to detect low-temperature (<50 °C) events within and below the temperature sensitivity of the AHe system. [ABSTRACT FROM AUTHOR]

A radiochemical analysis of the valence state of uranium isotopes in minerals involves isolation of the U(IV) and U(VI) valence forms and determination of the radioactivity of the 234 U and 238 U isotopes in each fraction. If the nuclear decay of the uranium in the minerals is accompanied by a redox process, the distribution of the 234 U isotope in the U(IV) and U(VI) forms will differ from that of the 238 U isotope: oxidation leads to enrichment of the U(VI) fraction with the radiogenic 234 U isotope; reduction facilitates enrichment of the U(IV) fraction with 234 U. If the mineral is heated to 600–700 °C before the radiochemical analysis, then an equilibrium activity ratio (AR) for both valences. The question arises: What are the processes that bring this about? The authors of this research studied changes of the AR in the U(IV) and U(VI) fractions after isochronous thermal annealing. [ABSTRACT FROM AUTHOR]

• Six commercially available zircon sands were ranked by metamictization level. • Milling efficiency was better on average with low metamict samples. • Clear trends between metamictization characteristics were difficult to define. • Heat treatment restored the hardness of zircon, worsening milling performance. • One previously calcined sample behaved distinctly differently when milled. Six commercially available zircon sands were characterised by XRD, SEM, BET and helium pycnometry to determine their degree of metamictization. These sands were categorized into pairs denoted as high, medium or low levels of metamictization. The six samples were subsequently dry milled under identical conditions and their milling behaviour was tracked by measuring the particle size distribution at regular intervals. Samples with low levels of metamictization were found to achieve a marginally smaller particle size than samples with high levels of metamictization after prolonged milling. This was attributed to two potential mechanisms during breakdown – brittle fracture in the former due to retained hardness, in comparison to a more ductile resistance to fracture in the latter due to reduced hardness. However, no clear trend between specific metamictization characteristics and milling behaviour was found. The results reveal a poorer overall milling efficiency for high metamict samples, which has implications such as increased energy costs, poor quality product and a need for further processing of samples exhibiting high levels of metamictization. This study creates a novel link between the milling behaviour of zircon and its level of metamictization. The knowledge gained holds strong importance for industrial entities wishing to carry out and maintain an efficient milling process, with feed material quality likely to become more variable in future years. [ABSTRACT FROM AUTHOR]

Zircon geochronology is a critical tool for establishing geologic ages and time scales of processes in the Earth's crust. However, for zircons compromised by open system behavior, achieving robust dates can be difficult. Chemical abrasion (CA) is a routine step prior to thermal ionization mass spectrometry (TIMS) dating of zircon to remove radiation-damaged parts of grains that may have experienced open system behavior and loss of radiogenic Pb. While this technique has been shown to improve the accuracy and precision of TIMS dating, its application to high-spatial resolution dating methods, such as secondary ion mass spectrometry (SIMS), is relatively uncommon. In our efforts to U-Pb date zircons from the late Eocene Caetano caldera by SIMS (SHRIMP-RG: sensitive high resolution ion microprobe, reverse geometry), some grains yielded anomalously young U-Pb ages that implicated Pb-loss and motivated us to investigate with a comparative CA and non-CA dating study. We present CA and non-CA 206 Pb/ 238 U ages and trace elements determined by SHRIMP-RG for zircons from three Caetano samples (Caetano Tuff, Redrock Canyon porphyry, and a silicic ring-fracture intrusion) and for R33 and TEMORA-2 reference zircons. We find that non-CA Caetano zircons have weighted mean or bimodal U-Pb ages that are 2–4% younger than CA zircons for the same samples. CA Caetano zircons have mean U-Pb ages that are 0.4–0.6 Myr older than the 40 Ar/ 39 Ar sanidine eruption age (34.00 ± 0.03 Ma; error-weighted mean, 2σ), whereas non-CA zircons have ages that are 0.7–1.3 Myr younger. U-Pb ages do not correlate with U (~ 100–800 ppm), Th (~ 50–300 ppm) or any other measured zircon trace elements (Y, Hf, REE), and CA and non-CA Caetano zircons define identical trace element ranges. No statistically significant difference in U-Pb age is observed for CA versus non-CA R33 or TEMORA-2 zircons. Optical profiler measurements of ion microprobe pits demonstrate consistent depths of ~ 1.6 μm for CA and non-CA Caetano, R33 and TEMORA-2 zircons, and do not indicate variations in secondary ion sputtering rates due to chemical or structural changes from the CA treatment. Our new data underscore the potential for cryptic Pb-loss to go unrecognized in other geologically young magmatic centers that do not have zircons with high U, statistically discordant isotope ratios, high common Pb, or metamict textures. [ABSTRACT FROM AUTHOR]

Betafite is a uranium–titanium–tantalum–niobium complex oxide mineral generally described as (Ca,U) 2 (Ti,Nb,Ta) 2 O 6 (OH). Significantly lower uranium extractions have been observed when betafite containing ores has been treated via conventional process flow sheets. Therefore it is necessary to understand the leaching behaviour of this mineral in order to open the potential for it to become an economic source of uranium in the future. The leaching kinetics and reaction mechanism of uranium from a natural, metamict betafite sample have been investigated using varied temperature under oxidative acidic conditions. The practically complete extraction of uranium was observed by leaching the natural betafite in a solution containing 214.5 g/L H 2 SO 4 and 2.0 g/L Fe 3 + at 89 °C for a period of 48 h. Alternative leaching conditions using 57.1 g/L H 2 SO 4 and 36.7 g/L Fe 3 + at the same temperature also resulted in practically complete extraction of uranium but improved the selectivity for uranium over titanium, tantalum and niobium. Kinetic modelling has indicated that the rate of the leaching process is controlled by the rate of diffusion of products or reactants involved in the dissolution reaction to the reacting surface through a solid product layer containing niobium. A portion of the betafite mineral sample used in the leaching testwork was recrystallised by heating in air at 1100 °C. The crystalline form of betafite was then leached under conditions similar to those applied to the metamict mineral to determine how crystal structure may affect the extraction of uranium. Less than 12% uranium was extracted from the recrystallised betafite under the conditions that gave practically complete extraction of uranium from the natural betafite sample which gives strong evidence that heat treatment prior to leaching should be avoided. The thermal recrystallisation of betafite in the present study appears to have resulted in tantalum enrichment on the surface of the betafite particles, which may be related to the lower extraction of uranium observed. [ABSTRACT FROM AUTHOR]

Sub-million year age precision on low to moderately metamict Precambrian zircon is often reproducible using the isotope dilution thermal ionization technique (ID-TIMS) exploiting U–Pb double spiking for precise mass fractionation correction. However, this requires total dissolution of sample and laborious chemical processing. On the other hand whole grain evaporation techniques of Pb extraction are simple and less time consuming but provide relatively inefficient ionization and are not amenable to double Pb isotope spiking for precise mass fractionation correction, which limits the precision of ages that they can provide (often restricted to ±few million years). A modified evaporation–condensation method is described that overcomes these limitations with the ability to use 202 Pb– 205 Pb double spiking for precise mass fractionation correction in order to achieve sub-million year age precision on low to highly metamict Precambrian samples. Examples are shown of age determinations on previously dated zircon populations from the Marmion tonalite and Nevison Lake rhyolite, western Superior province (U < 200 ppm), which give 3001.8 ± 0.5 Ma and 2998.2 ± 0.3 Ma, respectively, and from the black norite and the felsic norite in the Sudbury igneous complex (U > 1000 ppm), which give 1848.9 ± 0.2 Ma and 1851.3 ± 0.5 Ma, respectively (all errors are 95% confidence). [ABSTRACT FROM AUTHOR]

Abstract: Zircon (ZrSiO4) from Naegi and Ohro granitic pegmatites, Japan and from Saigon alkali basalt, Vietnam, were mineralogically characterized by inductively couples plasma mass spectrometry (ICP-MS), electron-microprobe analysis (EMPA), X-ray powder diffraction, micro-Raman spectroscopy and leaching experiment. The powder XRD and Raman spectra analyses show that the degree of metamictization increases in the following order: Saigon (crystalline), Ohro (partly metamict) and Naegi zircons (fully metamict). Quantitative analytical results by the EMPA indicate that the Naegi and Ohro zircon samples contain a large amount of REE2O3, while REE2O3 contents in Saigon zircon are below detection limit. The leaching experiments using a solvent 1M-HCl for the present zircons under the condition at a room temperature to 250°C and retention time of 30h resulted in about 100%, 50% and 1% recoveries of REE from the Naegi, Ohro and Saigon zircons, respectively. Leaching experiments for the Naegi zircon at different temperatures and retention time 30h, showed that a significant amount of REE was leached out at the temperature above 150°C, although REE were hard to be leached at a room temperature (about 25°C). Therefore, both low crystallinity of zircon and higher leaching temperature are requisite for effective leaching of REE from zircon. [Copyright &y& Elsevier]

• Crystalline domains coexist with REE-rich amorphous sectors in metamict titanite. • Titanite reactivity is strongly controlled by the density of actinide-induced defects. • Heat treatment anneals the defects rendering REE-rich metamict sectors less reactive. Titanite is a widespread accessory silicate which, in some deposits, hosts rare earth elements (REEs) at levels where it can be considered an important carrier. As titanite also accommodates Th and U at concentrations up to 2000 ppm, evidence of metamitctization, a process where radioactive decay of the actinides progressively damages the crystalline structure, is often observed. The current study aims to investigate how the extent of metamictization within a natural titanite specimen may impact its reactivity, principally in the context of REE recovery. Detailed structural characterization revealed the presence of crystalline domains coexisting with sectors having a dominant amorphous component. Compositionally, the density of irradiation-induced defects, leading to amorphization, shows a strong positive correlation not only with the abundance of actinides, but also with the REE concentration. Heat treatment of titanite performed at temperatures ranging from 400 to 800 °C indicates that, while the compositional zonation is maintained, thermal annealing of the defects results in progressive recovery of the crystalline structure. After treatment in sulfuric acid at 200 °C, the habit of reacted titanite grains is highly irregular, indicating distinct decomposition rates for specific sectors, where the more refractory regions coincide with the REE-depleted crystalline domains. A more detailed visualization of the impact of crystal properties on titanite reactivity, obtained by exposing polished grains to a 50% NaOH solution at 50 °C, reveals that, for pristine titanite, the extent of etching observed on crystal surfaces is controlled by the density of the actinide-induced defects, mainly concentrated in the REEs- and Th-enriched amorphous domains. On the other hand, for grains that were initially heat-treated, the etching features are much weaker, emphasizing that thermal annealing renders the crystals less reactive. From these observations, selective REE recovery, where only the more accessible amorphous titanite domains need to be decomposed, seems possible as long as the ore pre-treatment does not involve a high-temperature stage. [ABSTRACT FROM AUTHOR]

A strongly altered zircon-xenotime intergrowth in pegmatite from the Piława Górna (the Góry Sowie Block, SW Poland) was studied with transmission electron microscopy (TEM) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). Distinct domains demonstrate features related to fluid-induced coupled dissolution-reprecipitation processes resulting in microscale to nanoscale porosity in the zircon and in xenotime, and diffusion-reaction processes in the metamict core of the zircon. The inclusions of secondary phases include fluorapatite, unknown layered Fe-silicate, fibrous Fe-oxides, solid solutions of coffinite-thorite and uraninite-thorianite, uraninite and secondary U-rich zircon. The fluid had high concentrations of Ca and Fe, transporting these nonformula elements through the zircon and xenotime structure while mobilizing U, Th and Pb even in robust xenotime, thus forming small inclusions in nanopores. Nanoinclusions of galena in the zircon represent major Pb mobilization that may cause disturbance during U Pb geochronological analysis. The trace element composition of zircon matches patterns typical of altered zircon. The differentiation of geochemical characteristics between the metamict core and the altered rim of zircon implies different alteration mechanisms, with a stronger role of fluids in the alteration of the rim. Nanoscale observations complement trace element microanalysis and serve as an important and necessary tool to further understand the alterations of geochronometers in the presence of alkaline-rich fluid, especially in the complex environments of pegmatites. • TEM evaluation of nanoinclusions in the altered zircon-xenotime intergrowth. • Xenotime shows nanoscale records of coupled dissolution-reprecipitation processes. • Zircon domains show distinct submicron records of different alteration mechanisms. • The metamict core of zircon was partially annealed by diffusion-reaction processes. • Alteration involved fluid-induced supply of Fe, Ca, Al; and removal of U, Th and Pb. [ABSTRACT FROM AUTHOR]

High‑uranium (~4200 to 8500 ppm U) columbite-group minerals (CGMs) from No. 1 pegmatite at Dakalasu, the Chinese Altay orogen were used to assess the effect of metamictization on the U Pb isotopic systematics. Backscattered electron (BSE) imaging shows that the high U concentrations are due to the U in the crystal structure itself. In the rims, the part of CGM next to cracks or pores filled by titan-uranoan fluorcalciomicrolite is altered. The microlite was likely formed via a dissolution-reprecipitation process that resulted in fractionation between U and Pb and potential discordance of the U Pb isotopic systematics in the altered CGM. Raman spectroscopy indicates that the columbite samples are metamictized to various extents. However, the CGM samples dated by laser ablation – inductively coupled plasma – mass spectrometer (LA-ICP-MS) show excellent U Pb age concordance, with thirty eight out of forty analyses displaying concordant U Pb ages (229.0 ± 1.0 Ma to 228.1 ± 0.6 Ma) overlapping within analytical uncertainty (2σ). The alpha-decay doses are estimated to be 1.53 to 2.31 × 1015 α-decay events/mg, indicating that the CGMs are at a transition stage from being crystalline to completely metamict states. Although spatial separation between U and radiogenic Pb isotopes caused by α-recoil is inevitable, the displacement is on sub-micron scale, much smaller than the scale of laser ablation pits (43 μm) for LA-ICP-MS dating. Therefore, the U Pb isotopic systematics of partially metamict, U-rich CGM may still remain concordant for CGMs that have not suffered hydrothermal alteration or metasomatism and do not contain U- or Pb-rich inclusions within the laser ablation pits. Additionally, the chemical compositions of the CGM have no control over the U Pb isotopic systematics. • The effect of metamictization on columbite U Pb isotopic systematics is investigated. • The degree of metamictization is quantified using α-decay dose and displacements per atom. • Hydrothermal alteration can result in discordance of columbite U Pb isotopic systematics. [ABSTRACT FROM AUTHOR]