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The 238U/235U ratio was precisely measured in uranium minerals from 11 hydrothermal deposits of different geologic settings and ages situated in ore regions of Asia, Europe, Africa, and North America by MC-ICP-MS using a 233U-236U double spike. The spike was calibrated in reference to the CRM-112A standard with 238U/235U = 137.837 ± 0.015 (Richter et al, 2010). The long-term reproducibility of 238U/235U measurement was estimated as ±0.07‰ by the analysis of monitor samples and the IRMM-3184 standard. The analyses were performed using 0.02–0.04-mg microsamples of uraninite, pitchblende, and coffinite, which were locally extracted from polished sections under an optical microscope. The 238U/235U values obtained for 50 samples of U-bearing minerals range from 137.703 to 137.821, with a 0.86‰ difference and a mean 238U/235U value of 137.773 ± 0.056 (±2SD). The range of 238U/235U variations in seven deposits with uraninite is 0.41‰, which is twice as low as for the deposits with pitchblende-dominated ores. Our study provided the first results for 238U/235U variations in minerals from individual deposits. The largest variations were found in the Oktyabr’skii (Eastern Transbaikalia), Schlema-Alberoda (Erzgebirge), and Shea Creek (Athabasca basin) deposits: 0.70, 0.33, and 0.59‰, respectively. Uranium from the early growth zones of 4–5 mm thick pitchblende spherulitic crusts is isotopically heavier (by 0.22–0.45‰) than uranium from the latest growth zones. A similar isotopic shift in 238U/235U in terms of magnitude (0.31‰) and sense was observed between pitchblende and coffinite overgrowths. The uranium isotopic composition of late pitchblende generations, the products of dissolution and reprecipitation of early phases, is 0.46‰ lighter than that of early pitchblende phases. The character of uranium isotope distribution in pitchblende aggregates is consistent with nuclear-volume-dependent isotope fractionation accompanying U(VI) reduction to U(IV) (Bigeleisen, 1996; Schauble, 2007; Stirling et al., 2007), which causes an enrichment of the U(IV)-bearing solid phase in the heavy isotope 238U. The range of 238U/235U ratios for 11 hydrothermal (high-temperature) deposits (137.703–137.821) lies well within the broader (two-fold) range of values determined for the low-temperature deposits Dybryn in Transbaikalia (Golubev et al., 2013) and Pepegoona in South Australia (Murphy et al., 2014). This can be explained by the fact that the uranium isotopic fractionation associating with U(VI) → U(IV) reduction is accompanied by isotope shifts owing to the long-term interaction of groundwater with early phases within sandstone-type deposits. At the same time, owing to the higher temperatures (by 100–300°C) of formation of hydrothermal deposits compared with sandstone-type deposits, nuclear-volume-dependent uranium isotope fractionation decreases by more than a factor of 2 (Bopp et al., 2009).

Special methodology was used to study the distribution of REE and some other elements in zoned fluorites from the different deposits of Eastern Transbaikalia. Fluorites from the uranium and polymetallic ore fields sharply differ in their REE distribution pattern and the composition of fluid inclusions, which reflects the geochemical specifics and indicates the possible sources of parental solutions. A gradual change in REE distribution patterns established in the successive growth zones of fluorites clearly coincides with the gradual decrease of temperature and mineralization of fluid inclusions. It is suggested that a change in the REE distribution pattern was provoked by the crystallochemical differentiation related to the formation of nano-sized mineral admixtures of REE phosphates and/or fluorcarbonates, which possess an ability to the selective accumulation of different REE groups. It was found that the zoned fluorites from the Streltsovka and Garsonui deposits show an opposite trends in the change of REE pattern with zonation. With a general decrease in total REE contents, fluorite from the Streltsovka deposit shows a change from positive parabolic to subchondritic pattern, while that from the Garsonui deposit, varies from the negative via subchondritic to the positive patterns.

U-Pb systems were examined in samples (ranging from 4 to 10 cm3 in volume) of ore material taken from along a 3.5-m profile across a zone of U mineralization exposed in an underground mine at the Strel’tsovskoe U deposit in eastern Transbaikalia. The behaviors of two isotopic U-Pb systems (238U-206Pb and 235U-207Pb) are principally different in all samples from our profile. While the individual samples are characterized by a vast scatter of their T(206Pb/238U) age values (from 112 to 717 Ma), the corresponding T(207Pb/235U) values vary much less significantly (from 127 to 142 Ma) and are generally close to the true age of the U mineralization. The main reason for the distortion of the U-Pb system is the long-lasting (for tens of million years) migration of intermediate decay products in the 238U-206Pb(RD238U) in the samples. This process resulted in the loss of RD238U from domains with high U concentrations and the subsequent accommodation of RD238U at sites with low U concentrations. The long-term effect of these opposite processes resulted in a deficit or excess of 206Pb as the final product of 238U decay. The loss or migration of RD238U are explained by the occurrence of pitchblende in association with U oxides that have higher Si and OH concentrations than those in the pitchblende and a higher +6U/+4U ratio. The finely dispersed character of the mineralization and the loose or metamict texture of the material are the principal prerequisites for RD238U loss and an excess of 206Pb in adjacent domains with low U concentrations. Domains with low U contents in the zone with U mineralization serve as geochemical barriers (because of sulfides contained in them) at which long-lived RD238U(226Ra, 210Po, 210Bi, and 210Pb) were accommodated and subsequently caused an excess of 206Pb. The 235U-207Pb system remained closed because of the much briefer lifetime of the 235U decay products. This may account for the significant discrepancies between the T(206Pb/238U) and T(207Pb/235U) age values. RD238U was most probably lost via the migration of radioisotopes at the middle part and end of the 238U family (starting with 226Ra). The heavy Th, Pa, and U radioisotopes (234Th, 234Pa, 234U, and 230Th) that occur closer to the beginning of 238U decay, before 226Ra, only relatively insignificantly participated in the process. Our results show that the loss and migration of RD238U are, under certain conditions, the main (or even the only) process responsible for the distortion of the U-Pb system.