Natural fractionation of U/U

The isotopic composition of U in nature is generally assumed to be invariant. Here, we report variations of the ²³⁸U/²³⁵U isotope ratio in natural samples (basalts, granites, seawater, corals, black shales, suboxic sediments, ferromanganese crusts/nodules and BIFs) of ∼1.3‰, exceeding by far the analytical precision of our method (≈0.06‰, 2SD). U isotopes were analyzed with MC-ICP-MS using a mixed ²³⁶U-²³³U isotopic tracer (double spike) to correct for isotope fractionation during sample purification and instrumental mass bias. The largest isotope variations found in our survey are between oxidized and reduced depositional environments, with seawater and suboxic sediments falling in between. Light U isotope compositions (relative to SRM-950a) were observed for manganese crusts from the Atlantic and Pacific oceans, which display δ²³⁸U of −0.54‰ to −0.62‰ and for three of four analyzed Banded Iron Formations, which have δ²³⁸U of −0.89‰, −0.72‰ and −0.70‰, respectively. High δ²³⁸U values are observed for black shales from the Black Sea (unit-I and unit-II) and three Kupferschiefer samples (Germany), which display δ²³⁸U of −0.06‰ to +0.43‰. Also, suboxic sediments have slightly elevated δ²³⁸U (−0.41‰ to −0.16‰) compared to seawater, which has δ²³⁸U of −0.41 ± 0.03‰. Granites define a range of δ²³⁸U between −0.20‰ and −0.46‰, but all analyzed basalts are identical within uncertainties and slightly lighter than seawater (δ²³⁸U = −0.29‰).Our findings imply that U isotope fractionation occurs in both oxic (manganese crusts) and suboxic to euxinic environments with opposite directions. In the first case, we hypothesize that this fractionation results from adsorption of U to ferromanganese oxides, as is the case for Mo and possibly Tl isotopes. In the second case, reduction of soluble U^VI to insoluble U^IV probably results in fractionation toward heavy U isotope compositions relative to seawater. These findings imply that variable ocean redox conditions through geological time should result in variations of the seawater U isotope compositions, which may be recorded in sediments or fossils. Thus, U isotopes might be a promising novel geochemical tracer for paleo-redox conditions and the redox evolution on Earth. The discovery that ²³⁸U/²³⁵U varies in nature also has implications for the precision and accuracy of U-Pb dating. The total observed range in U isotope compositions would produce variations in ²⁰⁷Pb/²⁰⁶Pb ages of young U-bearing minerals of up to 3 Ma, and up to 2 Ma for minerals that are 3 billion years old.     

Isotopic composition (U/U) of some commonly used uranium reference materials

We have determined ²³⁸U/²³⁵U ratios for a suite of commonly used natural (CRM 112a, SRM 950a, and HU-1) and synthetic (IRMM 184 and CRM U500) uranium reference materials by thermal ionisation mass-spectrometry (TIMS) using the IRMM 3636 ²³³U-²³⁶U double spike to accurately correct for mass fractionation. Total uncertainty on the ²³⁸U/²³⁵U determinations is estimated to be <0.02% (2σ). These natural ²³⁸U/²³⁵U values are different from the widely used ‘consensus’ value (137.88), with each standard having lower ²³⁸U/²³⁵U values by up to 0.08%. The ²³⁸U/²³⁵U ratio determined for CRM U500 and IRMM 184 are within error of their certified values; however, the total uncertainty for CRM U500 is substantially reduced (from 0.1% to 0.02%). These reference materials are commonly used to assess mass-spectrometer performance and accuracy, calibrate isotope tracers employed in U, U-Th and U-Pb isotopic studies, and as a reference for terrestrial and meteoritic ²³⁸U/²³⁵U variations. These new ²³⁸U/²³⁵U values will thus provide greater accuracy and reduced uncertainty for a wide variety of isotopic determinations.     

<Superscript>238</Superscript>U and <Superscript>235</Superscript>U isotope fractionation upon oxidation of uranium-bearing rocks by fracture waters

The variations in ²³⁸U/²³⁵U values accompanying mobilization of U by fracture waters from uranium-bearing rocks, in which U occurs as a fine impregnation of oxides and silicates, were studied by the high-precision (±0.07‰) MC–ICP–MS method. Transition of U into the aqueous phase in the oxidized state U(VI) is accompanied by its isotope fractionation with enrichment of dissolved U(VI) in the heavy isotope ²³⁸U up to 0.32‰ in relation to the composition of the solid phases. According to the sign, this effect is consistent with the tendency of the behavior of ²³⁸U and ²³⁵U upon interaction of river waters with rocks of the catchment areas [11] and with the effect observed during oxidation of uraninite by the oxygen-bearing NaHCO₃ solution [12].     

U-Pb systems and U isotopic composition of the sandstone-hosted paleovalley Dybryn uranium deposit, Vitim uranium district, Russia

The isotopic (U-Pb, ²³⁸U-²³⁵U, ²³⁴U-²³⁸U) and chemical study of whole-rock samples and finegrained fractions of rocks in a vertical section of the terrigenous sequence at the Dybryn uranium deposit in the Khiagda ore field shows that a wide U-Pb isotopic age range (26.9-6.5 Ma) is caused by oxidation and disturbance of the U-Pb isotopic system in combination with protracted uranium ore deposition. The oxidation of rocks resulted in the loss of uranium relative to lead and eventually to an overestimated ²⁰⁶Pb/²³⁸U age at sites with a low U content. The ²³⁸U/²³⁵U ratios in the studied samples are within the range of 137.74–137.88. Samples with a high uranium content are characterized by a decreasing ²³⁸U/²³⁵U ratio with a decrease in ²⁰⁷Pb/²³⁵U and ²⁰⁶Pb/²³⁸U ages. A nonequilibrium ²³⁴U/²³⁸U ratio in most studied samples furnishes evidence for young (<1.5 Ma) transformation of the Miocene uranium ore, which is responsible for uranium migration and its redeposition.     

Characterization of a La-Ce-Sr-Ca aluminous hydroxy phosphate in nuclear zone 13 in the Oklo uranium deposit (Gabon)

A La-Ce-Sr-Ca aluminous hydroxy phosphate of the goyazite-florencite-crandallite series was observed in the nuclear reactor zone 13 in the Oklo uranium deposit (Gabon). It has a trigonal elementary cell with a?=?6.98 ± 0.03 Å and c?=?16.35?±?0.04?Å (space group P3m). It occurs in a U-rich sample depleted in ²³⁵U (²³⁵U/²³⁸U?=?0.0047). Its chemical composition, measured by ion microprobe analyses, shows that it contains fission products (Zr, LREE) whereas the isotopic composition of Ba and Sr is natural. Ion microprobe imaging indicates that the nearby uraninite crystals are depleted in fissiogenic LREE. This study shows that the migration of some fission products, probably related to a dolerite dike intrusion, is limited by the formation of aluminous hydroxy phosphates.     

Role of Suspended Particulate Matter in Regulating the Behavior of Dissolved Uranium in the Yellow River Estuary

In order to examine the mixing behavior of dissolved uranium (U) in estuaries under different suspended particulate matter (SPM) regimes, three laboratory-based experiments were conducted by mixing seawater with river water containing different concentrations of SPM. Comparing this study with other field and laboratory-based experiments, dissolved U behaved differently depending upon the concentration of SPM. When SPM concentrations are >?0.8 g/L in the Yellow River, desorption/dissolution of U from SPM becomes predominant and dissolved U is enriched relative to the theoretical mixing line. However, when SPM concentrations are <?0.8 g/L, dissolved U behaves conservatively with some extent of removal during estuarine mixing. ²³⁴U/²³⁸U activity ratios were somewhat constant showing no measurable isotopic fractionation during physical mixing and U sorption/desorption to/from particles. Addition of dissolved ²³⁸U desorbed/dissolved from SPM during the annual Yellow River water-sediment regulation scheme (Jun 30th–Jul 14th, 2014) was estimated at 6.4?×?10¹¹ dpm, about 9% of the total riverine flux of dissolved ²³⁸U during that same period. This study represents a contribution to studies of dissolved U in muddy rivers and estuaries throughout the world. Results reported here provide not only a perspective to better estimate U flux from rivers to the ocean but also new insights into better understanding its estuarine mixing behavior and controlling factors.     

Differential behavior of components of the <Superscript>238</Superscript>U-<Superscript>206</Superscript>Pb and <Superscript>235</Superscript>U-<Superscript>207</Superscript>Pb isotopic systems in polymineralic U ores

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.     

Activity disequilibrium of Th, U, and U in old stilbite: Effects of young U mobility and α-recoil

Stilbite from Malmberget and Svappavara is part of hydrothermal mineral assemblages occupying regionally occurring open Palaeoproterozoic fractures in northern Sweden. At these locations, stilbite is characterized by Pb_rad excess relative to U and by activity ratios of [²³⁴U]/[²³⁸U] > 1 and [²³⁰Th]/[²³⁸U] > 1. The activity disequilibrium requires a disturbance of the U-Th systematics within the last one million years. Leaching and infiltration experiments on Malmberget stilbite demonstrate: (i) preferential leaching in the order Pb >U >Th and uptake in the order Pb > U, and (ii) isotopic fractionation of U by preferential mobilization of ²³⁸U and ²³⁵U relative to ²³⁴U. Stepwise-leaching further indicates that the bulk of U is hosted in the channel sites of stilbite. The Th-U disequilibrium systematics observed in untreated Malmberget and Svappavara stilbite can be explained by: (1) addition of U with [²³⁴U]/[²³⁸U] > 1 from a fluid, or alternatively (2) loss of U from a two-component system, consisting of a component that is “open” or accessible and a component that is “closed” or inaccessible to mobilization. U addition requires a multistage history involving multiple gain or loss of U and/or Pb. In contrast, U loss does not necessarily require multistage processes but can also be explained by preferential removal of ²³⁸U (and ²³⁵U) relative to recoiled daughter isotopes such as ²³⁴U, ²³⁰Th, and ²⁰⁶Pb (and ²⁰⁷Pb) during a single event. Such a behavior could be obtained if the recoiled daughter isotopes of channel-sited uranium are implanted into the crystal lattice and, in such a way, become less mobile than their parent isotopes. This case implies an open-system behavior for ions in the channel sites and a closed-system behavior for ions in the silicate framework of stilbite. Each α-recoil directly or indirectly, i.e., through its recoil cascade, damages the silicate framework. Subsequent (continuous) low-temperature annealing of the damaged stilbite lattice could trap the recoiled daughter isotopes in the repaired crystal lattice or sealed-off channels. Such immobile recoiled material can, in part, represent the “closed” component of the system. This model can account for all observations regarding the Th-U-Pb systematics, including the Th-U disequilibrium systematics, the similarity in Th/U as deduced from Th-U disequilibrium and Pb isotope data, and the excess of radiogenic Pb (²⁰⁸Pb-parents also had been multiply recoiled). These two contrasting explanations involve either multistage or multicomponent systems. They do not permit the derivation of an accurate age.     

Th/U/U and Pa/U ages from a single fossil coral fragment by multi-collector magnetic-sector inductively coupled plasma mass spectrometry

The ²³⁰Th/²³⁴U/²³⁸U age dating of corals via alpha counting or mass spectrometry has significantly contributed to our understanding of sea level, radiocarbon calibration, rates of ocean and climate change, and timing of El Nino, among many applications. Age dating of corals by mass spectrometry is remarkably precise, but many samples exposed to freshwater yield inaccurate ages. The first indication of open-system ²³⁰Th/²³⁴U/²³⁸U ages is elevated ²³⁴U/²³⁸U_initial values, very common in samples older than 100,000 yr. For samples younger than 100,000 yr that have ²³⁴U/²³⁸U_initial values close to seawater, there is a need for age validation. Redundant ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in a single fossil coral fragment are possible by Multi-Collector Magnetic Sector Inductively Coupled Plasma Mass Spectrometry (MC-MS-ICPMS) and standard anion exchange column chemistry, modified to permit the separation of uranium, thorium, and protactinium isotopes from a single solution. A high-efficiency nebulizer employed for sample introduction permits the determination of both ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in fragments as small as 500 mg. We have obtained excellent agreement between ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U ages in Barbados corals (30 ka) and suggest that the methods described in this paper can be used to test the ²³⁰Th/²³⁴U/²³⁸U age accuracy.Separate fractions of U, Th, and Pa are measured by employing a multi-dynamic procedure, whereby ²³⁸U is measured on a Faraday cup simultaneously with all minor isotopes measured with a Daly ion counting detector. The multi-dynamic procedure also permits correcting for both the Daly to Faraday gain and for mass discrimination during sample analyses. The analytical precision of ²³⁰Th/²³⁴U/²³⁸U and ²³¹Pa/²³⁵U dates is generally better than ±0.3% and ±1.5%, respectively (2 Relative Standard deviation [RSD]). Additional errors resulting from uncertainties in the decay constant for ²³¹Pa and from undetermined sources currently limit the ²³¹Pa/²³⁵U age uncertainty to about ±2.5%. U isotope data and ²³⁰Th/²³⁴U/²³⁸U ages agree with National Institute of Standards and Technology (NIST) reference materials and with measurements made by Thermal Ionization Mass Spectrometry (TIMS) in our laboratory.     

New information on radionuclides concentration in phosphorites originating from Tunisia and Algeria

In this study we investigate the radiological hazard of naturally occurring radioactive material in Tunisian and Algerian phosphorite deposits. Eight samples of phosphorite were collected from the phosphorite mines. The Tunisian and Algerian phosphorites occur in the Late Paleocene and Lower Eocene (Ypresian-Lutetian) in age (Béji Sassi 1984 and Zaïer 1999). Activity concentrations in all the samples were measured by alpha spectrometry and gamma spectrometry. Alpha spectrometry analyses show that the specific activity values of ²³⁸U, ²³⁴U and ²³⁵U in the samples of Tunisian phosphorite were 327?±?7 (321–327), 326?±?6 (325–331) and 14.50?±?0.72 (13.90–15.57) Bq kg^?1, respectively. Specific activity measured by gamma spectrometry in the samples of the Tunisian and Algerian phosphorite shows a small difference. Specific activity levels of ⁴⁰K, ²²⁶Ra, ²³²Th, ²³⁵U and ²³⁸U in the phosphorite samples from Tunisia were, respectively, 71.10?±?3.80, 391.54?±?9.39, 60.38?±?3.74, 12.72?±?0.54 and 527.42?±?49.57 Bq kg^?1 and Algeria were 15.72?±?1.73, 989.65?±?12.52, 12.08?±?1.20, 47.50?±?1.52 and 1,148.78?±?7.30 Bq kg^?1, respectively. The measured value of specific activity of ²³²Th and ⁴⁰K in the Tunisian phosphorite samples is relatively higher than that found in the samples of Algerian phosphorite. The measured activity of uranium (²³⁸U) in the Tunisian phosphorite (527?±?49) Bq kg^?1 is lower than in Algerian phosphorite. The measured activity of ²³⁸U in the Tunisian phosphorite samples was (527–1,315?±?65) ²³⁸U Bq kg^?1 which is higher than its maximum background value of 110 Bq kg^?1 in soils of the various countries of the world (Tufail et al. Radiat Meas 41:443–451, 2006). Different geological origins of phosphorites deposits are the main reason for the large spread in worldwide specific activities. The obtained results of uranium concentrations in phosphorites of different types (Algerian and Tunisian) demonstrate that the uranium concentrations are mainly governed by the phosphatic material. The present study reveals that phosphorite deposits contain natural radioactivity higher than background level.     

Processes controlling 234U and 238U isotope fractionation and helium in the groundwater of the St. Lawrence Lowlands,Quebec: The potential role of natural rock fracturing

The goal of this study is to explain the origin of ²³⁴U–²³⁸U fractionation in groundwater from sedimentary aquifers of the St. Lawrence Lowlands (Quebec, Canada), and its relationship with ³He/⁴He ratios, to gain insight regarding the evolution of groundwater in the region. (²³⁴U/²³⁸U) activity ratios, or (²³⁴U/²³⁸U)_act, were measured in 23 groundwater samples from shallow Quaternary unconsolidated sediments and from the deeper fractured regional aquifer of the Becancour River watershed. The lowest (²³⁴U/²³⁸U)_act, 1.14 ± 0.01, was measured in Ca–HCO₃-type freshwater from the Quaternary Shallower Aquifer, where bulk dissolution of the carbonate allows U to migrate into water with little ²³⁴U–²³⁸U isotopic fractionation. The (²³⁴U/²³⁸U)_act increases to 6.07 ± 0.14 in Na–HCO₃–Cl-type groundwater. Preferential migration of ²³⁴U into water by α-recoil is the underlying process responsible for this isotopic fractionation. An inverse relationship between (²³⁴U/²³⁸U)_act and ³He/⁴He ratios has been observed. This relationship reflects the mixing of newly recharged water, with (²³⁴U/²³⁸U)_act close to the secular equilibrium and containing atmospheric/tritiogenic helium, and mildly-mineralized older water (¹⁴C ages of 6.6 kyrs), with (²³⁴U/²³⁸U)_act of ≥6.07 and large amounts of radiogenic ⁴He, in excess of the steady-state amount produced in situ. The simultaneous fractionation of (²³⁴U/²³⁸U)_act and the addition of excess ⁴He could be locally controlled by stress-induced rock fracturing. This process increases the surface area of the aquifer matrix exposed to pore water, from which produced ⁴He and ²³⁴U can be released by α-recoil and diffusion. This process would also facilitate the release of radiogenic helium at rates greater than those supported by steady-state U–Th production in the rock. Consequently, sources internal to the aquifers could cause the radiogenic ⁴He excesses measured in groundwater.     

In search of live Cm in the early solar system

The r-process only nuclide ²⁴⁷Cm decays to ²³⁵U with a characteristic half-life of ∼16 million years. ²⁴⁷Cm is presently extinct, but offers considerable potential as a short-lived r-process chronometer, providing constraints on the time interval between the last r-process nucleo-synthetic event and the formation of the solar system. The existence of “live” ²⁴⁷Cm in the early solar system should be manifested today as variations in ²³⁵U/²³⁸U, provided Cm was chemically fractionated from U when solids formed in the early solar system. Using multiple-collector ICPMS and a high-purity mixed ²³³U-²³⁶U spike to monitor instrumental mass fractionation, we are able to resolve variations in ²³⁵U/²³⁸U at the 1-2 epsilon level (2σ_M; 1 epsilon = 1 part in 10,000) on sample sizes consisting of 20 ng of uranium. Data can be acquired on smaller (<10 ng) samples with ±2-3 epsilon 2σ uncertainties. Uranium isotopic measurements and U, Nd and Sm concentrations were acquired on bulk samples of a suite of carbonaceous chondrites, unequilibrated and equilibrated ordinary chondrites and eucrites, for which conflicting results had previously been obtained. Our results show no well-resolved excursions in ²³⁵U/²³⁸U away from the terrestrial value at the ∼2 epsilon level, and constrain the amount of ²⁴⁷Cm-produced excess ²³⁵U atoms to less than ∼1 × 10⁸ atoms per gram of chondritic meteorite, with respect to terrestrial ²³⁵U/²³⁸U. Large (permil- level) anomalies in ²³⁵U/²³⁸U could, however, be artificially generated in the ordinary chondrites during laboratory processing. Therefore, U may be more susceptible to isotopic fractionation during chemical processing than previously recognized, and may reconcile some of the highly conflicting ε²³⁵U results reported by previous workers for chondritic meteorites. Our results indicate that a timescale of ∼1-2 × 10⁸ years between the last actinide producing r-process event and the formation of the solar system may not be unreasonable based on the ²⁴⁷Cm-²³⁵U system. However, this conclusion is far from robust at this stage because the only bulk meteorites analysed that display strong Nd/U fractionation are highly metamorphosed chondrites that may have experienced a protracted history of redistribution and re-equilibration. The search for “live” ²⁴⁷Cm in the early solar system can now be extended to early-formed condensates and mineral phases displaying strong Cm-U fractionations.     

Trace-element study and uranium-lead dating of perovskite from the Afrikanda plutonic complex, Kola Peninsula (Russia) using LA-ICP-MS

The U-Pb geochronology of perovskite is a powerful tool in constraining the emplacement age of silica-undersaturated rocks. The trace-element and U-Pb isotopic compositions of perovskite from clinopyroxenite and silicocarbonatite from the Afrikanda plutonic complex (Kola, Russia) were determined by laser-ablation inductively-coupled mass-spectrometry (LA-ICP-MS). In addition, the Sr isotopic composition of perovskite was measured by isotope-dilution mass-spectrometry to better constrain the relations between its host rocks. Perovskite from the two rock types shows a different degree of enrichment in Na, Mg, Mn, Pb, Fe, Al, V, rare-earth elements, Zr, Hf, Th, U and Ta. The perovskite ⁸⁷Sr/⁸⁶Sr values are within analytical uncertainty of one another and fall within the range of mantle values. The ²⁰⁶Pb/²³⁸U ages (corrected for common lead using ²⁰⁷Pb-method) of perovskite from silicocarbonatite statistically yield a single population with a weighted mean of 371?±?8 Ma (2σ; MSWD?=?0.071). This age is indistinguishable, within uncertainty, to the clinopyroxenite weighted mean ²⁰⁶Pb/²³⁸U age of 374?±?10 Ma (2σ; MSWD?=?0.18). Our data are in good agreement with the previous geochronological study of the Afrikanda complex. The observed variations in trace-element composition of perovskite from silicocarbonatite and clinopyroxenite indicate that these rocks are not related by crystal fractionation. The Sr isotopic ratios and the fact that the two rocks are coeval suggest that they were either produced from a single parental melt by liquid immiscibility, or from two separate magmas derived at different degrees of partial melting from an isotopically equilibrated, but modally complex mantle source.     

Fission-track ages of four meteorites

A method for selective annealing of cosmic-ray tracks has been developed, permitting determination of fission-track ages in the presence of a large background of cosmic-ray tracks. The mesosiderite Bondoc contains 41 fission tracks/cm², of which about 75% are due to neutron-induced fission of U²³⁵ during cosmic-ray exposure. Its net fission-track age is 140 ± 40 Myr, nearly identical to its cosmic-ray exposure age of 150 Myr. The mesosiderite Mincy has a fission-track age of 1500 ± 400 Myr.Nakhla (nakhlite) contains an excess of apparent fission tracks, which may be either genuine fission tracks from Pu²⁴⁴ or etch pits mimicking fission tracks in length, thermal stability, random orientation, and other characteristics. On the assumption that they are fission tracks, the Pu²⁴⁴/U²³⁸ ratio at the onset of track retention in Nakhla was (3.1 ± 1.3) × 10^?3, nearly an order of magnitude lower than the initial solar system ratio. This may reflect a chemical fractionation of Pu and U, or a late impact or magmatic event. Different minerals of the Washougal howardite have different Pu²⁴⁴/U²³⁸ ratios, from (24 ± 7) × 10^?3 to (2.3 ± 0.7) × 10^?3. This may imply a succession of impacts over a period of time. Additionally, Pu and U may have been chemically fractionated from each other in this meteorite.Shocked meteorites show no consistent pattern in the retentivity of fission tracks and of fissiogenic or radiogenic noble gases. Some meteorites, e.g. Bondoc, Serra de Magé, and Mincy, retain gases more completely than tracks; others, e.g. Nakhla and Allende, retain them less completely.Uranium was determined in feldspar and/or pyroxene from 19 Ca-rich achondrites and mesosiderites. For most, only upper limits of 0.01–0.03 ppb were obtained. Apparently the uranium in these meteorites resides almost exclusively in minor phases, as in terrestrial and lunar rocks.     

Spectroscopic active IVFe3+–VIFe3+ clusters in spinel–magnesioferrite solid solution crystals: a potential monitor for ordering in oxide spinels

Optical absorption spectra (OAS) of synthetic single crystals of the solid solution spinel sensu stricto (s.s.)–magnesioferrite, Mg(Fe³⁺Al_1???y)₂O₄ (0?y?≤ 0.3), have been measured between 12 500 and 28 500?cm^?1. Chemical composition and Fe³⁺ site distribution have been measured by electron microprobe and Mössbauer spectroscopy, respectively. Ferric iron is ordered to the tetrahedral site for samples with small magnesioferrite component, and this ordering is shown to increase with magnesioferrite component. The optical absorption spectra show a strong increase in band intensities with Fe³⁺→Al substitution. Prominent and relatively sharp absorption bands are observed at 25 300 and 21 300?cm^?1, while less intense bands occur at 22 350, 18 900, 17 900 and 15 100?cm^?1. On the basis of band energies, band intensities and the compositional effect on band intensity, as well as structural considerations, we assign the observed bands to electronic transitions in ^IVFe³⁺–^VIFe³⁺clusters. A linear relationship (R ²= 0.99) between the α_net value of the absorption band at 21 300?cm^?1 and [^IVFe³⁺]?·?[^VIFe³⁺] concentration product has been defined: α_net=2.2?+?15.8 [^IVFe³⁺]?·?[^VIFe³⁺]. Some of the samples have been heat-treated between 700 and 1000?°C to investigate the relation between Fe³⁺ ordering and absorption spectra. Increase of cation disorder with temperature is observed, which corresponds to a 4% reduction in the number of active clusters. Due to the high spatial resolution (??～?10?μm), the OAS technique may be used as a microprobe for determination of Fe³⁺ concentration or site partitioning. Potential applications of the technique include analysis of small crystals and of samples showing zonation with respect to total Fe³⁺ and/or ordering.     

Extreme fractionation of 234U238U and 230Th234U in spring waters,sediments, and fossils at the Pomme de Terre Valley,southwestern Missouri

Isotopic fractionation as great as 1600% exists between ²³⁴U and ²³⁸U in spring waters, sediments, and fossils in the Pomme de Terre Valley, southwestern Missouri. The activity ratios of ${}^{234}\text{U}{}^{238}\text{U}$ in five springs range from 7.2 to 16 in water which has been discharged for at least the past 30,000 years. The anomalies in ${}^{234}\text{U}{}^{238}\text{U}$ ratio in deep water have potential usefulness in hydrologic investigations in southern Missouri. Clayey units overlying the spring bog sediments of Trolinger Spring are enriched in ²³⁰Th relative to their parent ²³⁴U by as much as 720%. The results indicate that both preferential displacement via alpha recoil ejection and the preferential emplacement via recoiling and physical entrapment are significant processes that are occurring in the geologic environment.     

Formation and geochemical significance of micrometallic aggregates including fissiogenic platinum group elements in the Oklo natural reactor, Gabon

Metallic aggregates with a size of a few tens μm and consisting mainly of Ru, Rh, Pd, Te, Pb, As, Sb, S and Bi were found in the acid residue of SD37-S2/CD uraninite taken from Oklo natural reactor zone (RZ) 13. Quantitative analyses of major elements using an electron probe microanalyzer and in situ isotopic analyses of Zr, Mo, Ru, Pb and U using a sensitive high-resolution ion microprobe were performed on the metallic aggregates to determine the geochemical behaviors of fission products and actinides and to ascertain the processes of formation of the aggregates in the RZs. The chemical compositions of the aggregates investigated in this study are significantly different from those reported previously, showing lower Pb content and no correlation between the contents of Pb and S in the individual grains. The ²³⁵U/²³⁸U ratios in metallic aggregates vary significantly from 0.00478 to 0.01466, indicating chemical fractionation between U and Pu during the formation of the aggregates. The Pb isotopic data indicate that most of the Pb in the aggregates decayed from 2.05 Ga-old uraninite that existed in the RZ originally and that there was chemical fractionation between U and Pb in some aggregates. The Zr and Mo isotopic ratios, ⁹⁰Zr/⁹¹Zr and ⁹⁵Mo/⁹⁷Mo, for most of the aggregates had small variations, which can be simply explained by constant separate mixing of fissiogenic and nonfissiogenic components. On the other hand, a large variation in the ⁹⁹Ru/¹⁰¹Ru ratio (0.324-1.73) cannot be explained only by a two component mixing theory; thus, chemical fractionation between Tc and Ru during the reactor criticality is suggested. The large variations in the ²³⁵U/²³⁸U and ⁹⁹Ru/¹⁰¹Ru isotopic ratios suggest that the aggregates formed under various redox conditions owing to the radiolysis of water.     

Preferential solution of234U from recoil tracks and234U/238U radioactive disequilibrium in natural waters

A mathematical model to calculate the²³⁴U/²³⁸U activity ratio (AR) in an aqueous phase in contact with rock/soil is presented. The model relies on the supply of²³⁸U by dissolution and that of²³⁴U by dissolution and preferential release from radiation damaged regions (recoil tracks). The model predicts that values of²³⁴U/²³⁸U AR>1 in the aqueous phase can be obtained only from weathering “virgin” surfaces. Thus, to account for the observed steady-state supply of²³⁴U excess to the oceans by the preferential leaching model, ‘virgin’ rock/soil surfaces would have to be continually exposed and weathered. The²³⁸U concentration and²³⁴U/²³⁸U AR in continental waters allow us to estimate the exposure rates of “virgin” rock/soil surfaces.     

Geochemical fixation of rare earth elements into secondary minerals in sandstones beneath a natural fission reactor at Bangombé, Gabon

To study geochemical processes for migration and fixation of fissiogenic rare earth elements (REE) in association with uranium dissolution, in situ isotopic analyses using an ion microprobe were performed on U- and REE-bearing secondary minerals, such as coffinite, françoisite, uraniferous goethite, and uraninite found in a sandstone layer 30 to 110 cm beneath a natural fission reactor at Bangombé, Gabon. Phosphate minerals such as phosphatian coffinite and françoisite with depleted ²³⁵U (²³⁵U/²³⁸U = 0.00609 to 0.00638) contained large amount of fissiogenic light REE, while micro-sized uraninite grains in a solid bitumen aggregate have normal U isotopic values (²³⁵U/²³⁸U = 0.00725) and small amount of fissiogenic REE components. The proportions of fissiogenic and non-fissiogenic REE components in four samples from the core of BAX03 vary in depth ranging from 30 cm to 130 cm beneath the reactor, which suggests mixing between fissiogenic isotopes from the reactor and non-fissiogenic isotopes from original minerals in the sandstone. Significant chemical fractionation was observed between Ce and the other REE in the secondary minerals, which shows evidence of an oxidizing atmosphere during their formation. Pb-isotopic analyses of individual minerals do not directly provide chronological information because of the disturbance of U-Pb decay system due to recent geologic alteration. However, systematic Pb-isotopic results from all of the minerals reveal the mobilization of fissiogenic isotopes, Pb and U from the reactor in association with dolerite dyke intrusion ∼0.798 Ga ago and the formation of the secondary minerals by mixing event between 2.05 Ga-old original minerals and reactor materials due to recent alteration.     

Dependence of radon exhalation on grain size of sedimentary waste

Tailings resulted from sulphuric acid leaching process of uranium from sedimentary rocks contain high concentrations of ²²⁶Ra and its daughters, the most important of which is ²²²Rn. Movement of radon gas out of the tailings is strongly influenced by the physicochemical characteristics of these tailings especially their radium content and the grain size. So, the tailing samples were size fractionated into four sizes (>?250, 250–125, 125–74 and <?74 µm). The natural radioactivity was investigated using hyper-pure germanium detector and solid-state nuclear track detectors (CR-39) for bulk size and after size fractionation. The activity concentrations of different radionuclides in size-fractionated tailing samples have been shown to be strongly dependent on the size of the particles. In the range of >?250 and <?74 µm, the activity concentrations of ²³⁰Th, ²²⁶Ra, ²¹⁴Pb, ²¹⁴Bi, ²¹⁰Pb, ²³²Th and ⁴⁰K increased throughout with decreasing particle size, while that of ²³⁸U, ²³⁴U and ²³⁵U have an opposite effect. The results revealed an inverse relationship between the radon exhalation rate and size fractionation. Also, the results showed a good correlation between radium activity concentration and radon mass exhalation rate.