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.     

An analysis of naturally occurring radionuclides and <Superscript>137</Superscript>Cs in the soils of urban areas using gamma-ray spectrometry

This study of environmental radioactivity was carried out in the soils of an urban area. Naturally occurring gamma-emitting radionuclides and man-made ¹³⁷Cs were found in the soil profiles collected from four parks in the central Belgrade city area and the soil layer was examined every 10 cm and to a depth of 50 cm. Radioisotope activity concentrations (Bq kg^?1) in the samples of urban soil using the gamma-ray spectrometry method were in the range of 14–46 for ²³⁸U, 33–50 for ²²⁶Ra, 29–63 for ²¹⁰Pb, 1.2–3.4 for ²³⁵U, 28–50 for ²³²Th, 424–576 for ⁴⁰K and 0.7–35.8 for ¹³⁷Cs. Some of the basic physicochemical soil properties (pH, organic matter content, calcium-carbonate content, particle size distribution) were determined to investigate the impact on the vertical distribution of radionuclides. The results of this investigation showed that variations of activity concentration ratios of radionuclides that belong to the same (²³⁸U/²²⁶Ra) or different radioactive series (²³²Th/²²⁶Ra; ²³⁵U/²³⁸U), including ²¹⁰Pb/¹³⁷Cs ratios could well be explained by the properties of the soil. Alkaline pH reaction, the accumulation of organic matter in the uppermost and of carbonates in the deepest layers of urban soil had an effect on ²³⁸U/²²⁶Ra, and ²¹⁰Pb/¹³⁷Cs activity concentration ratio values, while ²³²Th/²²⁶Ra and partially ²³⁵U/²³⁸U ratios were associated with the particle sizes vertical distribution. A study of radionuclides in the samples of leaves of two deciduous tree species common for these parks was also conducted and ²¹⁰Pb and ⁴⁰K were found concentrated in leaves rather than other investigated radionuclides.     

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.     

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.     

Naturally occurring radionuclides and their geochemical interactions at a geothermal site in the North German Basin

The activities of the most common, naturally occurring radionuclides ²³⁸U, ²²⁶Ra, ²¹⁰Pb, ²²⁸Ra, ²²⁸Th, and ⁴⁰K were measured by gamma-ray spectrometry in samples from reservoir rocks, geothermal fluids, and mineral precipitates at the geothermal research site Groß Schönebeck (North German Basin). Results demonstrated that the specific activity of the reservoir rock is within the range of the mean concentration in the upper earth crust of <800 Bq/kg for ⁴⁰K and <60 Bq/kg for radionuclides of the ²³⁸U and ²³²Th series, respectively. The geothermal fluid showed elevated activity concentrations (up to 100 Bq/l) for ²²⁶Ra, ²¹⁰Pb, and ²²⁸Ra, as compared to concentrations found in natural groundwater. Their concentration in filter residues even increased up to 100 Bq/g. These residues contain predominantly two different mineral phases: a Sr-rich barite (Sr, BaSO₄) and laurionite (PbOHCl), which both precipitate upon cooling from the geothermal fluid. Thereby they presumably enrich the radionuclides of Ra (by substitution of Ba) and Pb. Analysis of these precipitates further showed an increased ²²⁶Ra/²²⁸Ra ratio from around 1–1.7 during the initial months of fluid production indicating a change in fluid composition over time which can be explained by different contributions of stimulated reservoir rock areas to the overall produced fluid.     

Natural and artificial radioactivity distribution in soil, rock and water of the Central Ashanti Gold Mine, Ghana

Direct gamma spectrometry study was carried out within and around the operational area of the Central Ashanti Gold of Ghana to ascertain the baseline radioactivity levels of naturally occurring radioactive materials (NORM), prior to processing of gold ore at the mine. The average activity concentrations of ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs in the soil/rock samples were 64.3, 68.4, 1243.9 and 3.5 Bqkg^?1, respectively. For the water samples, the average activity concentrations were 2.5, 2.6, 14.7 and 0.7 BqL^?1 for ²³⁸U, ²³²Th, ⁴⁰K and ¹³⁷Cs, respectively. The total annual effective dose to the public was estimated to be 0.141 mSv which is below the ICRP recommended level of 1 mSv for public exposure control. The average radium equivalent activity value was 257.8 Bqkg^?1 in the range of 72.9–402.3 Bqkg^?1. The average values of external and internal indices were 0.7 and 0.8, respectively. The concentrations of U, Th and K were variable in soil and rock samples taken from different locations in the study area with values varying in the range of 0.8–10.9, 2.4–39.4 μg/g and 0.7–6.3 %, respectively. The concentration values of gross-α and gross-β for all the water samples were below the Ghana Standards Board and Who Health Organisation recommended guideline values for drinking water quality. The results obtained in this study shows that radiation levels are within the natural background radiation levels found in literature and compared well with similar studies for other countries.     

Investigation of natural background radiation of sediments in Rameswaram Island,Tamil Nadu,India

The aim of the study is to assess the natural background radiation in and around Rameswaram Island. In this context, samples were collected to measure the gamma radiations of ²³⁸U, ²³²Th, and ⁴⁰K using NaI(Tl) detector-based gamma ray spectrometer. The average activity concentrations of ²³⁸U, ²³²Th, and ⁴⁰K are noted to be well below the world average values. The calculated absorbed dose rate, radium equivalent activity, and hazard index values were below the prescribed limit. The grain size of the sediment was analyzed following Trefethen’s nomenclature, and its correlation with the natural background radioactivity was studied. The sample that contained clay show elevated activity of ⁴⁰K. The percentage of heavy minerals shows concomitant variation in natural radioactivity, especially in the activity of ²³⁸U and ²³²Th.     

Natural radioactivity levels and evaluation of radiological hazards from Beni Haroun dam sediment samples,northeast Algeria

Levels of naturally occurring radioactivity in sediment samples of Beni Haroun dam have been investigated. The activity concentrations of ²³⁸U and ²³²Th decay chains and ⁴⁰K primordial radionuclide have been measured using high-resolution HPGe detector. Activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K radionuclides were found in the ranges 9–66, 14–37, and 177–288 Bq/kg with the mean values 24.67, 25.98, and 208.10 Bq/kg, respectively. Radiological hazard parameters were estimated based on the activity concentrations for ²²⁶Ra, ²³²Th, and ⁴⁰K to find out any radiation hazard associated with the sediments. Correlation studies between pairs of radionuclides were performed and discussed, and the obtained results are compared with international recommended values.     

Radioactivity in sediments and gross alpha–beta activities in surface water of Fırtına River, Turkey

The concentrations and distribution of natural and artificial radionuclides in sediment and water samples collected from Fırtına River in the Eastern Black Sea region of Turkey were investigated with an aim of evaluating the environmental radioactivity and radiation hazard. Natural gross α and gross β activities were determined for 21 different water samples, and the activity concentrations were obtained for ²²⁶Ra, ²¹⁴Pb, ²¹⁴Bi, ²²⁸Ac, ²⁰⁸Tl, ⁴⁰K and ¹³⁷Cs in 20 different sediment samples. The obtained results showed that natural gross α and gross β activity concentrations in water samples range from 12.4 ± 3.4 to 66.2 ± 9.2 mBq l⁻¹ and from 27.9 ± 3.3 to 133.3 ± 4.1 mBq l⁻¹, respectively. The mean activity concentrations were 32.6 ± 3.8 mBq l⁻¹ for gross α and 69.9 ± 4.4 mBq l⁻¹ for gross β. Generally, the gross β activities were higher than the corresponding gross α activities. The average concentrations of ²³⁸U and ²³²Th daughter products vary from 11 to 167 Bq kg⁻¹ and from 16 to 107 Bq kg⁻¹, respectively. The concentrations of ⁴⁰K and ¹³⁷Cs vary from 51 to 1,605 Bq kg⁻¹ and from 0.8 to 42 Bq kg⁻¹, respectively. Sediment characterization was also investigated using grain size, thin section and XRD analysis.     

Radionuclides measurements and mineralogical studies on beach sands, East Rosetta Estuary, Egypt

Radiometric measurements were carried out for the beach sands from East Rosetta estuary to determine the activity concentrations of 238 U, 226 Ra, 232 Th, and 40 K, using a Hyper Pure Germanium spectrometer, to estimate the dose rates and radiation hazard indices. The average specific activities are 778.20 Bq/kg for 238 U; 646.89 Bq/kg for 226 Ra; 621.92 and 627.85 Bq/kg for the 222 Rn daughters 214 Pb and 214 Bi respectively. The average specific activity of 232 Th is 1510.25 Bq/kg, while the calculated specific activity for 40 K has an average of 8.41 Bq/kg. The average specific activity of 235 U is 38.61 Bq/kg. The average absorbed dose rate is 1211.36 nGy/h, 20 times higher than the estimated average global primordial radiation of 60 nGy/h and 6 times higher than that of the world range (10-200 nGy/h). The radium equivalent (Ra eq ) values are from 6 to 9 times the recommended value. The internal and external hazard indices (H int , H ex ) indicate that their values are from 6 to 11 times the permissible values of these indices. These higher values may be due to the presence of economic heavy minerals containing radionuclides as zircon and monazite as well as some trace minerals, thorite and uranothorite. The mineralogical study indicates the beach sands contain heavy minerals, zircon, monazite, rutile, ilmenite, leucoxene, magnetite and garnet. The average abundance of zircon is 0.175 wt% ranging from 0.125 wt% to 0.239 wt%, while it is 0.004wt% ranging from 0.001 wt% to 0.007 wt% for monazite. The average abundance is 0.087 wt% for rutile; 2.029 wt% for ilmenite; 1.084 wt% for magnetite; 0.384 wt% for leucoxene and 0.295 wt% for garnet.     

Disturbance versus preservation of U–Th–Pb ages in monazite during fluid–rock interaction: textural, chemical and isotopic in situ study in microgranites (Velay Dome, France)

Monazite is extensively used to date crustal processes and is usually considered to be resistant to diffusive Pb loss. Nevertheless, fluid-assisted recrystallisation is known to be capable of resetting the monazite chronometer. This study focuses on chemical and isotopic disturbances in monazite grains from two microgranite intrusions in the French Central Massif (Charron and Montasset). Petrologic data and oxygen isotopes suggest that both intrusions have interacted with alkali-bearing hydrothermal-magmatic fluids. In the Charron intrusion, regardless of their textural location, monazite grains are sub-euhedral and cover a large domain of compositions. U–Pb chronometers yield a lower intercept age of 297 ± 4 Ma. An inherited component at 320 Ma is responsible for the scattering of the U–Th–Pb ages. The Montasset intrusion was later affected by an additional F-rich crustal fluid with crystallisation of Ca-REE-fluorocarbonates, fluorite, calcite and chloritisation. Pristine monazite is chemically homogeneous and displays ²⁰⁸Pb/²³²Th and ²⁰⁶Pb/²³⁸U concordant ages at 307 ± 2 Ma. By contrast, groundmass monazite shows dissolution-recrystallisation features associated with apatite and thorite precipitation (Th-silicate) and strong chemical reequilibration. ²⁰⁸Pb/²³²Th ages are disturbed and range between 270 and 690 Ma showing that the Th/Pb ratio is highly fractionated during the interaction with fluids. Apparent U–Pb ages are older due to common Pb incorporation yielding a lower intercept age at 312 ± 10 Ma, the age of the pristine monazite. These results show that F-rich fluids are responsible for Th mobility and incorporation of excess Pb, which thus strongly disturbed the U–Th–Pb chronometers in the monazite.     

Zircon M257 ‐ a Homogeneous Natural Reference Material for the Ion Microprobe U‐Pb Analysis of Zircon

We introduce and propose zircon M257 as a future reference material for the determination of zircon U‐Pb ages by means of secondary ion mass spectrometry. This light brownish, flawless, cut gemstone specimen from Sri Lanka weighed 5.14 g (25.7 carats). Zircon M257 has TIMS‐determined, mean isotopic ratios (2s uncertainties) of 0.09100 ± 0.00003 for ²⁰⁶pb/²³⁸U and 0.7392 ± 0.0003 for ²⁰⁷pb/²³⁵U. Its ²⁰⁶pb/²³⁸U age is 561.3 ± 0.3 Ma (unweighted mean, uncertainty quoted at the 95% confidence level); the U‐Pb system is concordant within uncertainty of decay constants. Zircon M257 contains ～ 840 μg g^?1 U (Th/U ～ 0.27). The material exhibits remarkably low heterogeneity, with a virtual absence of any internal textures even in cathodoluminescence images. The uniform, moderate degree of radiation damage (estimated from the expansion of unit‐cell parameters, broadening of Raman spectral parameters and density) corresponds well, within the “Sri Lankan trends”, with actinide concentrations, U‐Pb age, and the calculated alpha fluence of 1.66 × 10¹⁸ g^?1. This, and a (U+Th)/He age of 419 ± 9 Ma (2s), enables us to exclude any unusual thermal history or heat treatment, which could potentially have affected the retention of radiogenic Pb. The oxygen isotope ratio of this zircon is 13.9%o VSMOW suggesting a metamorphic genesis in a marble or calc‐silicate skarn.     

Determination of radioactivity levels in Akhisar,Gördes,Gölmarmara and Sindirgi regions,Western Turkey

In this study, radioactivity measurements in the environment of Akhisar, Gölmarmara, Gördes and Sindirgi regions in Western Turkey were investigated in order to evaluate the implications of any excess radioactivity in the environment of geological formation. The radioactivity concentrations of ⁴⁰K, ²³⁸U and ²³²Th radionuclides in the soil samples were measured by a NaI(Tl) gamma spectrometer system, and the radium activity concentrations in the water samples were also analyzed by an ZnS(Ag) alpha counter by the collector chamber method. The radioactivity of ⁴⁰K, ²³⁸U and ²³²Th in soils ranged 2.80–2,347.77, 9.90–256.19 and 9.66–106.53 Bq kg^?1, respectively. The activity of ²²⁶Ra in the water samples ranged from 0.03 Bq L^?1 (0.89pCi/L) to 0.80 Bq L^?1 (21.58pCi/L). In addition, the external terrestrial gamma dose rate in air (nGy h^?1), annual effective dose rate (mSv year^?1) and radium equivalent activity (Bq kg^?1) were calculated and compared with international standard values.     

In situ gamma ray measurements for deciphering of radioactivity level in Sarıhan pluton area of northeastern Turkey

The present work utilizes in situ gamma ray spectrometric measurement data to map the surface geology of Sar?han Granitoid and its surrounding area. The study area comprises three different lithological units, namely, Hozbirikyayla Formation (limestone and sandy limestones), Sar?han Granitoid (consist of quartz monzodiorite, granodiorite and quartz diorite) and the Ophiolitic olistostromal melange (andesite, basalt, sandstone, gravelly sandstone). When lithological units are assessed according to the radioactivity characteristics, natural radionuclide contents (⁴⁰K and radionuclides from ²³⁸U and ²³²Th series) of Hozbirikyayla limestones and ophiolitic melange rocks are lower than the Sar?han pluton. The U, Th and K radionuclide contents were found to be 0.8–5.4 ppm, 10.1–33.6 ppm and 1.29–4.41% in the Sar?han plutonic area and 0.9–5.3 ppm, 1.1–20.3 ppm and 0.04–2.71% in Horzbirikyayla formation, respectively. The element concentrations of ²³⁸U, ²³²Th and ⁴⁰K of the Ophiolitic melange are 1.1–4.5 ppm, 1.6–25.3 ppm and 0.09–3.63%, respectively. Radioelement ratio maps are created for the studied area, because the parameters of radioelement ratios, eU/eTh, eU/K and eTh/K, reflect the radioactive characters of the rock and soil. The Hozbirikyayla Formation is characterized by the highest value of eU/eTh and lowest value of eTh/K. While the lowest eU/eTh and eU/K ratios were observed in the Sar?han Granodiorite, the highest value of eU/K and eTh/K were obtained in the Ophiolitic olistostromal melange. By comparing these maps with the geology, it was found that the radioelement concentrations are in good agreement with the geological properties of the region. In addition to this, the radiation hazard parameters were evaluated to assess the radiation hazard for people living in this area. It has also been found that there is no significant radiologic hazard for humans and the environment in and around studied area.     

Assessment of natural radioactivity,associated radiological health hazards indices and soil-to-crop transfer factors in cultivated area around a fertilizer factory in Onne,Nigeria

Concentration of natural radionuclides in three major staple food crops cultivated around a fertilizer plant in Onne, Rivers State Nigeria and the cultivated soil samples were determined using gamma spectroscopy operated on a Canberra vertical high purity 3″ × 3″ NaI(TI) detector. The average activity concentration of ²³⁸U, ²³²Th and ⁴⁰K was determined, for cassava flour (U 19.3 ± 5.0, Th 11.4 ± 3.3, K 426.9 ± 33.8) Bq kg^?1, for yam flour (U 6.3 ± 1.8, Th 8.4 ± 2.6, K 227.0.9 ± 27.3) Bq kg^?1 while for cocoyam flour (U 7.5 ± 2.7, Th 7.1 ± 2.3, K 195.8 ± 25.83) Bq kg^?1. The mean activity concentration for soil samples is 18.7 ± 3.7 Bq kg^?1, 18.0 ± 3.8 Bq kg^?1 and 308.4 ± 22.4 Bq kg^?1 for ²³⁸U, ²³²Th and ⁴⁰K, respectively. These values obtained show enhanced ⁴⁰K concentration which is attributed to the effluent discharge from a fertilizer plant and its applications to farmlands, but ²³⁸U, ²³²Th values are well within the global average and values reported in some regions and countries of the world. Radiation hazard indices obtained to estimate potential radiological health risk in both foodstuffs and soil samples are well below their permissible limit as set by UNSCEAR [Sources and effects of ionizing radiation (Report to the General Assembly), 2000]. The rate of radionuclides transfer from soil to crops was moderate with mean transfer factors of ²³²Th < ²³⁸U < ⁴⁰K.     

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.     

Natural radionuclide mobility and its influence on U-Th-Pb dating of secondary minerals from the unsaturated zone at Yucca Mountain, Nevada

Extreme U and Pb isotope variations produced by disequilibrium in decay chains of ²³⁸U and ²³²Th are found in calcite, opal/chalcedony, and Mn-oxides occurring as secondary mineral coatings in the unsaturated zone at Yucca Mountain, Nevada. These very slowly growing minerals (mm my⁻¹) contain excess ²⁰⁶Pb and ²⁰⁸Pb formed from excesses of intermediate daughter isotopes and cannot be used as reliable ²⁰⁶Pb/²³⁸U geochronometers. The presence of excess intermediate daughter isotopes does not appreciably affect ²⁰⁷Pb/²³⁵U ages of U-enriched opal/chalcedony, which are interpreted as mineral formation ages.Opal and calcite from outer (younger) portions of coatings have ²³⁰Th/U ages from 94.6 ± 3.7 to 361.3 ± 9.8 ka and initial ²³⁴U/²³⁸U activity ratios (AR) from 4.351 ± 0.070 to 7.02 ± 0.12, which indicate ²³⁴U enrichment from percolating water. Present-day ²³⁴U/²³⁸U AR is ∼1 in opal/chalcedony from older portions of the coatings. The ²⁰⁷Pb/²³⁵U ages of opal/chalcedony samples range from 0.1329 ± 0.0080 to 9.10 ± 0.21 Ma, increase with microstratigraphic depth, and define slow long-term average growth rates of about 1.2-2.0 mm my⁻¹, in good agreement with previous results. Measured ²³⁴U/²³⁸U AR in Mn-oxides, which pre-date the oldest calcite and opal/chalcedony, range from 0.939 ± 0.006 to 2.091 ± 0.006 and are >1 in most samples. The range of ⁸⁷Sr/⁸⁶Sr ratios (0.71156-0.71280) in Mn-oxides overlaps that in the late calcite. These data indicate that Mn-oxides exchange U and Sr with percolating water and cannot be used as a reliable dating tool.In the U-poor calcite samples, measured ²⁰⁶Pb/²⁰⁷Pb ratios have a wide range, do not correlate with Ba concentration as would be expected if excess Ra was present, and reach a value of about 1400, the highest ever reported for natural Pb. Calcite intergrown with opal contains excesses of both ²⁰⁶Pb and ²⁰⁷Pb derived from Rn diffusion and from direct α-recoil from U-rich opal. Calcite from coatings devoid of opal/chalcedony contains ²⁰⁶Pb and ²⁰⁸Pb excesses, but no appreciable ²⁰⁷Pb excesses. Observed Pb isotope anomalies in calcite are explained by Rn-produced excess Pb. The Rn emanation may strongly affect ²⁰⁶Pb-²³⁸U ages of slow-growing U-poor calcite, but should be negligible for dating fast-growing U-enriched speleothem calcite.     

Alpha-recoil in U–Pb geochronology: effective sample size matters

Displacement of the daughter isotope by a-recoil results in an open system on the nanoscale. For a heterogeneous distribution of U and Th, this redistribution of intermediate and stable daughter isotopes results in subvolumes with a deficit of Pb and others with an excess of Pb. Whether such heterogeneities affect the analyzed U–Pb system depends on: (1) the volume of the analyzed sample, (2) the degree and scale of heterogeneity in the U and Th distribution, and (3) the analytical procedure. Spatial separation of parent and daughter through a-recoil affects the U–Pb systematics of leached samples, where leaching gives access to domains less than 1 µm wide. Anomalous data patterns originating from recoil induced parent-to-daughter fractionation are more important if there are strong heterogeneities in the U and Th distribution, whereby Pb excess appears more pronounced than Pb deficit. Fractionation of parent and daughter elements through selective dissolution of U-REE-rich growth zones in zircon and U-inclusions in columbite, as well as the presence of U–Th-rich micro-inclusions in silicates dated using a step-leaching scheme, may result in anomalous ²⁰⁷Pb _rad/ ²⁰⁶Pb _rad, scattered ²⁰⁶Pb _rad/ ²³⁸U and ²⁰⁷Pb _rad/ ²³⁵U, and reverse discordance. The accumulated structural damage controls the leaching and dissolution behavior, but may also influence the non-stoichiometric element mobilization during sputtering or ablation in the analysis of U-rich samples by SHRIMP and LA-MC-ICP-MS.     

Origin of zircon in jadeitite from the Nishisonogi metamorphic rocks,Kyushu, Japan

On the basis of internal structures, laser ablation U–Pb ages and trace element compositions, the origin of zircon in jadeitite in the Nishisonogi metamorphic rocks was examined. The zircon comprises euhedral zoned cores overgrown by euhedral rims. The cores contain inclusions of muscovite, quartz, albite and possibly K‐feldspar, yield ²³⁸U–²⁰⁶Pb ages of 126 ± 6 Ma (±2 SD, n = 45, MSWD = 1.0), and have Th/U ratios of 0.48–1.64. The rims contain inclusions of jadeite, yield ²³⁸U–²⁰⁶Pb ages of 84 ± 6 Ma (±2 SD, n = 14, MSWD = 1.1), and have Th/U ratios of <0.06. The cores are richer in Y, Th, Ti and rare earth elements (REEs), but the rims are richer in Hf and U. Chondrite‐normalized REE patterns of the cores indicate higher Sm_N/La_N ratios, lower Yb_N/Gd_N ratios and larger positive Ce anomalies compared with those of the rims. Thus, the cores and rims have different ²³⁸U–²⁰⁶Pb ages and trace element compositions, suggesting two stages of zircon growth. Although the ²³⁸U–²⁰⁶Pb ages of the rims are consistent with the reported ⁴⁰Ar/³⁹Ar spot‐fusion ages of matrix muscovite in the jadeitite, the ²³⁸U–²⁰⁶Pb ages of the cores are older. The mineral inclusions and high Th/U ratios in the cores are best explained by crystallization from felsic magma. Therefore, the cores are considered relicts from igneous precursor rocks. The rims surrounding the inherited cores possibly precipitated from aqueous fluids during jadeitite formation. The elevated U concentrations in the rims suggest that infiltration of external fluids was responsible for the precipitation. This study provides an example of jadeitite formation by metasomatic replacement of a protolith.     

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.