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Uranium-series disequilibria as a means to study recent migration of uranium in a sandstone-hosted uranium deposit, NW China.

Uranium concentration and alpha specific activities of uranium decay series nuclides (234)U, (238)U, (230)Th, (232)Th and (226)Ra were measured for 16 oxidized host sandstone samples, 36 oxic-anoxic (mineralized) sandstone samples and three unaltered primary sandstone samples collected from the Shihongtan deposit. The results show that most of the ores and host sandstones have close to secular equilibrium alpha activity ratios for (234)U/(238)U, (230)Th/(238)U, (230)Th/(234)U and (226)Ra/(230)Th, indicating that intensive groundwater-rock/ore interaction and uranium migration have not taken place in the deposit during the last 1.0 Ma. However, some of the old uranium ore bodies have locally undergone leaching in the oxidizing environment during the past 300 ka to 1.0 Ma or to the present, and a number of new U ore bodies have grown in the oxic-anoxic transition (mineralized) subzone during the past 1.0 Ma. Locally, uranium leaching has taken place during the past 300 ka to 1.0 Ma, and perhaps is still going on now in some sandstones of the oxidizing subzone. However, uranium accumulation has locally occurred in some sandstones of the oxidizing environment during the past 1 ka to 1.0 Ma, which may be attributed to adsorption of U(VI) by clays contained in oxidized sandstones. A recent accumulation of uranium has locally taken place within the unaltered sandstones of the primary subzone close to the oxic-anoxic transition environment during the past 300 ka to 1.0 Ma. Results from the present study also indicate that uranium-series disequilibrium is an important tool to trace recent migration of uranium occurring in sandstone-hosted U deposits during the past 1.0 Ma and to distinguish the oxidation-reduction boundary.

Journal Article↗

Uranium ores and depleted uranium in the environment, with a reference to uranium in the biosphere from the Erzgebirge/Sachsen, Germany.

The Erzgebirge ('Ore Mountains') area in the eastern part of Germany was a major source of uranium for Soviet nuclear programs between 1945 and 1989. During this time, the former German Democratic Republic became the third largest uranium producer in the world. The high abundance of uranium in the geological formations of the Erzgebirge are mirrored in the discovery of uranium by M. Klaproth close to Freiberg City in 1789 and the description of the so-called 'Schneeberg' disease, lung cancer caused in miners by the accumulation of the uranium decay product, radon, in the subsurfaces of shafts. Since 1991, remediation and mitigation of uranium at production facilities, rock piles and mill tailings has taken place. In parallel, efforts were initiated to assess the likely adverse effects of uranium mining to humans. The costs of these activities amount to about 6.5 10(9) Euro. A comparison with concentrations of depleted uranium at certain sites is given.

Costs and Cost Analysis↗

Uranium and uranium decay series radionuclide dynamics in bone of rats following chronic uranium ore dust inhalation.

The accumulation and release of uranium and some uranium decay chain radionuclides were measured in the bones of rats that had been chronically exposed to inhaled uranium ore dust during the first half (approximately) of their natural adult lifespan. Endochondral bone (femur, tibia, humerus, radius, and ulna), membrane bone (skull roofing bones) and muscle of Sprague-Dawley rats (n = 55) that died at various times up to 65 weeks after the end of chronic inhalation of uranium ore dust aerosol (4.2 h d(-1) for 65 wk) and from age matched controls (n = 10), were analyzed for uranium, 230Th, 226Ra, 210Pb, and 210Po. Overall, during the period of dust inhalation, the nuclides accumulated in the above order of decreasing concentration in dry bone. However, the results demonstrate that there was some differential accumulation of uranium and uranium decay series radionuclides in muscle and two bone types of rats during the chronic inhalation period. The data also show that the bone levels of some, but not all, radionuclides decreased significantly with time after inhalation ceased. Lung uranium concentration at the time of death was a highly significant covariant for temporal changes in the levels of some radionuclides in both endochondral bone and membrane bone, indicating that lung remained a major source of these isotopes for accumulation in these bone types after ore dust inhalation had ceased. For some isotopes, the two bone types behaved differently during the dust inhalation period, and differently again after the dust inhalation ceased. The relative behavior of one bone type compared to the other for a particular isotope during the dust inhalation period did not predict the relative behavior after dust inhalation ceased. However, a faster accumulation of one bone type compared to the other for a particular isotope during the dust inhalation period predicted a faster decrease after dust inhalation ended.

Administration, Inhalation↗

Elevated urine uranium excretion by soldiers with retained uranium shrapnel.

The use of depleted uranium in munitions has given rise to a new exposure route for this chemically and radioactively hazardous metal. A cohort of U.S. soldiers wounded while on or in vehicles struck by depleted uranium penetrators during the Persian Gulf War was identified. Thirty-three members of this cohort were clinically evaluated, with particular attention to renal abnormalities, approximately 3 y after their injury. The presence of retained shrapnel was identified by x ray, and urine uranium concentrations were measured on two occasions. The absorption of uranium from embedded shrapnel was strongly suggested by measurements of urine uranium excretion at two time intervals: one in 1993/1994 and one in 1995. Mean urine uranium excretion was significantly higher in soldiers with retained shrapnel compared to those without shrapnel at both time points (4.47 vs. 0.03 microg g(-1) creatinine in 1993/1994 and 6.40 vs. 0.01 microg g(-1) creatinine in 1995, respectively). Urine uranium concentrations measured in 1995 were consistent with those measured in 1994/1993, with a correlation coefficient of 0.9. Spot urine measurements of uranium excretion were also well correlated with 24-h urine collections (r = 0.95), indicating that spot urine samples can be reliably used to monitor depleted uranium excretion in the surveillance program for this cohort of soldiers. The presence of uranium in the urine can be used to determine the rate at which embedded depleted uranium fragments are releasing biologically active uranium ions. No evidence of a relationship between urine uranium excretion and renal function could be demonstrated. Evaluation of this cohort continues.

Amputation, Surgical↗

Influence of uranium(VI) speciation for the evaluation of in vitro uranium cytotoxicity on LLC-PK1 cells.

Very few data are available concerning the in vitro toxicity of uranium. In this work, we have determined the experimental chemical conditions permitting the observation of uranium(VI) cytotoxicity on LLC-PK1 cells. Uranium solutions made either by dissolving uranyl acetate or nitrate crystals, or by complexing uranium with bicarbonate, phosphate or citrate ligands, were prepared and tested. Experiments demonstrated that only uranium solutions containing citrate and bicarbonate ligands concentrations tenfold higher than the metal, were soluble in the cell culture medium. Cytotoxicity studies of all these uranium compounds were performed on LLC-PK1 cells and compared using LDH release, neutral red uptake and MTT assays. Dose dependent cytotoxicity curves were only obtained with uranium-bicarbonate medium. This study has revealed a toxicity of uranium-bicarbonate complexes for 24 h expositions and for concentrations ranging from 7 x 10(-4)-10(-3) M, under these conditions, the CI50 (cytotoxicity index) was evaluated between 8.5 and 9 x 10(-4) M. In contrast, we noticed a lack of cytotoxicity response for uranium(VI)-citrate complexes. Electron transmission microscopy studies revealed, when LLC-PK1 cells were exposed to the uranium-bicarbonate system, that uranium penetrated and precipitated within the cytoplasmic compartment. Morphological studies conducted with citrate complexes did not show any cellular intake of uranium.

Animals↗

Uranium tris-aryloxide derivatives supported by triazacyclononane: engendering a reactive uranium(III) center with a single pocket for reactivity.

The synthesis and spectroscopic characterization of the mononuclear uranium complex [((ArO)(3)tacn)U(III)(NCCH(3))] is reported. The uranium(III) complex reacts with organic azides to yield uranium(IV) azido as well as uranium(V) imido complexes, [((ArO)(3)tacn)U(IV)(N(3))] and [((ArO)(3)tacn)U(V)(NSi(CH(3))(3))]. Single-crystal X-ray diffraction, spectroscopic, and computational studies of this analogous series of uranium tris-aryloxide complexes supported by triazacyclononane are described. The hexadentate, tris-anionic ligand coordinates to the large uranium ion in unprecedented fashion, engendering coordinatively unsaturated and highly reactive uranium centers. The macrocyclic triazacyclononane tris-aryloxide derivative occupies six coordination sites, with the three aryloxide pendant arms forming a trigonal plane at the metal center. DFT quantum mechanic methods were applied to rationalize the reactivity and to elucidate the electronic structure of the newly synthesized compounds. It is shown that the deeply colored uranium(III) and uranium(V) species are stabilized via pi-bonding interaction, involving uranium f-orbitals and the axial acetonitrile and imido ligand, respectively. In contrast, the bonding in the colorless uranium(IV) azido complex is purely ionic in nature. The magnetism of the series of complexes with an [N3O3-N(ax)] core structure and oxidation states +III, +IV, and +V is discussed in context of the electronic structures.

Heterocyclic Compounds, Bridged-Ring↗

Determination of irradiated reactor uranium in soil samples in Belarus using 236U as irradiated uranium tracer.

This work presents experimental results on the distribution of irradiated reactor uranium from fallout after the accident at Chernobyl Nuclear Power Plant (NPP) in comparison to natural uranium distribution in different soil types. Oxidation processes and vertical migration of irradiated uranium in soils typical of the 30 km relocation area around Chernobyl NPP were studied using 236U as the tracer for irradiated reactor uranium and inductively coupled plasma mass spectrometry as the analytical method for uranium isotope ratio measurements. Measurements of natural uranium yielded significant variations of its concentration in upper soil layers from 2 x 10(-7) g g(-1) to 3.4 x 10(-6) g g(-1). Concentrations of irradiated uranium in the upper 0-10 cm soil layers at the investigated sampling sites varied from 5 x 10(-12) g g(-1) to 2 x 10(-6) g g(-1) depending on the distance from Chernobyl NPP. In the majority of investigated soil profiles 78% to 97% of irradiated "Chernobyl" uranium is still contained in the upper 0-10 cm soil layers. The physical and chemical characteristics of the soil do not have any significant influence on processes of fuel particle destruction. Results obtained using carbonate leaching of 236U confirmed that more than 60% of irradiated "Chernobyl" uranium is still in a tetravalent form, ie. it is included in the fuel matrix (non-oxidized fuel UO2). The average value of the destruction rate of fuel particles determined for the Western radioactive trace (k = 0.030 +/- 0.005 yr(-1)) and for the Northern radioactive trace (k = 0.035 + 0.009 yr(-1)) coincide within experimental errors. Use of leaching of fission products in comparison to leaching of uranium for study of the destruction rate of fuel particles yielded poor coincidence due to the fact that use of fission products does not take into account differences in the chemical properties of fission products and fuel matrix (uranium).

Environmental Monitoring↗

Solubility characterization of airborne uranium from a uranium recycling plant.

Solubility profiles of uranium dusts in a uranium recycling plant were determined by performing in vitro solubility tests on breathing zone air samples conducted in all process areas of the processing plant. The recycling plant produces high density shields, closed end tubes that are punched and formed from uranium sheet metal, and high-fired uranium oxide, which is used as a catalyst. The recycled uranium is cut and melted in a vacuum furnace, and part of the molten uranium is poured into molds for further processing. Air samples were taken in process areas under normal working conditions. The dissolution rate of the uranium in a simulant solution of extracellular airway lining fluid (Gamble's solution) was then determined over the next 28 d. Airborne uranium in the oxide section of the plant was found to be highly insoluble with 99% of the uranium having a dissolution half time in excess of 100 d. The solubility of the airborne uranium in other areas of the facility was only slightly more soluble with over 90% of the airborne uranium having dissolution half times in excess of 90 d.

Air Pollutants, Occupational↗

Decontamination of uranium-contaminated steel surfaces by hydroxycarboxylic acid with uranium recovery.

We developed a simple, safe method to remove uranium from contaminated metallic surfaces so that the materials can be recycled or disposed of as low-level radioactive or nonradioactive waste. Surface analysis of rusted uranium-contaminated plain carbon-steel coupons by X-ray photoelectron spectroscopy and Rutherford backscattering spectroscopy showed that uranium was predominantly associated with ferrihydrite, lepidocrocite, and magnetite, or occluded in the matrix of the corrosion product as uranyl hydroxide and schoepite (UO3 x 2H2O). Citric acid formulations, consisting of oxalic acid-hydrogen peroxidecitric acid (OPC) or citric acid-hydrogen peroxidecitric acid (CPC), were used to remove uranium from the coupons. The efficiency of uranium removal varied from 68% to 94% depending on the extent of corrosion, the association of uranium with the iron oxide matrix, and the accessibility of the occluded contaminant. Decontaminated coupons clearly showed evidence of the extensive removal of rust and uranium. The waste solutions containing uranium and iron from decontamination by OPC and CPC were treated first by subjecting them to biodegradation followed by photodegradation. Biodegradation of a CPC solution by Pseudomonas fluorescens resulted in the degradation of the citric acid with concomitant precipitation of Fe (>96%), whereas U that remained in solution was recovered (>99%) by photodegradation as schoepite. In contrast, in an OPC solution citric acid was biodegraded but not oxalic acid, and both Fe and U remained in solution. Photodegradation of this OPC solution resulted in the precipitation of iron as ferrihydrite and uranium as uranyl hydroxide.

Biodegradation, Environmental↗

Distribution of uranium in rats implanted with depleted uranium pellets.

During the Persian Gulf War, soldiers were injured with depleted uranium (DU) fragments. To assess the potential health risks associated with chronic exposure to DU, Sprague Dawley rats were surgically implanted with DU pellets at 3 dose levels (low, medium and high). Biologically inert tantalum (Ta) pellets were used as controls. At 1 day and 6, 12, and 18 months after implantation, the rats were euthanized and tissue samples collected. Using kinetic phosphorimetry, uranium levels were measured. As early as 1 day after pellet implantation and at all subsequent sample times, the greatest concentrations of uranium were in the kidney and tibia. At all time points, uranium concentrations in kidney and bone (tibia and skull) were significantly greater in the high-dose rats than in the Ta-control group. By 18 months post-implantation, the uranium concentration in kidney and bone of low-dose animals was significantly different from that in the Ta controls. Significant concentrations of uranium were excreted in the urine throughout the 18 months of the study (224 +/- 32 ng U/ml urine in low-dose rats and 1010 +/- 87 ng U/ml urine in high-dose rats at 12 months). Many other tissues (muscle, spleen, liver, heart, lung, brain, lymph nodes, and testicles) contained significant concentrations of uranium in the implanted animals. From these results, we conclude that kidney and bone are the primary reservoirs for uranium redistributed from intramuscularly embedded fragments. The accumulations in brain, lymph nodes, and testicles suggest the potential for unanticipated physiological consequences of exposure to uranium through this route.

Animals↗

The utility of spot collection for urinary uranium determinations in depleted uranium exposed Gulf War veterans.

The utility of spot urine collections for uranium bioassay determinations was examined in a small cohort of depleted uranium exposed Gulf War veterans. Some members of the group are excreting elevated concentrations of urinary uranium resulting from the metabolism of retained metal fragments, the residua of several friendly fire incidents. Uranium determinations were performed on both 24-h timed collections and spot urine samples using kinetic phosphorescence analyzer (KPA) methodology. Results ranged from non-detectable to 30.7 mcg g(-1) creatinine in a 24-h collection. A creatinine-standardized spot sample and a 24-h uncorrected sample both correlated highly (R2=0.99) with a creatinine corrected 24-h collection, presumed to be the best estimate of the urinary uranium measure. This relationship was upheld when the population was stratified by uranium concentration into a high uranium group (> or = 0.05 mcg U/g creatinine) but for the lower uranium group (< 0.05 mcg U/g creatinine) more variability and a lower correlation was seen. The uncorrected spot sample, unadjusted for volume, concentration or creatinine had the lowest correlation with the 24-h creatinine adjusted result, especially at lower urinary uranium concentrations. This raises questions regarding the representativeness of such a sample in bioassay programs.

Adult↗

Uranium-series disequilibrium dating of secondary uranium ore from the south Eastern Desert of Egypt.

The secondary uranium ore of Um Ara mining area, south Eastern Desert of Egypt, is composed mainly of uranophane and beta-uranophane. They occur in the oxidized zone as idiomorphic crystals filling cavities and as coatings on the fracture surfaces of the alkali-feldspar and albitized granites. The activity ratios 234U/238U and 230Th/234U of the secondary uranium ore and host rocks indicate that there were two main phases of uranium mobility in recent geological time. An earlier precipitation of uranium from solutions forming the secondary ore and a subsequent mobilization resulted in adsorption of uranium to the host granitic rocks. The 230Th/234U age of secondary uranium ore varies from (50 +/- 10) to (159 +/- 69/-45) ka whereas, the age of uranium adsorption to the rocks ranges from (18 +/- 6) to (38 +/- 5) ka. The time of secondary uranium ore precipitation can be attributed to the Saharan II pluvial period which prevailed in Egypt during humid oxygen isotope climatic stage 5. The later uranium mobility and subsequent adsorption by the rocks took place during Kubbaniyan and Nabtian pluvial periods that coincided with oxygen isotope stages 3 and 1, respectively.

Journal Article↗

Intracellular behaviour of uranium(VI) on renal epithelial cell in culture (LLC-PK1): influence of uranium speciation.

The main objective of this work was to assess the potentiality of in vitro models to study and understand the uranium-induced cytotoxicity on renal cells. Cytotoxicity and morphological studies were performed in a tubular proximal original established cell line (LLC-PK1 cell line). Dose-dependent cytotoxicity response was obtained with the uranium bicarbonate complex. In vitro experiments revealed a toxicity of uranium-bicarbonate complexes after a 24-h exposition and for concentrations ranging from 7 x 10(-4) M to 10(-3) M. In contrast, a lack of cytotoxicity of uranium(VI) citrate complexes studied using the same experimental conditions was noticed. Furthermore, electron transmission microscopy and X-ray microanalysis studies, after exposition of LLC-PK1 cells to the uranium-bicarbonate system ([U] = 8 x 10(-4) M) revealed that uranium entered into the cells and it was precipitated within the cytoplasmic compartment as uranyl phosphate needles. Similar morphological studies conducted with citrate complexes did not show any intake of uranium by LLC-PK1 cells. Experiments conducted in phosphate free culture medium showed that uranium was incorporated as a soluble material and that the association of the metal with phosphate ions occurred in the cytoplasmic compartment of LLC-PK1 cells.

Animals↗

Bench- and pilot-scale studies relating to the removal of uranium from uranium-contaminated soils using carbonate and citrate lixiviants.

Development of the nuclear industry has resulted in soil becoming contaminated with uranium from a variety of sources. To avoid the disposal of these soils in conventional low-level radwaste burial sites, a technology is needed to extract/leach and concentrate uranium in soil into small volumes of an acceptable waste form and returning the soil to its original place. Two lixiviants, carbonate and citrate, were evaluated as to their ability to extract uranium from soil in a soil washing engineering process. The objective was to use a washing/extracting process to selectively remove the uranium from soil without seriously degrading the soil's physicochemical characteristics or generating a secondary waste form that is difficult to manage and/or dispose. Both carbonate and citric acid lixiviants were observed to be effective extractants to remove uranium from the soils tested. Carbonate, because of the its ability to be recycled and its tendency to be more selective for uranium, is preferred for most soils. A major obstacle for using citric acid as well as mineral-based acids is their generation of waste streams from which it is difficult to remove uranium and manage (and dispose of any residual waste water sludges) in an environmentally acceptable manner. The removal of uranium was examined for three soils sampled from two US Department of Energy sites. Two soils were from the facility formerly called the Feed Materials Production Center at Fernald, Ohio and the other soil was from the Oak Ridge Tennessee Y-12 Plant. In the bench-scale studies, general relationships, such as the effect of carbonate and citrate concentrations, pH, the presence of oxidants, such as KMnO4, temperature, and extraction time were investigated. The best pilot-scale treatment consisted of three successive extractions with 0.25 M carbonate-bicarbonate (in presence of KMnO4 as an oxidant) at 40 degrees C followed with two water rinses.

Carbonates↗

Diurnal urinary volume and uranium output in uranium workers and unexposed controls.

Volume and uranium content were determined in individual urine voids over a 76-h (3.25-d) period from six unexposed normal male subjects and three male uranium workers. Uranium analyses were accomplished by a newly developed high-precision kinetic phosphorescence analysis technique with a lower level of detection of 0.007 ng mL-1. Urinary uranium concentrations in individual voids varied by a factor of 2 or less for any one unexposed subject, although there was an order of magnitude variation among the group of unexposed men. The fractional urinary volume excreted in the "standard" so-called simulated 24-h sample was the same for both the unexposed and exposed groups and averaged 0.42 +/- 0.13 of the total daily urine volume. The fraction of uranium in the simulated 24-h samples was 0.43 +/- 0.15 in the unexposed group but only 0.31 +/- 0.13 in the uranium worker group, suggesting that the use of the simulated 24-h urine sample would underestimate the total daily urinary uranium output by approximately a factor of 2 in the uranium workers. Daily urinary excretion relative to intake from drinking water (essentially equal to the gastrointestinal uptake fraction) among the unexposed group ranged from 0.002-0.028, averaging 0.011 +/- 0.008, with an indication that the gastrointestinal uptake factor was inversely proportional to total intake via drinking water.

Adult↗

Can we predict uranium bioavailability based on soil parameters? Part 2: soil solution uranium concentration is not a good bioavailability index.

The present study aimed to quantify the influence of soil parameters on uranium uptake by ryegrass. Ryegrass was established on eighteen distinct soils, spiked with (238)U. Uranium soil-to-plant transfer factors (TF) ranged from 0.0003 to 0.0340kgkg(-1). There was no significant relation between the U soil-to-plant transfer (or total U uptake or flux) and the uranium concentration in the soil solution or any other soil factor measured, nor with the U recovered following selective soil extractions. Multiple linear regression analysis resulted in a significant though complex model explaining up to 99% of variation in TF. The influence of uranium speciation on uranium uptake observed was featured: UO(2)(+2), uranyl carbonate complexes and UO(2)PO(4)(-) seem the U species being preferentially taken up by the roots and transferred to the shoots. Improved correlations were obtained when relating the uranium TF with the summed soil solution concentrations of mentioned uranium species.

Biological Availability↗

Radon exhalation rate and uranium estimation in rock samples from Bihar uranium and copper mines using the SSNTD technique.

Widespread uranium mineralization is associated with copper, nickel and other sulphides in the Singhbhum shear zone developed at the northern margin of the Singhbhum craton in the state of Bihar of India. The south-eastern part of the shear zone between Surda-Mosabani-Badia is rich in copper mineralization while the central part between Jaduguda-Bhatin-Nimdih and Narwapahar-Garadih-Turamdih is enriched in uranium. In the present study, trace uranium concentration in geological samples from the Mosabani copper mine and the Narwapahar and Jaduguda uranium mine areas have been determined using fission track registration technique. For the measurement of the radon exhalation rate, the 'can technique' using alpha sensitive LR-115 type II plastic track detectors were used. Uranium concentrations were found to vary from 1.5 to 2097.9 ppm whereas the radon exhalation rate varied from 0.2 to 19.2 Bq m-2 h-1. The values of radon exhalation rate from crushed rock and soil samples are found to correspond with the measured values of uranium in the corresponding samples. A positive correlation has been found between radon exhalation rate and uranium concentration in the samples. The linear coefficients are found to be 0.40, 0.98 and 0.95 in the Mosabani, Narwapahar and Jaduguda mine areas respectively. High values of radon exhalation in subsurface mines like Jaduguda (depth approximately 800 m) and Mosabani (depth > 1000 m) seem to emphasize the need for adequate ventilation for the removal of radon and its progenies from the mines.

Copper↗

Uranium bioassay and radioactive dust measurements at some uranium processing sites in Egypt--health effects.

The safety of radiation workers in the uranium mining industry requires close and continuous monitoring of their working conditions. In this study, external radiation surveillance, radioactive dust monitoring and the bioassay of uranium were carried out in some processing sites. As dust represents one of the most important sources of radiation exposure in mills and mines, dust monitoring and bioassays were performed for a sample of workers on the production lines. The concentration of uranium in air ranged from 22.6 x 10(-7) to 11.1 x 10(-5) Bq cm-3, and the exposure levels ranged from 1 to 80 microSv h-1. Laser fluorimetric determination of uranium in urine samples showed concentrations in the range 8.4-29.2 micrograms L-1. Renal function parameters, such as serum creatinine and urea, and hematological parameters were determined in an attempt to correlate them with radiation exposure and the health status of the workers. Urine specimens collected from workers at the ore crushing and separation site showed elevated concentrations of uranium (up to 29.2 micrograms L-1) and a strong correlation between these concentrations and the registered serum creatinine. The mean uranium excretion in the investigated group was more than 20 times the occupational exposure decision level for urine uranium of 0.8 microgram L-1.

Adult↗