Uranium In Environment Research Articles

Mononuclear U(IV) complexes and ningyoite as major uranium species in lake sediments

Natural attenuation of uranium in subsurface environments is usually assigned to immobilisation processes due to microbially mediated reduction of U(VI). Recent laboratory studies have established that the end products of such a process include both low solubility biogenic uraninite and more labile non-crystalline U(IV) species. Indeed, biogenic uraninite formation may be inhibited in the presence of organic or inorganic phosphoryl ligands, leading to the formation of non-crystalline U(IV)-phosphate complexes or nanoscale U(IV)-phosphate solids. Such species have been observed in shallow contaminated alluvial aquifers and can thus be suspected to form in other important environments, among which lacustrine sediments have a global environmental significance since they may represent major uranium accumulation reservoirs in riverine watersheds. Here, on the basis of microscopic, spectroscopic and chemical extraction analyses, we report the occurrence of mononuclear U(IV)-phosphate/silicate complexes, accompanied by nano-crystalline ningyoite-like U(IV)-phosphate minerals, as major scavengers for uranium in lacustrine sediments downstream from a former uranium mine in France. This observation reveals that uranium trapping mechanisms during early diagenesis of lacustrine sediments can virtually exclude uraninite formation, which has important implications for better modelling uranium cycling in natural and contaminated freshwaters. Moreover, our results raise issues concerning the long term fate of mononuclear U(IV) complexes and U(IV) phosphate nano-minerals, especially with respect to re-oxidation events. © 2016 European Association of Geochemistry.

Effects of calcium and phosphate on uranium(IV) oxidation: Comparison between nanoparticulate uraninite and amorphous UIV–phosphate

The mobility of uranium in subsurface environments depends strongly on its redox state, with UIV phases being significantly less soluble than UVI minerals. This study compares the oxidation kinetics and mechanisms of two potential products of UVI reduction in natural systems, a nanoparticulate UO2 phase and an amorphous UIV–Ca–PO4 analog to ningyoite (CaUIV(PO4)2·1–2H2O). The valence of U was tracked by X-ray absorption near-edge spectroscopy (XANES), showing similar oxidation rate constants for UIVO2 and UIV–phosphate in solutions equilibrated with atmospheric O2 and CO2 at pH 7.0 (kobs,UO2=0.17±0.075h−1 vs. kobs,UIVPO4=0.30±0.25h−1). Addition of up to 400μM Ca and PO4 decreased the oxidation rate constant by an order of magnitude for both UO2 and UIV–phosphate. The intermediates and products of oxidation were tracked by electron microscopy, powder X-ray diffraction (pXRD), and extended X-ray absorption fine-structure spectroscopy (EXAFS). In the absence of Ca or PO4, the product of UO2 oxidation is Na–uranyl oxyhydroxide (under environmentally relevant concentrations of sodium, 15mM NaClO4 and low carbonate concentration), resulting in low concentrations of dissolved UVI (<2.5×10−7M). Oxidation of UIV–phosphate produced a Na-autunite phase (Na2(UO2)PO4·xH2O), resulting in similarly low dissolved U concentrations (<7.3×10−8M). When Ca and PO4 are present in the solution, the EXAFS data and the solubility of the UVI phase resulting from oxidation of UO2 and UIV–phosphate are consistent with the precipitation of Na-autunite. Bicarbonate extractions and Ca K-edge X-ray absorption spectroscopy of oxidized solids indicate the formation of a Ca–UVI–PO4 layer on the UO2 surface and suggest a passivation layer mechanism for the decreased rate of UO2 oxidation in the presence of Ca and PO4. Interestingly, the extractions were unable to remove all of the oxidized U from partially oxidized UO2 solids, suggesting that oxidized U is distributed between the interior of the UO2 nanoparticles and the labile surface layer. Accounting for the entire pool of oxidized U by XANES is the likely reason for the higher UO2 oxidation rate constants determined here relative to prior studies. Our results suggest that the natural presence or addition of Ca and PO4 in groundwater could slow the rates of UIV oxidation, but that the rates are still fast enough to cause complete oxidation of UIV within days under fully oxygenated conditions.

Adsorption/desorption of uranium on iron-bearing soil mineral surface

In this study, we evaluated the adsorption/desorption of uranium (U) in pure soil environment using continuous column reactor. We additionally investigated the adsorption/desorption mechanism of U on vivianite surface in molecular scale using quantum calculation. We observed that below <TEX>$0.1{\mu}M$</TEX> of U was detected after 20 d from U injection (<TEX>$1{\mu}M$</TEX>) in adsorption test. However, all of absorbed U was detached from vivianite surface in 24 h by injection of CARB solution (<TEX>$1.44{\times}10^{-2}M\;NaHCO_3$</TEX> and <TEX>$2.8{\times}10^{-3}M\;Na_2CO_3$</TEX>). Based on exchange energy calculation, we found that <TEX>$UO_2(CO_3)_2{^{2-}}$</TEX> and <TEX>$UO_2(CO_3)_3{^{4-}}$</TEX> species have higher repulsive energy than <TEX>$UO_2(OH)_2$</TEX> species. The results obtained from this study could be applied to predict the behavior of uranium in contaminated and remediation sites.

Biosorption of Radionuclide Uranium by Deinococcus radiodurans

As a biological adsorbent, Living Deinococcus radiodurans was used for removing radionuclide uranium in the aqueous solution. The effect factors on biosorption of radionuclide uranium were researched in the present paper, including solution pH values and initial uranium concentration. Meanwhile, the biosorption mechanism was researched by the method of FTIR and SEM/EDS. The results show that the optimum conditions for biosorption are as follows: pH = 5, co = 100 mg · L(-1) and the maximum biosorption capacity is up to 240 mgU · g(-1). According to the SEM results and EDXS analysis, it is indicated that the cell surface is attached by lots of sheet uranium crystals, and the main biosorpiton way of uranium is the ion exchange or surface complexation. Comparing FTIR spectra and FTIR fitting spectra before and after biosorption, we can find that the whole spectra has a certain change, particularly active groups (such as amide groups of the protein, hydroxy, carboxyl and phosphate group) are involved in the biosorption process. Then, there is a new peak at 906 cm(-1) and it is a stretching vibration peak of UO2(2+). Obviously, it is possible that as an anti radiation microorganism, Deinococcus radiodurans could be used for removing radionuclide uranium in radiation environment.

Efficient removal of uranium from aqueous solution by zero-valent iron nanoparticle and its graphene composite

Zero-valent iron nanoparticle (ZVI-np) and its graphene composites were prepared and applied in the removal of uranium under anoxic conditions. It was found that solutions containing 24ppm U(VI) could be completely cleaned up by ZVI-nps, regardless of the presence of NaHCO3, humic acid, mimic groundwater constituents or the change of solution pH from 5 to 9, manifesting the promising potential of this reactive material in permeable reactive barrier (PRB) to remediate uranium-contaminated groundwater. In the measurement of maximum sorption capacity, removal efficiency of uranium kept at 100% until C0(U)=643ppm, and the saturation sorption of 8173mgU/g ZVI-nps was achieved at C0(U)=714ppm. In addition, reaction mechanisms were clarified based on the results of SEM, XRD, XANES, and chemical leaching in (NH4)2CO3 solution. Partially reductive precipitation of U(VI) as U3O7 was prevalent when sufficient iron was available; nevertheless, hydrolysis precipitation of U(VI) on surface would be predominant as iron got insufficient, characterized by releases of Fe2+ ions. The dissolution of Fe0 cores was assigned to be the driving force of continuous formation of U(VI) (hydr)oxide. The incorporation of graphene supporting matrix was found to facilitate faster removal rate and higher U(VI) reduction ratio, thus benefitting the long-term immobilization of uranium in geochemical environment.

Inhibition of U(VI) reduction by synthetic and natural pyrite.

Reductive precipitation is an effective method of attenuating the mobility of uranium (U) in subsurface environments. The reduction of U(VI) by synthetic and naturally occurring pyrite was investigated at pH 3.0-9.5. In contrast to thermodynamic calculations that were used to predict UO2(s) precipitation, a mixed U(IV) and U(VI) product (e.g., U3O8/U4O9/U3O7) was only observed at pH 6.21-8.63 and 4.52-4.83 for synthetic and natural pyrite, respectively. Under acidic conditions, the reduction of UO2(2+) by surface-associated Fe(2+) may not be favored because the mineral surface is nearly neutral or not negative enough. At high pH, the sorption of negatively charged U(VI) species is not favored on the negatively charged mineral surface. Thus, the redox reaction is not favored. Trace elements generally contained within the natural pyrite structure can affect the reactivity of pyrite and lead to a different result between the natural and synthetic pyrite. Because UO2(s) is extremely redox-sensitive toward U(VI), the observed UO2+x(s) phase reduction product indicates a surface reaction that is largely controlled by reaction kinetics and pyrite surface chemistry. These factors may explain why most laboratory experiments have observed incomplete U(VI) reduction on Fe(II)-bearing minerals.

Sorption of uranyl and arsenate on SiO2, Al2O3, TiO2 and FeOOH

Migration of uranium and arsenic in aquatic environments is often controlled by sorption on minerals present along the water flow path. To investigate the sorption behaviour, batch experiments were conducted for uranium and arsenic as single components and also solutions containing both uranium and arsenic in the presence of SiO2, Al2O3, TiO2 and FeOOH at a pH ranging from 3 to 9. In solutions containing only U(VI) or As(V) with the minerals, the sorption of U(VI) was low at acidic pH range and increases with increasing pH, whereas As(V) showed opposite sorption behaviour to Al2O3, TiO2 and FeOOH from acidic pH range to alkaline condition. For the As(V)–SiO2 system, the sorption was low for almost all pH. Sorption of U(VI) and As(V) on SiO2 and FeOOH is almost similar in solutions containing either U(VI) or As(V) separately, or both together. In the U(VI)–As(V)–Al2O3 system, a significant retardation in uranyl sorption and an enhancement in arsenate sorption on Al2O3 were observed for a wide range of pH. The sorption behaviour of U(VI) and As(V) was changed when Al2O3 was replaced by TiO2, where an increase in sorption was observed for both elements. The sorption behaviour of uranyl and arsenate in the U(VI)–As(V)–TiO2 system gives evidence for the formation of uranyl–arsenate complexes. The change in sorption retardation/enhancement of U(VI) and As(V) could be explained by the formation of uranyl–arsenate complexes or due to the competitive sorption between uranyl and arsenate species.

Molecular Dynamics Simulations of Uranyl and Uranyl Carbonate Adsorption at Aluminosilicate Surfaces

Adsorption at mineral surfaces is a critical factor controlling the mobility of uranium(VI) in aqueous environments. Therefore, molecular dynamics (MD) simulations were performed to investigate uranyl(VI) adsorption onto two neutral aluminosilicate surfaces, namely, the orthoclase (001) surface and the octahedral aluminum sheet of the kaolinite (001) surface. Although uranyl preferentially adsorbs as a bidentate inner-sphere complex on both surfaces, the free energy of adsorption on the orthoclase surface (-15 kcal mol(-1)) is significantly more favorable than that at the kaolinite surface (-3 kcal mol(-1)), which is attributed to differences in surface functional groups and the ability of the orthoclase surface to release a surface potassium ion upon uranyl adsorption. The structures of the adsorbed complexes compare favorably with X-ray absorption spectroscopy results. Simulations of the adsorption of uranyl complexes with up to three carbonate ligands revealed that uranyl complexes coordinated to up to two carbonate ions are stable on the orthoclase surface whereas uranyl carbonate surface complexes are unfavored at the kaolinite surface. Combining the MD-derived equilibrium adsorption constants for orthoclase with aqueous equilibrium constants for uranyl carbonate species indicates the presence of adsorbed uranium complexes with one or two carbonates under alkaline conditions, in support of current uranium(VI) surface complexation models.

The corrosion of depleted uranium in terrestrial and marine environments

Depleted Uranium alloyed with titanium is used in armour penetrating munitions that have been fired in a number of conflict zones and testing ranges including the UK ranges at Kirkcudbright and Eskmeals. The study presented here evaluates the corrosion of DU alloy cylinders in soil on these two UK ranges and in the adjacent marine environment of the Solway Firth.The estimated mean initial corrosion rates and times for complete corrosion range from 0.13 to 1.9 g cm−2 y−1 and 2.5–48 years respectively depending on the particular physical and geochemical environment.The marine environment at the experimental site was very turbulent. This may have caused the scouring of corrosion products and given rise to a different geochemical environment from that which could be easily duplicated in laboratory experiments.The rate of mass loss was found to vary through time in one soil environment and this is hypothesised to be due to pitting increasing the surface area, followed by a build up of corrosion products inhibiting further corrosion. This indicates that early time measurements of mass loss or corrosion rate may be poor indicators of late time corrosion behaviour, potentially giving rise to incorrect estimates of time to complete corrosion.The DU alloy placed in apparently the same geochemical environment, for the same period of time, can experience very different amounts of corrosion and mass loss, indicating that even small variations in the corrosion environment can have a significant effect. These effects are more significant than other experimental errors and variations in initial surface area.

Insights into the interactions of cyanobacteria with uranium

Due to various activities associated with nuclear industry, uranium is migrated to aquatic environments like groundwater, ponds or oceans. Uranium forms stable carbonate complexes in the oxic waters of pH 7-10 which results in a high degree of uranium mobility. Microorganisms employ various mechanisms which significantly influence the mobility and the speciation of uranium in aquatic environments. Uranyl bioremediation studies, this far, have generally focussed on low pH conditions and related to adsorption of positively charged UO2 (2+) onto negatively charged microbial surfaces. Sequestration of anionic uranium species, i.e. [UO2(CO3) 2 (2-) ] and [UO2(CO3) 3 (4-) ] onto microbial surfaces has received only scant attention. Marine cyanobacteria are effective metal adsorbents and represent an important sink for metals in aquatic environment. This article addresses the cyanobacterial interactions with toxic metals in general while stressing on uranium. It focusses on the possible mechanisms employed by cyanobacteria to sequester uranium from aqueous solutions above circumneutral pH where negatively charged uranyl carbonate complexes dominate aqueous uranium speciation. The mechanisms demonstrated by cyanobacteria are important components of biogeochemical cycle of uranium and are useful for the development of appropriate strategies, either to recover or remediate uranium from the aquatic environments.

Bioreduction of Hydrogen Uranyl Phosphate: Mechanisms and U(IV) Products

The mobility of uranium (U) in subsurface environments is controlled by interrelated adsorption, redox, and precipitation reactions. Previous work demonstrated the formation of nanometer-sized hydrogen uranyl phosphate (abbreviated as HUP) crystals on the cell walls of Bacillus subtilis, a non-U(VI)-reducing, Gram-positive bacterium. The current study examined the reduction of this biogenic, cell-associated HUP mineral by three dissimilatory metal-reducing bacteria, Anaeromyxobacter dehalogenans strain K, Geobacter sulfurreducens strain PCA, and Shewanella putrefaciens strain CN-32, and compared it to the bioreduction of abiotically formed and freely suspended HUP of larger particle size. Uranium speciation in the solid phase was followed over a 10- to 20-day reaction period by X-ray absorption fine structure spectroscopy (XANES and EXAFS) and showed varying extents of U(VI) reduction to U(IV). The reduction extent of the same mass of HUP to U(IV) was consistently greater with the biogenic than with the abiotic material under the same experimental conditions. A greater extent of HUP reduction was observed in the presence of bicarbonate in solution, whereas a decreased extent of HUP reduction was observed with the addition of dissolved phosphate. These results indicate that the extent of U(VI) reduction is controlled by dissolution of the HUP phase, suggesting that the metal-reducing bacteria transfer electrons to the dissolved or bacterially adsorbed U(VI) species formed after HUP dissolution, rather than to solid-phase U(VI) in the HUP mineral. Interestingly, the bioreduced U(IV) atoms were not immediately coordinated to other U(IV) atoms (as in uraninite, UO2) but were similar in structure to the phosphate-complexed U(IV) species found in ningyoite [CaU(PO4)2·H2O]. This indicates a strong control by phosphate on the speciation of bioreduced U(IV), expressed as inhibition of the typical formation of uraninite under phosphate-free conditions.

Fertilizer-Derived Uranium and its Threat to Human Health

P fertilization remains the main source of uranium contamination of agricultural land, primarily due to impurities in the phosphate rock used for fertilizer manufacture. In particular, long-term application of uranium-bearing fertilizers can significantly elevate the uranium concentration in fertilized soils. The magnitude of uranium enrichment of cultivated soils varies, depending on phosphate fertilizer application rate, uranium content of applied fertilizer, soil type and prevailing climate. In Germany, the use of phosphate fertilizer from 1951 to 2011 has resulted in a cumulative application of approximately 14 000 t of uranium on agricultural land, corresponding to an average cumulative loading of 1 kg of uranium per hectare. Fertilizer-derived uranium in soils is prone to leaching because uranium is mobile in surface soils as uranyl complex depending on prevailing pH and Eh conditions. Alternatively, uranium can be immobilized in subsurface materials by sorption or coprecipitation mechanisms. The fate of uranium in soil and subsurface environment is therefore influenced by a delicate balance of U association between immobile and mobile phases. Yet, uranium is highly soluble as uranyl (U) complex under oxidizing conditions. Consequently, mobility of fertilizerderived uranium from agricultural soils into ground and surface waters has been recognized in agricultural catchments and, numerous studies have established the transfer of fertilizerderived uranium from soils into ground, surface and marine coastal waters. For example in Germany, rivers and streams of agricultural catchments have 10 times higher uranium concentrations (0.08 versus 0.8 μg/L U) than those dominated by forestry. Significantly enriched uranium concentrations (>2 μg/L U) were detected in heavily cultivated catchments. Moreover, unconfined aquifers below agricultural land, groundwater has 3 to 17 times higher uranium concentrations than that below forested regions. Generally, there is a concurrent and strong correlation of dissolved uranium concentrations in groundwater with those of other highly mobile and fertilizerderived elements such as boron, magnesium, and potassium as well as nitrate. The likely reason for the strong uranium-nitrate correlation in groundwater could be due to (a) increased fertilization of agricultural land using NP and NPK fertilizers; (b) significant mobility of fertilizer-derived uranium as uranylcarbonate complex and transfer into the underlying aquifer; and (c) pronounced solubility of uranium as uranyl−nitrate complex into groundwater. In northern Germany, unmineralized groundwater used as drinking water supply contains variable uranium contents, with one-quarter to two-thirds likely impacted by fertilizer-derived uranium. Thus, agricultural soils and nearby land and water resources are becoming increasingly contaminated by uranium due to fertilizer use. Fertilizer-derived uranium has entered German drinking water supplies. Principal route of exposure of humans to uranium occurs via ingestion, skin contact, and inhalation. In particular, naturally mineralized groundwaters and bottled mineral waters can contribute significantly to uranium uptake. In Germany, more than 2 million people currently receive drinking water that contains >10 μg/L uranium. Here, a carnivore with a skewed taste for offal, shellfish, and bottled mineral water can achieve the highest uranium uptake. A considerable body of evidence suggests that overexposure to uranium in drinking water may cause significant health effects in both humans and animals. Reported health effects of uranium derive from experimental animal studies and human epidemiology. Uranium may damage biological systems through its chemical toxicity as well as its radioactivity, with the chemical toxicity perceived as the primary health hazard and the effects from uranium’s ionizing radiation being of secondary concern. The main health concerns with respect to uranium are renal, developmental, reproductive, diminished bone growth, as well as DNA and brain damage. In humans uranium is particularly known for its nephrotoxic nature, with short-term and long-term exposure to uranium through drinking water leading to renal effects. The information available on the chronic health effects caused by the exposure to uranium in drinking water points to the fact that regions with elevated groundwater uranium concentrations and more groundwater use have an increased incidence of certain diseases. For example, increasing incidence in chronic kidney disease in Sri Lankan nationals has been related to the low-level fertilizer-

Polonium, uranium and plutonium radionuclides in aquatic and land ecosystem of Poland

This article presents the results of study about distribution, inflow and accumulation of polonium, uranium and plutonium in aquatic and land environment of Poland and the southern Baltic Sea. Radionuclides of 210Po, 234U and 238U as well as 239+240Pu and 241Pu are strongly accumulated in Baltic organisms and plants and transferred through the trophic chain. The values of bioconcentration factor (BCF) in Baltic plants and animals are higher for polonium and plutonium in comparison with uranium. The principal source of radionuclides in the southern Baltic Sea is their inflow with rivers. Total annual runoff of polonium, uranium and plutonium from the Vistula and the Odra as well as the Pomeranian rivers were calculated at 95 GBq of 210Po, 750 GBq of 234+238U and 160 MBq of 238+239+240Pu. Seasonal and spatial variability of 210Po, 238U and 239+240Pu levels in the Vistula and the Odra drainage basins were assessed by application of neural-network based classification, especially cluster analysis (CA), principal component analysis (PCA) and self-organizing maps (SOM). The result for the Vistula river indicated correlation between polonium and plutonium as well as polonium and uranium. In the Odra drainage basin, the biggest differences were observed in the case of 238U. To assess if there are statistically significant differences in mean concentration values of 210Po, 238U and 239+240Pu for the Vistula and the Odra rivers drainage basins were obtained by used of the non-parametric tests. Comparing to the Vistula catchment area, statistically differences concentration of 210Po and 239+240Pu in all year was observed for river samples collected on the Odra drainage basin.

Fragmentation of extracellular DNA by long-term exposure to radiation from uranium in aquatic environments

Persistent harmful scenarios associated with disposal of radioactive waste, high-background radiation areas and severe nuclear accidents are of great concern regarding consequences to both human health and the environment. Of particular concern is the extracellular DNA in aquatic environments contaminated by radiological substances. Strand breaks induced by radiation promote decrease in the transformation efficiency for extracellular DNA. The focus of this study is the quantification of DNA damage following long-term exposure (over one year) to low doses of natural uranium (an alpha particle emitter) to simulate natural conditions, since nothing is known about alpha radiation induced damage to extracellular DNA. A high-resolution Atomic Force Microscope was used to evaluate DNA fragments. Double-stranded plasmid pBS as a model for extracellular DNA was exposed to different amounts of natural uranium. It was demonstrated that low concentrations of U in water (50 to 150 ppm) produce appreciable numbers of double strand breaks, scaling with the square of the average doses. The importance of these findings for environment monitoring of radiological pollution is addressed.

Playa sediments of the Didwana Lake, Rajasthan: A new environment for surficial-type uranium mineralisation in India

The Didwana playa, the second largest playa in the eastern part of the Thar desert, is 5.6 km long and 2.4 km wide and supports commercial salt production. The thickness of lake sediment package is reported to be 20 m and comprises fine grained clays and silts, with abundant calcite, gypsum, and halite, associated with hypersaline water. Isolated hills of graphitic phyllite and quartzite are seen on the western side of the lake. During the course of investigations for uranium in surficial environment of semi-arid terrain of Rajasthan, ground water sampling defined a NE-SW trending uranium halo encompassing the Didwana playa. Subsequent sampling of unlined dug wells, up to water table in central part of the playa, indicated uranium values up to 190 ppm and 2072 ppb in lake sediments and brine respectively. These values are of the order of 21 ppm and 192 ppb towards the southwestern periphery of the lake. The average uranium content, as inferred from 12 samples in the central part of the lake, is around 60 ppm over a thickness of 5 m. It appears that the uranium is loosely bonded to the sediments in amorphous form and is, hence, easily leachable. Samples of brine (n=10), from both the central and southwestern portions of the lake, analysed high (1,67,500–3,00,000 mg/l) TDS, HCO3− (1128–8395 mg/l), and SO4 (30,536–88,000 mg/l). These are of alkaline (pH: 7.2–9.3) and reducing (Eh: −200 to −340 mV) nature. Under these Eh-pH conditions below the groundwater table, and for such uranium bearing groundwater, precipitation of primary uranium is expected. It is, therefore, modelled that uranium in lake sediment package above water table is concentrated by evaporation process and by chemical reduction below the water table.

Pre-concentration and determination of trace uranium (VI) in environments using ion-imprinted chitosan resin via solid phase extraction

The uranyl-ion-imprinted and non-imprinted cross-linked chitosan resins possessing quinoline-8-ol moiety have been prepared. In all the cases, a significant imprinting effect was noticed on comparing percent extraction of uranium (VI). The resulting ion-imprinted resin was used for solid phase extractive preconcentration of uranium (VI) prior to its determination by spectrophotometry. Experimental variables that influence the quantitative extraction of uranium (VI) were optimized by both static and column methods. The retention capacity found for uranium (VI) was 218 mg g-1 of resin which is higher than the corresponding non-imprinted resins and other solid phase extraction sorbents possessing quinoline-8-ol moiety. The optimum pH range was 4.5-7.0. Uranium adsorbed was easily and quantitatively eluted with 1 mol L-1 HCl (10 mL) at a flow rate of 2 mL min-1. Interference studies showed a high tolerance of diverse ions and electrolyte species. The limit of detection was 2 µg L-1 and the dynamic linear range was 5-100 µg L-1. The accuracy of the developed method was tested with one uranium ore standard reference material. Furthermore, the proposed method was successfully applied for the determination of uranium in contaminated soil and sediment samples.

Corrosion and transport of depleted uranium in sand-rich environments

The firing of depleted uranium (DU) weapons during conflicts and military testing has resulted in the deposition of DU in a variety of sand-rich environments. In this study, DU-amended dune sand microcosm and column experiments were carried out to investigate the corrosion of DU and the transport of corrosion products. Under field-moist conditions, DU corroded to metaschoepite ((UO 2) 8O 2(OH) 12·(H 2O) 10) at a rate of 0.10 ± 0.012 g cm −2 y −1. This loosely bound corrosion product detached easily from the coupon and became distributed heterogeneously within the sand. The corrosion of DU caused significant changes in the geochemical environment, with NO 3 - and Fe(III) reduction observed. Column experiments showed that transport of metaschoepite was mainly dependent on its dissolution and the subsequent interaction of the resulting dissolved uranyl ( UO 2 2 + ) species with sand particles. The modelling results predict that the transport of U released from metaschoepite dissolution is retarded, due to a slowly desorbing surface species (first order desorption rate constant = 5.0 (±1.0) × 10 −8 s −1). The concentrations of U eluting from the metaschoepite column were orders of magnitude higher than the World Health Organisation’s recommended maximum admissible concentration for U in drinking water of 15 μg L −1. Therefore, a relatively high level of mobile U contamination would be expected in the immediate proximity of a corroding penetrator in a sand-rich environment.

Identification of Uranyl Surface Complexes on Ferrihydrite: Advanced EXAFS Data Analysis and CD-MUSIC Modeling

Previous spectroscopic research suggested that uranium(VI) adsorption to iron oxides is dominated by ternary uranyl-carbonato surface complexes across an unexpectedly wide pH range. Formation of such complexes would have a significant impact on the sorption behavior and mobility of uranium in aqueous environments. We therefore reinvestigated the identity and structural coordination of uranyl sorption complexes using a combination of U LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopy and iterative transformation factor analysis, which enhances the resolution in comparison to conventional EXAFS analysis. A range of conditions (pH, CO2 partial pressure, ionic strength) made it possible to quantify the variations in surface speciation. In the resulting set of spectral data (N=11) the variance is explained by only two components, which represent two structurally different types of surface complexes: (1) a binary uranyl surface complexwith a bidentate coordination to edges of Fe(O,OH)6 octahedra and (2) a uranyl triscarbonato surface complex where one carbonate ion bridges uranyl to the surface. This ternary type B complex differs from a type A complex where uranyl is directly attached to surface atoms and carbonate is bridged by uranyl to the surface. Both surface complexes agree qualitatively and quantitatively with predictions by a charge distribution (CD) model. According to this model the edge-sharing uranyl complex has equatorial ligands (-OH2, -OH, or one -CO3 group) that point away from the surface. The monodentate uranyl triscarbonato surface complex (type B) is relevant only at high pH and elevated pC0O. At these conditions, however, it is responsible for significant uranyl sorption, whereas standard models would predict only weak sorption. This paper presents the first spectroscopic evidence of this ternary surface complex, which has significant implications for immobilization of uranyl in carbonate-rich aqueous environments.

Dissolution kinetics of meta-torbernite under circum-neutral to alkaline conditions

Environmental context. Uranium-phosphate minerals have been identified as a long-term controlling phase that limit the mobility of uranium to groundwater in many contaminated subsurface environments. Complex, coupled processes confound the ability to isolate the rates attributed to individual processes. Results of this investigation provide the necessary information to refine current prediction on the release and long-term fate of uranium in subsurface environments. Abstract. The purpose of this investigation was to conduct a series of single-pass flow-through (SPFT) tests to (1) quantify the effect of temperature (23–90°C) and pH (6–10) on meta-torbernite dissolution; (2) compare the dissolution of meta-torbernite to other autunite-group minerals; and (3) evaluate the effect of aqueous phosphate on the dissolution kinetics of meta-torbernite. Results presented here illustrate meta-torbernite dissolution rates increase by ~100× over the pH interval of 6 to 10, irrespective of temperature. The power law coefficient for meta-torbernite, η = 0.59 ± 0.07, is greater than that quantified for Ca-meta-autunite, η = 0.42 ± 0.12. This suggests the stability of meta-torbernite is greater than that of meta-autunite, which is reflected in the predicted stability constants. The rate equation for the dissolution of meta-torbernite as a function of aqueous phosphate concentration is log rdissol (mol m–2 s–1) = –4.7 × 10–13 + 4.1 × 10–10[PO43–].

Behavior and Distribution of Rare Earth Elements, Thorium and Uranium in Soil Environment

Consequently, the following matters have been mainly clarified. (1)REEs in soils mainly exists in the form of F(rd)fraction(i.e., silicate), although F(om) or F(fm) was relatively large proportion fraction(F(om):8-28%; F(fm):6-20%); while U in soils may be present as the fraction bound to carbonate (15%) in addition to as F(rd)(60-70%). (2)The total concentrations of U in soil in agricultural field is remarkably larger (about 2 times) than that in non-agricultural field, although the concentrations of REEs and Th are not greatly varied regardless of soil utilizations(i.e., paddy field, upland field or no plow). (3)The value of pH(H2O)-pH(KCl) in soil of the upland field is smallest. Moreover, EC(electric conductivity) in soil of the upland field is much higher than that of the paddy field or of the non-agricultural field. (4)REE pattern of the crops and fertilizers is generally similar to that of soils, although the order of the concentration of REEs is “soils” > “fertilizers” > “crops”.