Biogeochemical behaviour and bioremediation of uranium in waters of abandoned mines

The discharges of uranium and associated radionuclides as well as heavy metals and metalloids from waste and tailing dumps in abandoned uranium mining and processing sites pose contamination risks to surface and groundwater. Although many more are being planned for nuclear energy purposes, most of the abandoned uranium mines are a legacy of uranium production that fuelled arms race during the cold war of the last century. Since the end of cold war, there have been efforts to rehabilitate the mining sites, initially, using classical remediation techniques based on high chemical and civil engineering. Recently, bioremediation technology has been sought as alternatives to the classical approach due to reasons, which include: (a) high demand of sites requiring remediation; (b) the economic implication of running and maintaining the facilities due to high energy and work force demand; and (c) the pattern and characteristics of contaminant discharges in most of the former uranium mining and processing sites prevents the use of classical methods. This review discusses risks of uranium contamination from abandoned uranium mines from the biogeochemical point of view and the potential and limitation of uranium bioremediation technique as alternative to classical approach in abandoned uranium mining and processing sites.     

Effects of organic matter on the distribution of uranium in soil and plant matrices

This work studied interactions of uranium with pure organic compounds, such as glutathione, and more complex mixtures, such as humic acid and aqueous plant extracts. High performance liquid chromatography with UV absorption interfaced to inductively coupled plasma mass spectrometry sequential detection was used to detect organouranium complexes in a variety of soils and plant materials, indicating that nearly 100% of the uranium extracted from certain plant tissues was bound to organic ligands. In addition, soil sorption experiments indicated that humic acid generally decreased uranium sorption to soils and promoted subsequent desorption of uranium because of uranium partitioning to the organic phase. These experiments demonstrate that organic compounds influence the mobility and chemistry of uranium in the environment.     

改性玉米芯吸附溶液中的铀

以KMnO4改性玉米芯为吸附剂来吸附溶液中的铀,并与未改性玉米芯的吸附能力进行比较。考察了玉米芯用量、溶液pH值、铀初始质量浓度以及吸附时间等因素对铀吸附效果的影响。实验结果表明,当溶液pH=5.5、改性玉米芯用量为0.12 g、未改性玉米芯用量为0.2 g、铀初始质量浓度为30 mg/L、接触时间为2.5 h时,改性玉米芯对铀的去除率为93.54%,未改性玉米芯对铀的去除率为59.68%,改性玉米芯对铀的吸附效果明显优于未改性玉米芯。     

Experimental study on radon exhalation behavior of heap leaching uranium ore column with dilute sulfuric acid

Environmental Science and Pollution Research - In order to study the radon release behavior when heap leaching uranium ores with dilute sulfuric acid, unleached uranium ores from a uranium mine in...     

Chemical reactions of uranium in ground water at a mill tailings site

We studied soil and ground water samples from the tailings disposal site near Tuba City, AZ, located on Navajo sandstone, in terms of uranium adsorption and precipitation. The uranium concentration is up to 1 mg/l, 20 times the maximum concentration for ground water protection in the United States. The concentration of bicarbonate (HCO₃⁻) in the ground water increased from ≤7×10⁻⁴ M, the background concentration, to 7×10⁻³ M. Negatively charged uranium carbonate complexes prevail at high carbonate concentrations and uranium is not adsorbed on the negatively charged mineral surfaces. Leaching experiments using contaminated and uncontaminated sandstone and 1 N HCl show that adsorption of uranium from the ground water is negligible. Batch adsorption experiments with the sandstone and ground water at 16°C, the in situ ground water temperature, show that uranium is not adsorbed, in agreement with the results of the leaching experiments. Adsorption of uranium at 16°C is observed when the contaminated ground water is diluted with carbonate-free water. The observed increase in pH from 6.7 to 7.3 after dilution is too small to affect adsorption of uranium on the sandstone. Storage of undiluted ground water to 24°C, the temperature in the laboratory, causes coprecipitation of uranium with aragonite and calcite. Our study provides knowledge of the on-site uranium chemistry that can be used to select the optimum ground water remediation strategy. We discuss our results in terms of ground water remediation strategies such as pump and treat, in situ bioremediation, steam injection, and natural flushing.     

Ultrastructural localization of uranium biosorption in Penicillium digitatum by stem X-ray microanalysis

When Penicillium digitatum Saccardo cultures are exposed to aqueous solutions containing soluble uranium salts, considerable amounts of this element are accumulated in the fungal mycelium. The accumulated uranium is retained after thorough rinsing with distilled water but is removed by alkali carbonate solutions. Analysis of thick sections (0.5 microm) of the fungal hyphae with TEM, after incubation in UO(2)Cl(2) solutions of varying concentrations under both light and dark conditions, revealed conspicuous crystal-like deposits in UO(2)Cl(2)-exposed hyphae, but none in the control hyphae. Thick sections were necessary for crystal visualization. Using energy-dispersive X-ray analysis, uranium was detected as the only heavy element in these crystals. Uranium crystal biosorption was localized on the outside surface of the hyphal cell wall (following short exposures to relatively low uranium concentrations) or inside the cell wall (following long exposure to relatively high uranium concentrations). In some cases, crystal-like deposits of uranium salts were located on the outside surface as well as inside the cell.     

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.     

Exposure of Chironomus riparius larvae to uranium: effects on survival, development time, growth, and mouthpart deformities

Among non-biologically essential metals, data concerning uranium effects on freshwater benthic macroinvertebrates are scarce. The effects of uranium on survival, development time, growth and mouthpart deformities of midge Chironomus riparius were investigated. A 10-day static laboratory bioassay was performed exposing first instar larvae to artificial sediment spiked with four concentrations of uranium (2.97; 6.07; 11.44; 23.84 microg U g(-1) dry wt). As uranium was released from the sediment to the overlying water during this bioassay, both the sediment and the water column act as contamination pathways in giving rise to the observed effects. Significant negative effects on survival, development time, and growth were detected at 6.07, 6.07 and 2.97 microg U g(-1) dry wt, respectively. An LC20 of 2.49 microg U g(-1) dry wt (95% CI=1.48-4.27), and an LC50 of 5.30 microg U g(-1) dry wt (95% CI=3.94-7.25) were estimated. With respect to effects of uranium on larvae mouthpart deformities, we found that the lower the concentrations, the higher the deformity rates. These results highlight the potential impact of uranium at population level in environmentally realistic concentrations.     

Uranium contents in plants and mushrooms grown on a uranium-contaminated site near Ronneburg in Eastern Thuringia/Germany

Uranium concentrations in cultivated (sunflower, sunchoke, potato) and native plants, plant compartment specimens, and mushrooms, grown on a test site within a uranium-contaminated area in Eastern Thuringia, were analyzed and compared. This test site belongs to the Friedrich-Schiller University Jena and is situated on the ground of a former but now removed uranium mine waste leaching heap. For determination of the U concentrations in the biomaterials, the saps of the samples were squeezed out by using an ultracentrifuge, after that, the uranium concentrations in the saps and the remaining residue were measured, using ICP-MS. The study further showed that uranium concentrations observed in plant compartment and mushroom fruiting bodies sap samples were always higher than their associated solid residue sample. Also, it was found that the detected uranium concentration in the root samples were always higher than were observed in their associated above ground biomass, e.g., in shoots, leaves, blossoms etc. The highest uranium concentration was measured with almost 40 ppb U in a fruiting body of a mushroom and in roots of butterbur. However, the detected uranium concentrations in plants and mushrooms collected in this study were always lower than in the associated surface and soil water of the test site, indicating that under the encountered natural conditions, none of the studied plant and mushroom species turned out to be a hyperaccumulator for uranium, which could have extracted uranium in sufficient amounts out of the uranium-contaminated soil. In addition, it was found that the detected uranium concentrations in the sap samples, despite being above the sensitivity limit, proved to be too low—in combination with the presence of fluorescence quenching substances, e.g., iron and manganese ions, and/or organic quenchers—to extract a useful fluorescence signal, which could have helped to identify the uranium speciation in plants.     

Interactions of uranium with polyphosphate

Inorganic polyphosphates (PolyP) are simple linear phosphate (PO(4)(3-)) polymers which are produced by a variety of microorganisms. One of their functions is to complex metals resulting in their precipitation. We investigated the interaction of phosphate and low-molecular-weight PolyP (1400-1900Da) with uranyl ion at various pHs. Potentiometric titration of uranyl ion in the presence of phosphate showed two sharp inflection points at pHs 4 and 8 due to uranium hydrolysis reaction and interaction with phosphate. Titration of uranyl ion and PolyP revealed a broad inflection point starting at pH 4 indicating that complexation of U-PolyP occurs over a wide range of pHs with no uranium hydrolysis. EXAFS analysis of the U-HPO(4) complex revealed that an insoluble uranyl phosphate species was formed below pH 6; at higher pH (> or = 8) uranium formed a precipitate consisting of hydroxophosphato species. In contrast, adding uranyl ion to PolyP resulted in formation of U-PolyP complex over the entire pH range studied. At low pH (< or = 6) an insoluble U-PolyP complex having a monodentate coordination of phosphate with uranium was observed. Above pH 6 however, a soluble bidentate complex with phosphate and uranium was predominant. These results show that the complexation and solubility of uranium with PO(4) and PolyP are dependent upon pH.     

Spectrophotometric determination of uranium with arsenazo-III in perchloric acid

A short, sensitive and reliable spectrophotometric method, which has advantages over all known "wet chemistry" methods for uranium determination with regard to tolerance to common interferences, has been developed for the determination of uranium. Selectivity, molar absorptivity and the determination range of uranium have been enhanced by using 0.07% arsenazo-III as a chromogenic reagent. The use of 3 mol dm(-3) perchloric acid as a medium of determination was found to be excellent in terms of good solvent compatibility on dilution, destruction of organic contamination and simplicity of operation. The uranium-arsenazo-III complex formed instantly, and was found to be stable for more than 3 weeks with constant absorbance. Beer's law was obeyed up to a uranium concentration of 16 microg g(-1), with a molar absorptivity at 651 nm of 1.45x10(5) mol(-1) dm(3) cm(-1) at 24+/-2 degrees C. Only phosphate and citrate at 70-fold excess over uranium interfere seriously, whereas other anions studied could be tolerated up to a 70-fold excess over uranium. Of the cations studied, only Mn(II), Co(II), Ni(II), Cu(II) and Cr(III) decreased the normal absorbance of the complex. Iron(III), Ce(III) and Y(III) enhanced the absorbance. Other cations studied did not affect the absorbance up to a 50-fold excess. The accuracy was checked by determining uranium from standard solutions in the range 10-50 microg g(-1). It was found to be accurate with a 96.0-98.6% recovery rate. The method has been successfully applied to standard reference materials and ore samples at microg g(-1) levels.     

Efficient removal of uranium(VI) from aqueous systems by heat-treated carbon microspheres

In this study, uranium(VI) was successfully removed from aqueous solutions using heat-treated carbon microspheres based on a batch adsorption technique. Influence of the parameters, such as solution pH, contact time, initial uranium(VI) concentration, and temperature on the removal efficiency have been investigated in detail. The results reveal that the maximum adsorption capacity of the heat-treated carbon microspheres toward uranium(VI) is 92.08 mg g^?1, displaying a high efficiency for the removal of uranium(VI) from aqueous solution. The experimental data are analyzed using sorption kinetic models. It is revealed that the process obey the pseudo-second-order kinetic model, the determining step might be chemical sorption. The thermodynamic parameters, such as ΔH°, ΔS°, and ΔG° show that the process is endothermic and spontaneous. This work provides an efficient, fast, and convenient approach for the removal of uranium(VI) from aqueous solutions.     

Lichens as biomonitors of uranium in the Balkan area

The contribution of the conflict of 1999 to the environmental levels of uranium in the Balkan area was evaluated by means of lichens used as biomonitors. The average U concentration found in lichens in the present study was in line with the values reported for lichens from other countries and well below the levels found in lichens collected in areas with natural or anthropogenic sources of U. Measurement of isotopic ratios 235U/238U allowed to exclude the presence of depleted uranium. According to these results, we could not detect widespread environmental contamination by depleted uranium in the Balkan area.     

Airborne uranium contamination--as revealed through elemental and isotopic analysis of tree bark

A new strategy for characterisation of airborne uranium contamination based on ICP mass spectrometric analysis of tree bark is described. The uranium content of tree barks (50 samples) obtained from diverse locations (remote, rural, industrial) varied over almost four orders of magnitude (0.001-8.3 micrograms/g U) with maximum concentrations recorded in the vicinity of a nuclear fuel fabrication plant (0.70-8.3 micrograms/g U). Elevated concentrations were also observed near a coal-fired power station (0.25-0.38 microgram/g U). Isotopic analysis revealed significant deviation from the natural uranium isotope ratio (235U/238U, 0.00725) at four nuclear installations (235U/238U, 0.0055-0.0097). These findings indicate that tree bark serves as an effective biomonitor for uranium and, with isotopic analysis, discrimination between nuclear and non-nuclear emissions is realised.     

铀尾矿对地下水的环境影响研究

在越来越多的铀矿冶场面临退役的情况下,有关铀废石、尾矿的环境影响研究日益受到人们的重视并成为铀矿冶场退役环境影响评价的重要组成部分.本文在广泛搜集国内外有关研究资料的基础上,对前人所做的工作进行了总结,指出了目前研究中存在的问题和未来研究发展的方向.     

Depleted uranium mobility and fractionation in contaminated soil (Southern Serbia)

GOAL, SCOPE AND BACKGROUND: During the Balkan conflict in 1999, soil in contaminated areas was enriched in depleted uranium (DU) isotopic signature, relative to the in-situ natural uranium present. After the military activities, most of kinetic DU penetrators or their fragments remained buried in the ground in certain geomorphological and geochemical environments exposed to local weathering conditions. The contamination distribution, mobility and/or fixation of DU in the contaminated soil profile at one hot spot were the subject of our study. The results should disclose what happened with released DU corrosion products in three years elapsed, given the scope of their geochemical fractionation, and mark out the most probable host substrates in investigated soil type. METHODS: Gamma-spectrometric analysis of soil samples taken in the DU penetrator impact-zone was done to obtain present contamination levels. Set of samples is subjected to five-step and three-step sequential extraction procedures, specifically selective to different physical/chemical associations in soil. The stable elements are determined in extracts by the atomic absorption spectroscopy. After the ion-exchange based uranium separation procedure, alpha-spectrometric analysis of obtained fractions was done and DU distribution in five extraction phases found from 235U/238U and 234U/238U isotopic ratios. RESULTS: Depleted uranium concentration falls down to the 1% of the initial value, at approximately 150 mm distance to the source. Carbonates and iron/manganese hydrous oxides are indicated as the most probable substrates for depleted uranium in the characterized soil type. Therefore, in the highly contaminated soil samples, depleted uranium is still weakly bonded and easy exchangeable. The significant levels of organic-bonded depleted uranium are found in surface soil only. DISCUSSION: Dependence of the fractionation on the contamination levels is evident. Samples with higher DU contents have shown a longer maintenance in the exchangeable phases, probably because adsorption/desorption mass transfer through the medium was not very fast. Organic-bonded, depleted uranium is present in surface soil samples due to its higher humus content. Considering geochemical composition of investigated soil, the indicating chemical associations as substrates are in agreement with some considerations based on the results for low-level waste unsaturated zones. CONCLUSIONS: The soil contamination with depleted uranium in investigated area is still 'spot' type and not widespread. Dependence of the fractionation on the contamination levels and presence of weakly bonded, depleted uranium in the hot spots areas is evident. RECOMMENDATIONS AND PERSPECTIVES: A detailed study may be undertaken with suitable extractive reagents to define a bio-available fraction of depleted uranium in soil. The comparison of results for different soil types investigated by the same methodology may be useful. An applied combination of physical/chemical procedures and analysis may help in the decision making on the remediation strategy for sites contaminated with depleted uranium used in military operations.     

Reduction of U(VI) by the deep subsurface bacterium, Thermus scotoductus SA-01, and the involvement of the ABC transporter protein

In this study we investigated the effect of uranium on the growth of the bacterium Thermus scotoductus strain SA-01 as well as the whole cell U(VI) reduction capabilities of the organism. Also, site-directed mutagenesis confirmed the identity of a protein capable of a possible alternative mechanism of U(VI) reduction. SA-01 can grow aerobically in up to 1.25 mM uranium and has the capability to reduce low levels of U(VI) in under 20 h. TEM analysis performed on cells exposed to uranium showed extracellular and membrane-bound accumulation of uranium. The reductase-like protein was surprisingly identified as a peptide ABC transporter, peptide-binding protein. This study showcases the concept of protein promiscuity, where this protein with a distinct function in situ can also have the unintended function of a reactant for the reduction of U(VI).     

The migration of uranium into peat-rich soils at Broubster, Caithness, Scotland, U.K.

Uranium is being actively transported from uraniferous sedimentary rocks into a peat bog at the Broubster natural analogue site in Caithness, Scotland. Massive calcareous sandstone within the Caithness Flags sequence is the main source of uranium which resides primarily within diagenetic apatite and dispersed U---Si---Ti phases. Supergene weathering processes have decalcified the sandstone and are effective in mobilising uranium by groundwater leaching, primarily along a fault zone. Uranium transport in solution by means of groundwater and surface flows is effectively terminated by retardation within 4-kyr-old peat deposits laid down on boulder clay. This process of secondary fixation has resulted in a young uranium anomaly in the peat which comprises in excess of 0.1 wt% U. The site has been investigated comprehensively to define the geometry of the anomaly together with the hydrogeology, hydrochemistry, petrology, mineralogy and the nature of the peat sink-term. The main physical and geochemical properties of the system, including the uranium decay series radionuclide distributions in water and solid samples, are documented in this paper. From these data, the processes governing the distribution of uranium have been quantified using a three-dimensional groundwater flow package and an equilibrium speciation model incorporating a recently developed electrostatic surface complexation model to account for cation-organic interactions. The results described form part of a coordinated project on natural radionuclide migration undertaken to improve confidence in predictive methods used for radiological assessment.     

Investigation of uranium binding forms in selected German mineral waters

Cryogenic time-resolved laser-induced fluorescence spectroscopy was successfully used to identify uranium binding forms in selected German mineral waters of extremely low uranium concentrations (<2.0 μg/L). The measurements were performed at a low temperature of 153 K. The spectroscopic data showed a prevalence of aquatic species Ca₂UO₂(CO₃)₃ in all investigated waters, while other uranyl–carbonate complexes, viz, UO₂CO_3(aq) and UO₂(CO₃)₂ ^2?, only existed as minor species. The pH value, alkalinity (CO₃ ^2?), and the main water inorganic constituents, specifically the Ca²⁺ concentration, showed a clear influence on uranium speciation. Speciation modeling was performed using the most recent thermodynamic data for aqueous complexes of uranium. The modeling results for the main uranium binding form in the investigated waters indicated a good agreement with the spectroscopy measurements.