Uranium-contaminated Sites Research Articles

Microbial production of methyl-uranium via the Wood-Ljungdahl pathway

The misuse of uranium is a major threat to human health and the environment. In microbial ecosystems, microbes deploy various strategies to cope with uranium-induced stress. However, the exact ecological strategies and mechanisms underlying uranium tolerance in microbes remain unclear. Therefore, this study aimed to investigate the survival strategies and tolerance mechanisms of microbial communities in uranium-contaminated soil and groundwater. Microbial co-occurrence networks and molecular biology techniques were used to analyze the properties of microbes in groundwater and soil samples from various depths of uranium-contaminated areas in Northwest China. Uranium pollution altered microbial ecological strategies. Uranium stress facilitated the formation of microbial community structures, leading to symbiosis. Furthermore, microbes primarily resisted uranium hazards by producing polysaccharides and phosphate groups that chelate uranium, releasing phosphate substances that precipitate uranium, and reducing U(VI) through sulfate- and iron-reducing processes. The relative abundance of metal-methylation genes in soil microorganisms positively correlated with uranium concentration, indicating that soil microorganisms can produce methyl uranium via the Wood-Ljungdahl pathway. Furthermore, soil and groundwater microorganisms demonstrated different responses to uranium stress. This study provides new insights into microbial responses to uranium stress and novel approaches for the bioremediation of uranium-contaminated sites.

Study on the remediation of uranium-contaminated soils by compound leaching: Screening of leaching agents and a pilot-scale application

To solve the problem of soil environmental pollution resulting from uranium mine development and production, a soil slurry reactor was used to evaluate the use of chemical leaching to remediate uranium-contaminated soils and to analyze possible uranium removal mechanisms through laboratory-scale trials and pilot-scale trials. A laboratory-scale trial comparing different reagents and operating methods revealed that the removal of total uranium from contaminated soil could reach 91.18% under optimal conditions when FeCl3, OA, NaClO2, and HEDP were used as eluents.Based on the optimal ratio and operating conditions determined from laboratory-scale trials, a pilot-scale trial was conducted around a uranium mining area: soil leaching remediation was conducted in two 3 m3 soil-slurry reactors to verify the practicality of the leaching technology and examine the functionality of the remediated soil. The experimental results showed that the rate of uranium removal from contaminated soil by the chemical leaching method was greater than 80%. FTIR, XRF and enzyme activity analysis proved that remediation restored the original soil function and reduced the ecological risk, indicating that the chemical leaching technology was environmentally friendly and economical. These findings provide insight to guide the future assessment and remediation practices of uranium-contaminated sites.

Modeling evaluation of the impact of residual source material on remedial time frame at a former uranium mill site

Groundwater contamination at legacy uranium processing sites is an ongoing global challenge. Plumes at many uranium-contaminated sites are more persistent than originally predicted by groundwater modeling. Previous investigations of uranium plume persistence identified residual and secondary sources that contribute to plume longevity, but there is a remaining need to revise forecasted cleanup times using information about these ongoing sources. The purpose of this study is to investigate the quantitative impact of residual vadose zone sources of uranium on groundwater remediation time frame. This objective was approached by applying numerical uranium transport simulations and uncertainty analysis to a former uranium mill site in the southwestern United States. Information from recent site investigations provided details about the distribution and release characteristics of uranium accumulations in the vadose zone. The residual uranium characteristics were incorporated as decaying source terms in the transport model. A stochastic approach using an iterative ensemble smoother was applied for history matching, and the transport model was used to assess the impact of multiple remedial alternatives on forecasted time frame. The forecasted time frame to achieve the groundwater remediation goal for uranium by monitored natural attenuation is on the order of thousands of years, and treatment of the dissolved plume does not reduce the projected time frame. The large proportion of residual uranium mass remaining in the vadose zone and the gradual leaching rate due to the site's semiarid climate create a long-lived source that can sustain a dissolved plume for thousands of years despite an estimated 99% mass removal achieved during mill tailings disposal. Residual uranium in vadose zone sediments beneath former tailings impoundments could present comparable uranium plume persistence and remediation challenges at other legacy uranium mill sites in semiarid climates. Other remaining uranium-impacted sites are similarly complex, and forecasted remedial time frames are needed to effectively achieve compliance, manage risk, assess the benefits of additional treatment, manage and project costs, and support beneficial site reuse.

Rigidity and Flexibility: Unraveling the Role of Fulvic Acid in Uranyl Sorption on Graphene Oxide Using Molecular Dynamics Simulations.

Using molecular dynamics simulations, this work targets a molecular understanding on the rigidity and flexibility of fulvic acid (FA) in uranyl sorption on graphene oxide (GO). The simulations demonstrated that both rigid Wang's FA (WFA) and flexible Suwannee River FA (SRFA) can provide multiple sites to cooperate with GO for uranyl sorption and act as "bridges" to connect uranyl and GO to form GO-FA-U (type B) ternary surface complexes. The presence of flexible SRFA was more beneficial to uranyl sorption on GO. The interactions of WFA and SRFA with uranyl were primarily driven by electrostatics, and the electrostatic interaction of SRFA-uranyl was significantly stronger owing to the formation of more complexes. The flexible SRFA could markedly enhance the bonding strength of uranyl with GO by folding itself to provide more sites to coordinate with uranyl. The rigid WFAs tended to be adsorbed on the GO surface in parallel due to π-π interactions, whereas the flexible SRFAs took more slant configurations resulting from intermolecular hydrogen bonds. This work provides new insights into the sorption dynamics, structure, and mechanism and addresses the effect of molecular rigidity and flexibility, with great significance for FA-based remediation strategies of uranium-contaminated sites.

Optimization of Environmental Conditions for Microbial Stabilization of Uranium Tailings, and the Microbial Community Response.

Uranium pollution in tailings and its decay products is a global environmental problem. It is of great significance to use economical and efficient technologies to remediate uranium-contaminated soil. In this study, the effects of pH, temperature, and inoculation volume on stabilization efficiency and microbial community response of uranium tailings were investigated by a single-factor batch experiment in the remediation process by mixed sulfate-reducing bacteria (SRB) and phosphate-solubilizing bacteria (PSB, Pantoea sp. grinm-12). The results showed that the optimal parameters of microbial stabilization by mixed SRB-PSB were pH of 5.0, temperature of 25°C, and inoculation volume of 10%. Under the optimal conditions, the uranium in uranium tailings presented a tendency to transform from the acid-soluble state to residual state. In addition, the introduction of exogenous SRB-PSB can significantly increase the richness and diversity of endogenous microorganisms, effectively maintain the reductive environment for the microbial stabilization system, and promote the growth of functional microorganisms, such as sulfate-reducing bacteria (Desulfosporosinus and Desulfovibrio) and iron-reducing bacteria (Geobacter and Sedimentibacter). Finally, PCoA and CCA analyses showed that temperature and inoculation volume had significant effects on microbial community structure, and the influence order of the three environmental factors is as follows: inoculation volume > temperature > pH. The outcomes of this study provide theoretical support for the control of uranium in uranium-contaminated sites.

Response and Dynamic Change of Microbial Community during Bioremediation of Uranium Tailings by Bacillus sp.

Bacillus sp. is widely used in the remediation of uranium-contaminated sites. However, little is known about the competitive process of microbial community in the environment during bioremediation. The bioremediation of uranium tailings using Bacillus sp. was explored, and the bacterial community was analyzed by high-throughput sequencing at different stages of remediation. Bacillus sp. reduced the leaching of uranium from uranium tailings. The lowest uranium concentration was 17.25 μg/L. Alpha diversity revealed that the abundance and diversity of microorganisms increased with the extension of the culture time. The microbial abundance and diversity were higher in the treatment group than in the control group. The dominant species at the phyla level were Firmicutes and Proteobacteria in the uranium tailings environment, whereas the phylum of Proteobacteria was significantly increased in the treatment group. Based on the genus level, the proportions of Arthrobacter, Rhodococcus and Paenarthrobacter decreased significantly, whereas those of Clostridium sp., Bacillus and Pseudomonas increased dramatically. Hence, the remediation of uranium contamination in the environment was due to the functional microorganisms, which gradually became the dominant strain in the treatment, such as Desulfotomaculum, Desulfosporporosinus, Anaerocolumna, Ruminiclostridium and Burkholderia. These findings provided a promising outlook of the potential for remediation strategies of soil contaminated by uranium. The dynamic characteristics of the microbial community are likely to provide a foundation for the bioremediation process in practice.

Bacterial Community Shift and Coexisting/Coexcluding Patterns Revealed by Network Analysis in a Uranium-Contaminated Site after Bioreduction Followed by Reoxidation.

A site in Oak Ridge, TN, USA, has sediments that contain >3% iron oxides and is contaminated with uranium (U). The U(VI) was bioreduced to U(IV) and immobilized in situ through intermittent injections of ethanol. It then was allowed to reoxidize via the invasion of low-pH (3.6 to 4.0), high-nitrate (up to 200 mM) groundwater back into the reduced zone for 1,383 days. To examine the biogeochemical response, high-throughput sequencing and network analysis were applied to characterize bacterial population shifts, as well as cooccurrence and coexclusion patterns among microbial communities. A paired t test indicated no significant changes of α-diversity for the bioactive wells. However, both nonmetric multidimensional scaling and analysis of similarity confirmed a significant distinction in the overall composition of the bacterial communities between the bioreduced and the reoxidized sediments. The top 20 major genera accounted for >70% of the cumulative contribution to the dissimilarity in the bacterial communities before and after the groundwater invasion. Castellaniella had the largest dissimilarity contribution (17.7%). For the bioactive wells, the abundance of the U(VI)-reducing genera Geothrix, Desulfovibrio, Ferribacterium, and Geobacter decreased significantly, whereas the denitrifying Acidovorax abundance increased significantly after groundwater invasion. Additionally, seven genera, i.e., Castellaniella, Ignavibacterium, Simplicispira, Rhizomicrobium, Acidobacteria Gp1, Acidobacteria Gp14, and Acidobacteria Gp23, were significant indicators of bioactive wells in the reoxidation stage. Canonical correspondence analysis indicated that nitrate, manganese, and pH affected mostly the U(VI)-reducing genera and indicator genera. Cooccurrence patterns among microbial taxa suggested the presence of taxa sharing similar ecological niches or mutualism/commensalism/synergism interactions.IMPORTANCE High-throughput sequencing technology in combination with a network analysis approach were used to investigate the stabilization of uranium and the corresponding dynamics of bacterial communities under field conditions with regard to the heterogeneity and complexity of the subsurface over the long term. The study also examined diversity and microbial community composition shift, the common genera, and indicator genera before and after long-term contaminated-groundwater invasion and the relationship between the target functional community structure and environmental factors. Additionally, deciphering cooccurrence and coexclusion patterns among microbial taxa and environmental parameters could help predict potential biotic interactions (cooperation/competition), shared physiologies, or habitat affinities, thus, improving our understanding of ecological niches occupied by certain specific species. These findings offer new insights into compositions of and associations among bacterial communities and serve as a foundation for future bioreduction implementation and monitoring efforts applied to uranium-contaminated sites.

Multi-scale investigation of uranium attenuation by arsenic at an abandoned uranium mine, South Terras

Detailed mineralogical analysis of soils from the UK’s historical uranium mine, South Terras, was performed to elucidate the mechanisms of uranium degradation and migration in the 86 years since abandonment. Soils were sampled from the surface (0–2 cm) and near-surface (25 cm) in two distinct areas of ore processing activities. Bulk soil analysis revealed the presence of high concentrations of uranium (<1690 p.p.m.), arsenic (1830 p.p.m.) and beryllium (~250 p.p.m.), suggesting pedogenic weathering of the country rock and ore extraction processes to be the mechanisms of uranium ore degradation. Micro-focus XRF analysis indicated the association of uranium with arsenic, phosphate and copper; µ-XRD data confirmed the presence of the uranyl-arsenate minerals metazeunerite (Cu(UO2)2(AsO4)2·8H2O) and metatorbernite (Cu(UO2)2(PO4)2·8H2O) to be ubiquitous. Our data are consistent with the solid solution of these two uranyl-mica minerals, not previously observed at uranium-contaminated sites. Crystallites of uranyl-mica minerals were observed to coat particles of jarosite and muscovite, suggesting that the mobility of uranium from degraded ores is attenuated by co-precipitation with arsenic and phosphate, which was not previously considered at this site.

Reactive transport of uranium in a groundwater bioreduction study: Insights from high-temporal resolution 238U/235U data

We conducted a detailed investigation of U isotopes in conjunction with a broad geochemical investigation during field-scale biostimulation and desorption experiments. This investigation was carried out in the uranium-contaminated alluvial aquifer of the Rifle field research site. In this well-characterized setting, a more comprehensive understanding of U isotope geochemistry is possible. Our results indicate that U isotope fractionation is consistently observed across multiple experiments at the Rifle site. Microbially-mediated reduction is suggested to account for most or all of the observed fractionation as abiotic reduction has been demonstrated to impart much smaller, often near-zero, isotopic fractionation or isotopic fractionation in the opposite direction. Data from some time intervals are consistent with a simple model for transport and U(VI) reduction, where the fractionation factor (ε=+0.65‰ to +0.85‰) is consistent with experimental studies. However, during other time intervals the observed patterns in our data indicate the importance of other processes in governing U concentrations and 238U/235U ratios. For instance, we demonstrate that departures from Rayleigh behavior in groundwater systems arise from the presence of adsorbed species. We also show that isotope data are sensitive to the onset of oxidation after biostimulation ends, even in the case where reduction continues to remove contaminant uranium downstream. Our study and the described conceptual model support the use of 238U/235U ratios as a tool for evaluating the efficacy of biostimulation and potentially other remedial strategies employed at Rifle and other uranium-contaminated sites.

Metals other than uranium affected microbial community composition in a historical uranium-mining site.

To understand the links between the long-term impact of uranium and other metals on microbial community composition, ground- and surface water-influenced soils varying greatly in uranium and metal concentrations were investigated at the former uranium-mining district in Ronneburg, Germany. A soil-based 16S PhyloChip approach revealed 2358 bacterial and 35 archaeal operational taxonomic units (OTU) within diverse phylogenetic groups with higher OTU numbers than at other uranium-contaminated sites, e.g., at Oak Ridge. Iron- and sulfate-reducing bacteria (FeRB and SRB), which have the potential to attenuate uranium and other metals by the enzymatic and/or abiotic reduction of metal ions, were found at all sites. Although soil concentrations of solid-phase uranium were high, ranging from 5 to 1569 μg·g (dry weight) soil(-1), redundancy analysis (RDA) and forward selection indicated that neither total nor bio-available uranium concentrations contributed significantly to the observed OTU distribution. Instead, microbial community composition appeared to be influenced more by redox potential. Bacterial communities were also influenced by bio-available manganese and total cobalt and cadmium concentrations. Bio-available cadmium impacted FeRB distribution while bio-available manganese and copper as well as solid-phase zinc concentrations in the soil affected SRB composition. Archaeal communities were influenced by the bio-available lead as well as total zinc and cobalt concentrations. These results suggest that (i) microbial richness was not impacted by heavy metals and radionuclides and that (ii) redox potential and secondary metal contaminants had the strongest effect on microbial community composition, as opposed to uranium, the primary source of contamination.

A spectroscopic study on U(VI) biomineralization in cultivated Pseudomonas fluorescens biofilms isolated from granitic aquifers.

The interaction between the Pseudomonas fluorescens biofilm and U(VI) were studied using extended X-ray absorption fine structure spectroscopy (EXAFS), and time-resolved laser fluorescence spectroscopy (TRLFS). In EXAFS studies, the formation of a stable uranyl phosphate mineral, similar to autunite (Ca[UO2]2[PO4]2•2-6H2O) or meta-autunite (Ca[UO2]2[PO4]2•10-12H2O) was observed. This is the first time such a biomineralization process has been observed in P. fluorescens. Biomineralization occurs due to phosphate release from the cellular polyphosphate, likely as a cell's response to the added uranium. It differs significantly from the biosorption process occurring in the planktonic cells of the same strain. TRLFS studies of the uranium-contaminated nutrient medium identified aqueous Ca2UO2(CO3)3 and UO2(CO3)3 (4-) species, which in contrast to the biomineralization in the P. fluorescens biofilm, may contribute to the transport and migration of U(VI). The obtained results reveal that biofilms of P. fluorescens may play an important role in predicting the transport behavior of uranium in the environment. They will also contribute to the improvement of remediation methods in uranium-contaminated sites.

Effects of Mn(II) on UO2 dissolution under anoxic and oxic conditions.

Groundwater composition and coupled redox cycles can affect the long-term stability of U(IV) products from bioremediation. The effects of Mn(II), a redox active cation present at uranium-contaminated sites, on UO2 dissolution in both oxic and anoxic systems were investigated using batch and continuous-flow reactors. Under anoxic conditions Mn(II) inhibited UO2 dissolution, which was probably due to adsorption of Mn(II) and precipitation of MnCO3 that decreased exposure of U(IV) surface sites to oxidants. In contrast, Mn(II) promoted UO2 dissolution under oxic conditions through Mn redox cycling. Oxidation of Mn(II) by O2 produced reactive Mn species, possibly short-lived Mn(III) in solution or at the surface, that oxidatively dissolved the UO2 more rapidly than could the O2 alone. At pH 8 the Mn cycling was such that there was no measurable accumulation of particulate Mn oxides. At pH 9 Mn oxides could be produced and accumulate, while they were continuously reduced by UO2, with Mn(II) returning to the aqueous phase. With the rapid turnover of Mn in the redox cycle, concentrations of Mn as low as 10 μM could maintain an enhanced UO2 dissolution rate. The presence of the siderophore desferrioxamine B (a strong Mn(III)-complexing ligand) effectively decoupled the redox interactions of uranium and manganese to suppress the promotional effect of Mn(II).

Biogeochemical Controls on the Product of Microbial U(VI) Reduction

Biologically mediated immobilization of radionuclides in the subsurface is a promising strategy for the remediation of uranium-contaminated sites. During this process, soluble U(VI) is reduced by indigenous microorganisms to sparingly soluble U(IV). The crystalline U(IV) phase uraninite, or UO2, is the preferable end-product of bioremediation due to its relatively high stability and low solubility in comparison to biomass-associated nonuraninite U(IV) species that have been reported in laboratory and under field conditions. The goal of this study was to delineate the geochemical conditions that promote the formation of nonuraninite U(IV) versus uraninite and to decipher the mechanisms of its preferential formation. U(IV) products were prepared under varying geochemical conditions and characterized with X-ray absorption spectroscopy (XAS), scanning transmission X-ray microscopy (STXM), and various wet chemical methods. We report an increasing fraction of nonuraninite U(IV) species with decreasing initial U concentration. Additionally, the presence of several common groundwater solutes (sulfate, silicate, and phosphate) promote the formation of nonuraninite U(IV). Our experiments revealed that the presence of those solutes promotes the formation of bacterial extracellular polymeric substances (EPS) and increases bacterial viability, suggesting that the formation of nonuraninite U(IV) is due to a biological response to solute presence during U(VI) reduction. The results obtained from this laboratory-scale research provide insight into biogeochemical controls on the product(s) of uranium reduction during bioremediation of the subsurface.

Abiotic Reductive Immobilization of U(VI) by Biogenic Mackinawite

During subsurface bioremediation of uranium-contaminated sites, indigenous metal and sulfate-reducing bacteria may utilize a variety of electron acceptors, including ferric iron and sulfate that could lead to the formation of various biogenic minerals in situ. Sulfides, as well as structural and adsorbed Fe(II) associated with biogenic Fe(II)-sulfide phases, can potentially catalyze abiotic U(VI) reduction via direct electron transfer processes. In the present work, the propensity of biogenic mackinawite (Fe 1+x S, x = 0 to 0.11) to reduce U(VI) abiotically was investigated. The biogenic mackinawite produced by Shewanella putrefaciens strain CN32 was characterized by employing a suite of analytical techniques including TEM, SEM, XAS, and Mössbauer analyses. Nanoscale and bulk analyses (microscopic and spectroscopic techniques, respectively) of biogenic mackinawite after exposure to U(VI) indicate the formation of nanoparticulate UO2. This study suggests the relevance of sulfide-bearing biogenic minerals in mediating abiotic U(VI) reduction, an alternative pathway in addition to direct enzymatic U(VI) reduction.

Effect of Competing Electron Acceptors on the Reduction of U(VI) by Desulfotomaculum reducens

The biological reduction of soluble U(VI) to the less soluble U(IV) has been proposed as a strategy to remediate uranium-contaminated sites. However, the majority of the contaminated sites contain, in addition to U(VI), competing electron acceptors (CEAs) that can either enhance or inhibit U(VI) reduction. Desulfotomaculum reducens MI-1 is a sulfate-reducing bacterium able to reduce a variety of electron acceptors including U(VI). We characterized U(VI) reduction by D. reducens in the presence of pyruvate and three CEAs: sulfate, nitrate or soluble ferric iron. In the presence of sulfate or ferric iron and U(VI), cell growth was driven by respiration of the CEA. Nitrate was not used as an electron acceptor for growth and vegetative cells grew instead by fermenting pyruvate. Sulfate remaining after sulfate reduction has ceased or the presence of nitrate did not affect U(VI) reduction. However, in the case of sulfate, the addition of H2 after the depletion of pyruvate greatly enhanced U(VI) reduction. Contrary to sulfate and nitrate, the presence of Fe(II), the product of Fe(III) reduction, abolished U(VI) reduction. The results from this investigation suggest that this microorganism and others with similar characteristics may play a role in U(VI) bioremediation efforts but only after the soluble Fe(II) produced by Fe(III) reduction has been advected away.

Metal reduction by spores of Desulfotomaculum reducens

The bioremediation of uranium-contaminated sites is designed to stimulate the activity of microorganisms able to catalyze the reduction of soluble U(VI) to the less soluble mineral UO(2). U(VI) reduction does not necessarily support growth in previously studied bacteria, but it typically involves viable vegetative cells and the presence of an appropriate electron donor. We characterized U(VI) reduction by the sulfate-reducing bacterium Desulfotomaculum reducens strain MI-1 grown fermentatively on pyruvate and observed that spores were capable of U(VI) reduction. Hydrogen gas - a product of pyruvate fermentation - rather than pyruvate, served as the electron donor. The presence of spent growth medium was required for the process, suggesting that an unknown factor produced by the cells was necessary for reduction. Ultrafiltration of the spent medium followed by U(VI) reduction assays revealed that the factor's molecular size was below 3 kDa. Pre-reduced spent medium displayed short-term U(VI) reduction activity, suggesting that the missing factor may be an electron shuttle, but neither anthraquinone-2,6-disulfonic acid nor riboflavin rescued spore activity in fresh medium. Spores of D. reducens also reduced Fe(III)-citrate under experimental conditions similar to those for U(VI) reduction. This is the first report of a bacterium able to reduce metals while in a sporulated state and underscores the novel nature of the mechanism of metal reduction by strain MI-1.

Visualizing different uranium oxidation states during the surface alteration of uraninite and uranium tetrachloride

Low-temperature alteration reactions on uranium phases may lead to the mobilization of uranium and thereby poses a potential threat to humans living close to uranium-contaminated sites. In this study, the surface alteration of uraninite (UO(2)) and uranium tetrachloride (UCl(4)) in air atmosphere was studied by confocal laser scanning microscopy (CLSM) and laser-induced fluorescence spectroscopy using an excitation wavelength of 408 nm. It was found that within minutes the oxidation state on the surface of the uraninite and the uranium tetrachloride changed. During the surface alteration process U(IV) atoms on the uraninite and uranium tetrachloride surface became stepwise oxidized by a one-electron step at first to U(V) and then further to U(VI). These observed changes in the oxidation states of the uraninite surface were microscopically visualized and spectroscopically identified on the basis of their fluorescence emission signal. A fluorescence signal in the wavelength range of 415-475 nm was indicative for metastable uranium(V), and a fluorescence signal in the range of 480-560 nm was identified as uranium(VI). In addition, the oxidation process of tetravalent uranium in aqueous solution at pH 0.3 was visualized by CLSM and U(V) was fluorescence spectroscopically identified. The combination of microscopy and fluorescence spectroscopy provided a very convincing visualization of the brief presence of U(V) as a metastable reaction intermediate and of the simultaneous coexistence of the three states U(IV), U(V), and U(VI). These results have a significant importance for fundamental uranium redox chemistry and should contribute to a better understanding of the geochemical behavior of uranium in nature.

Bioreduction of Uranium(VI) Complexed with Citric Acid by Clostridia Affects Its Structure and Solubility

Uranium contamination of the environment from mining and milling operations, nuclear-waste disposal, and ammunition use is a widespread global problem. Natural attenuation processes such as bacterial reductive precipitation and immobilization of soluble uranium is gaining much attention. However, the presence of naturally occurring organic ligands can affect the precipitation of uranium. Here, we report that the anaerobic spore-forming bacteria Clostridia, ubiquitous in soils, sediments, and wastes, capable of reduction of Fe(III) to Fe(II), Mn(IV) to Mn(II), U(VI) to U(IV), Pu(IV) to Pu(III), and Tc(VI) to Tc(IV); reduced U(VI) associated with citric acid in a dinuclear 2:2 U(VI): citric acid complex to a biligand mononuclear 1:2 U(IV):citric acid complex,which remained in solution, in contrast to reduction and precipitation of uranium. Our findings show that U(VI) complexed with citric acid is readily accessible as an electron acceptor despite the inability of the bacterium to metabolize the complexed organic ligand. Furthermore, it suggests that the presence of organic ligands at uranium-contaminated sites can affect the mobility of the actinide under both oxic and anoxic conditions by forming such soluble complexes.

Acidobacteria Phylum Sequences in Uranium-Contaminated Subsurface Sediments Greatly Expand the Known Diversity within the Phylum

The abundance and composition of bacteria of the phylum Acidobacteria were surveyed in subsurface sediments from uranium-contaminated sites using amplification of 16S rRNA genes followed by clone/sequence analysis. Analysis of sequences from this study and public databases produced a revised and greatly expanded phylogeny of the Acidobacteria phylum consisting of 26 subgroups.

Geomicrobiological factors that control uranium mobility in the environment: Update on recent advances in the bioremediation of uranium-contaminated sites

Understanding the behavior of uranium (U) in the environment is essential not only for the protection of aquifers from U contamination but also for predicting the fate of U and other actinides disposed of in deep geological settings. It has long been believed that the redox chemistry of U can be simply predicted by thermodynamics and that the development of a low redox potential is a sufficient condition for U reduction. However, recent studies have demonstrated that redox transformations of U are controlled by kinetic factors that are strongly influenced by microbial activity. Although abiological U oxidation proceeds efficiently under oxygenic conditions, abiological reduction of U is inhibited by the formation of negatively charged U(VI)-CO3 complexes that prevail in nature. Phylogenetically diverse microorganisms are capable of enzymatically reducing U(VI)-CO3 complexes to form U(IV)-bearing minerals such as uraninite (UO2+x). The only abiological pathway currently known for the reduction of U(VI)-CO3 complexes involves the Fe(II) monohydroxo surface complex ≡FeIIIOFeIIOH0. This complex is mainly produced by the microbial reduction of Fe(III) in natural systems. Thus, U(VI) reduction is controlled both directly and indirectly, at least in part, by microbial activity. Several mechanisms of U oxidation under anoxic conditions have been revealed recently by laboratory and field studies. U(IV) is abiologically oxidized by Fe(III) and Mn(IV) oxides. Microbial reduction of nitrate to molecular nitrogen, which occurs following the depletion of O2, produces nitrogen intermediates including nitrite (NO2−), nitrous oxide (NO), and nitric oxide (N2O). Although the nitrogen intermediates oxidize U(IV), poorly crystalline Fe(III)-oxide minerals resulting from the oxidation of aqueous Fe(II) species by the nitrogen intermediates oxidize U(IV) more efficiently than the nitrogen intermediates alone. Remarkably, the formation of Ca-U(VI)-CO3 complexes resulting from increased levels of Ca2+ and/or HCO3− leads to the reoxidation of bioreduced U(IV) under reducing conditions. These geomicrobiological factors pose challenges in manipulating and/or predicting the mobility and fate of U in complex and heterogeneous environmental settings.