Rapid mobilization of noncrystalline U(IV) coupled with FeS oxidation

The reactivity of disordered, noncrystalline U(IV) species remains poorly characterized despite their prevalence in biostimulated sediments. Because of the lack of crystalline structure, noncrystalline U(IV) may be susceptible to oxidative mobilization under oxic conditions. The present study investigated the mechanism and rate of oxidation of biogenic noncrystalline U(IV) by dissolved oxygen (DO) in the presence of mackinawite (FeS). Previously recognized as an effective reductant and oxygen scavenger, nanoparticulate FeS was evaluated for its role in influencing U release in a flow through system as a function of pH and carbonate concentration. The results demonstrated that noncrystalline U(IV) was more susceptible to oxidation than uraninite (UO2) in the presence of dissolved carbonate. A rapid release of U occurred immediately after FeS addition without exhibiting a temporary inhibition stage, as was observed during the oxidation of UO2, although FeS still kept DO levels low. X-ray photoelectron spectroscopy (XPS) characterized a transient surface Fe(III) species during the initial FeS oxidation, which was likely responsible for oxidizing noncrystalline U(IV) in addition to oxygen. In the absence of carbonate, however, the release of dissolved U was significantly hindered as a result of U adsorption by FeS oxidation products. This study illustrates the strong interactions between iron sulfide and U(IV) species during redox transformation and implies the lability of biogenic noncrystalline U(IV) species in the subsurface environment when subjected to redox cycling events

Hydropower plants: pride and prejudice

The development of alternative energy solutions to meet the increasing energy demand requires the expansion of the production network. In this context hydropower plants (HPPs) represent a reliable renewable energy source [3] and the possibility of integrating a pumping storage system makes HPPs an excellent way to stock energy. Besides energy generation, hydropower plants present numerous benefits, including flood control and water supply, leisure and storage of electricity [7]. Nevertheless in the recent years some criticism was raised against megaprojects and few studies pointed out that budgets are constantly exceeded and schedules overrun. The methodology proposed by Gomez and Probst [4] is hereafter used allowing to study the hydropower cost evaluation as a complex problem and to reveal the key factors that have a strong influence. The purpose is to identify the processes which leads to an increase of the final cost of large dam project. Results clearly showed the involvement of uncontrollable factors in the process. The reasoning leads to a final statement: the human impossibility to foresee the unpredictable does not justify the criticism and the prejudice that was risen against hydropower plants, whose benefits remain undeniable

Mechanism of uranium reduction and immobilization in Desulfovibrio vulgaris biofilms

The prevalent formation of noncrystalline U(IV) species in the subsurface and their enhanced susceptibility to reoxidation and remobilization, as compared to crystalline uraninite, raise concerns about the long-term sustainability of the bioremediation of U-contaminated sites. The main goal of this study was to resolve the remaining uncertainty concerning the formation mechanism of noncrystalline U(IV) in the environment. Controlled laboratory biofilm systems (biotic, abiotic, and mixed biotic abiotic) were probed using a combination of U isotope fractionation and X-ray absorption spectroscopy (XAS). Regardless of the mechanism of U reduction, the presence of a biofilm resulted in the formation of noncrystalline U(IV). Our results also show that biotic U reduction is the most effective way to immobilize and reduce U. However, the mixed biotic abiotic system resembled more closely an abiotic system: (i) the U(IV) solid phase lacked a typically biotic isotope signature and (ii) elemental sulfur was detected, which indicates the oxidation of sulfide coupled to U(VI) reduction. The predominance of abiotic U reduction in our systems is due to the lack of available aqueous U(VI) species for direct enzymatic reduction. In contrast, in cases where bicarbonate is present at a higher concentration, aqueous U(VI) species dominate, allowing biotic U reduction to outcompete the abiotic processes

Uranium Isotopes Fingerprint Biotic Reduction

Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium

Uranium Isotopes Fingerprint Biotic Reduction

Knowledge of paleo-redox conditions in the Earth's history provides a window into events that shaped the evolution of life on our planet. The role of microbial activity in paleo-redox processes remains unexplored due to the inability to discriminate biotic from abiotic redox transformations in the rock record. The ability to deconvolute these two processes would provide a means to identify environmental niches in which microbial activity was prevalent at a specific time in paleo-history and to correlate specific biogeochemical events with the corresponding microbial metabolism. Here, we demonstrate that the isotopic signature associated with microbial reduction of hexavalent uranium (U), i.e., the accumulation of the heavy isotope in the U(IV) phase, is readily distinguishable from that generated by abiotic uranium reduction in laboratory experiments. Thus, isotope signatures preserved in the geologic record through the reductive precipitation of uranium may provide the sought-after tool to probe for biotic processes. Because uranium is a common element in the Earth's crust and a wide variety of metabolic groups of microorganisms catalyze the biological reduction of U(VI), this tool is applicable to a multiplicity of geological epochs and terrestrial environments. The findings of this study indicate that biological activity contributed to the formation of many authigenic U deposits, including sandstone U deposits of various ages, as well as modern, Cretaceous, and Archean black shales. Additionally, engineered bioremediation activities also exhibit a biotic signature, suggesting that, although multiple pathways may be involved in the reduction, direct enzymatic reduction contributes substantially to the immobilization of uranium

Biogeochemical controls on the product of microbial U(VI) reduction

Biologically mediated immobilization of radio-nuclides 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(TV). 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

Uranium redox transition pathways in acetate-amended sediments

Redox transitions of uranium [from U(VI) to U(IV)] in low-temperature sediments govern the mobility of uranium in the environment and the accumulation of uranium in ore bodies, and inform our understanding of Earth's geochemical history. The molecular-scale mechanistic pathways of these transitions determine the U(IV) products formed, thus influencing uranium isotope fractionation, reoxidation, and transport in sediments. Studies that improve our understanding of these pathways have the potential to substantially advance process understanding across a number of earth sciences disciplines. Detailed mechanistic information regarding uranium redox transitions in field sediments is largely nonexistent, owing to the difficulty of directly observing molecular-scale processes in the subsurface and the compositional/physical complexity of subsurface systems. Here, we present results from an in situ study of uranium redox transitions occurring in aquifer sediments under sulfate-reducing conditions. Based on molecular-scale spectroscopic, pore-scale geochemical, and macroscale aqueous evidence, we propose a biotic-abiotic transition pathway in which biomass-hosted mackinawite (FeS) is an electron source to reduce U(VI) to U(IV), which subsequently reacts with biomass to produce monomeric U(IV) species. A species resembling nanoscale uraninite is also present, implying the operation of at least two redox transition pathways. The presence of multiple pathways in low-temperature sediments unifies apparently contrasting prior observations and helps to explain sustained uranium reduction under disparate biogeochemical conditions. These findings have direct implications for our understanding of uranium bioremediation, ore formation, and global geochemical processes

Reduction and immobilization of uranium in the subsurface:controls, mechanisms, and implications for in situ bioremediation

Decades of uranium (U) mining, milling and military use left a legacy of U contamination around the world. The radioactivity and chemical toxicity of U at contaminated sites pose an acute and long-term hazard to human health and the surrounding environment. In order to diminish the risk, in situ bioremediation methods, which contribute to contaminant immobilization, are proposed. Nevertheless, the reported prevalent formation of labile and non-crystalline U(IV) species as a result of microbial U(VI) reduction, in contrast to more stable and crystalline uraninite, undermines the effectiveness of the applied bioremediation. Therefore, a holistic understanding of the controls and mechanisms that govern the formation of non-crystalline U(IV) in the environment is at the core of this thesis. Presence of common groundwater solutes (sulfate, silicate and phosphate) were shown to induce the production of bacterial extracellular polymeric substances (biofilm matrix components), which in turn increases the formation of non-crystalline U(IV) as a result of microbial U reduction. In contrast, a field study suggested that non-crystalline U(IV) was a product of abiotic U reduction followed by the sequestration of U(IV) ions by the biofilm matrix. Those contrasting theories, motivated us to look for an indicator capable of differentiating between biotic and abiotic U reduction in the environment. Uranium isotope fractionation proved to be an excellent tool. Based on our results, the isotopic signature of biotic U reduction (accumulation of 238U in the reduced phase) is easily distinguishable from the abiotic U reduction signature (either no isotopic fractionation or fractionation in the opposite direction). When contrasted with U isotope signatures recorded in the sediments, the findings of this study indicated that biological activity contributed to the formation of many ancient and modern U(IV) deposits. Equipped with a tool capable of assessing the origin of the U(IV) product, and with an understanding of the relationship between the biofilm matrix and the formation of non-crystalline U(IV), we embarked on a project to validate the mechanism responsible for non-crystalline U(IV) formation in the subsurface. Results show that regardless whether U is reduced enzymatically or though abiotic agents, the formed U(IV) species are always non-crystalline if the biofilm matrix is present. However, according to our experiments, biological U reduction resulted in better immobilization and overall reduction of U. The mechanism of U reduction in our systems was shown to be controlled by U speciation, which in turn, is govern by the presence of bicarbonate. Under low carbonate concentrations, the majority of U(VI) adsorbs onto the mineral phase thus promoting abiotic U reduction mediated by redox active minerals. However, at higher carbonate concentrations, most of U(VI) is present as aqueous U(VI)-carbonate complexes precluding sorption and thus allowing for enhanced enzymatic U reduction. The results obtained here shed light on the processes occurring at U-contaminated sites and have several field implications. The effectiveness of applied bioremediation was shown to depend on the geochemical conditions at the field site. However, the injection of bicarbonate during in situ clean-up operation enhances microbial U reduction and by this, the overall reductive immobilization of U