Pentavalent U Reactivity Impacts U Isotopic Fractionation during Reduction by Magnetite.

Meaningful interpretation of U isotope measurements relies on unraveling the impact of reduction mechanisms on the isotopic fractionation. Here, the isotope fractionation of hexavalent U [U(VI)] was investigated during its reductive mineralization by magnetite to intermediate pentavalent U [U(V)] and ultimately tetravalent U [U(IV)]. As the reaction proceeded, the remaining aqueous phase U [containing U(VI) and U(V)] systematically carried light isotopes, whereas in the bicarbonate-extracted solution [containing U(VI) and U(V)], the δ238U values varied, especially when C/C0 approached 0. This variation was interpreted as reflecting the variable relative contribution of unreduced U(VI) (δ238U < 0‰) and bicarbonate-extractable U(V) (δ238U > 0‰). The solid remaining after bicarbonate extraction included unextractable U(V) and U(IV), for which the δ238U values consistently followed the same trend that started at 0.3-0.5‰ and decreased to ∼0‰. The impact of PIPES buffer on isotopic fractionation was attributed to the variable abundance of U(V) in the aqueous phase. A few extremely heavy bicarbonate-extracted δ238U values were due to mass-dependent fractionation resulting from several hypothesized mechanisms. The results suggest the preferential accumulation of the heavy isotope in the reduced species and the significant influence of U(V) on the overall isotopic fractionation, providing insight into the U isotope fractionation behavior during its abiotic reduction process.

Coupling flow and electric fields to simulate migration and remediation of uranium in groundwater remediated by electroosmosis and a permeable reactive bio-barrier.

Combined remediation technologies are increasingly being considered to uranium contaminated groundwater, such as the joint utilize of permeable reactive bio-barrier (Bio-PRB) and electrokinetic remediation (EKR). While the assessment of uranium plume evolution in the combined remediation system (CRS) have often been impeded by insufficient understanding of multi-physical field superposition. Therefore, advanced knowledge in multi-physical field coupling in groundwater flow will be crucial to the practical application of these techniques. A two-dimensional multi-physical field coupling model was constructed for predicting the uranium degradation in CRS. The study demonstrates that the coupling model is able to predict the uranium plume evolution and rapidly evaluate the performance of CRS components. The results show that field electric direction and flow field strength are the key factors that affect the retardation and remediation performance of CRS. The reverse electric field direction significantly affected the contact reaction time of uranium in the system. The uranium residence time in the reverse electric field was 3.8 d, which was significantly greater than the original electric field (2.0 d). Depending on the voltage, the reverse electric field direction was 16%-36% more efficient than the original direction. The strength of the flow field was about two orders of magnitude higher than that of the electric field, so the groundwater flow rate dominated remediation efficiency. Reducing the flow rate by 1/2 could improve the performance of the system by approximately 66%. In addition, the coupling model can be utilized to design standard CRS for real site of uranium contaminated groundwater. To meet the optimal performance, the direction of the electric field should be set opposite to the flow field. This work has successfully used a coupling model to predict uranium contaminant-plume evolution in CRS and estimate the performance of each component.

Baseline assessment of marine actinobacterial diversity around the nuclear power plant sites, India and its application to uranium remediation.

Baseline assessments of marine microbial studies are very limited around ecologically sensitive areas of the Nuclear Power Plant (NPP) site with respect to their occurrence, distribution, role in adaptation, and their potential remediation process. The distribution and diversity of marine microbes are largely dependent on the physicochemical parameters relating to a specific area, especially spore-producing marine actinobacteria are a source for indigenous bioremediation agents. Marine actinobacterial diversity with conventional and 16 S rRNA gene analysis was done with different pre-treatment conditions and selective media. Totally, 170 different strains are identified in genera level and it belongs to 18 genera with dominant by Streptomyces sp. (75species) followed by Nocardiposis sp, (18species) Rhodococcus sp. (14species). Multiple k-dominance plots simplified the perception of marine actinobacteria according to genera level influence to standard stock. This is the first kind of study in India and the results could act as baseline inventory in terms of microbial diversity around NPP sites. Further, a potential strain of Actinomadura sp. (T5S13) produced 243.7 mg/L of EPS and remediate the Uranium radionuclides. The functional group shifting and adsorption nature were also confirmed by SEM with EDS analysis.

A critical review of uranium contamination in groundwater: Treatment and sludge disposal.

Dissolved uranium in groundwater at high concentrations is an emerging global threat to human and ecological health due to its radioactivity and chemical toxicity. Uranium can enter groundwater by geochemical reactions, natural deposition from minerals, mining, uranium ore processing, and spent fuel disposal. Although much progress has been made in uranium remediation in recent years, most published reviews on uranium treatment have focused on specific methods, particularly adsorption. This article systematically reviews the major treatment technologies, explains their mechanism and progress of uranium removal, and compares their performance under various environmental conditions. Of all treatment methods, adsorption has received much attention due to its ease of use and adaptability under various conditions. However, salinity and competition from other ions limit its application in actual field conditions. Biosorption and bioremediation are also promising methods due to their low-cost and chemical-free operation. Strong base anion exchange resins are more effective at typical groundwater pH conditions. Advanced oxidation processes like photocatalysis produce less sludge and are effective even at low uranium concentrations. Electrocoagulation shows significantly improved performance when organic ligands are added prior to treatment. The significant advantages of membrane filtration are high removal efficiency and the ability to recover uranium. While each technology has its merits and demerits, no single technology is entirely suitable under all conditions. One major area of concern with all technologies is the need to dispose of liquid and solid waste generated after treatment safely. Future research must focus on developing hybrid and state-of-the-art technologies for effective and sustainable uranium removal from groundwater. Developing holistic management strategies for uranium removal will hinge on understanding its speciation, mechanisms of fate and transport, and socio-economic conditions of the affected areas.

Persistence of the Isotopic Signature of Pentavalent Uranium in Magnetite.

Uranium isotopic signatures can be harnessed to monitor the reductive remediation of subsurface contamination or to reconstruct paleo-redox environments. However, the mechanistic underpinnings of the isotope fractionation associated with U reduction remain poorly understood. Here, we present a coprecipitation study, in which hexavalent U (U(VI)) was reduced during the synthesis of magnetite and pentavalent U (U(V)) was the dominant species. The measured δ238U values for unreduced U(VI) (∼-1.0‰), incorporated U (96 ± 2% U(V), ∼-0.1‰), and extracted surface U (mostly U(IV), ∼0.3‰) suggested the preferential accumulation of the heavy isotope in reduced species. Upon exposure of the U-magnetite coprecipitate to air, U(V) was partially reoxidized to U(VI) with no significant change in the δ238U value. In contrast, anoxic amendment of a heavy isotope-doped U(VI) solution resulted in an increase in the δ238U of the incorporated U species over time, suggesting an exchange between incorporated and surface/aqueous U. Overall, the results support the presence of persistent U(V) with a light isotope signature and suggest that the mineral dynamics of iron oxides may allow overprinting of the isotopic signature of incorporated U species. This work furthers the understanding of the isotope fractionation of U associated with iron oxides in both modern and paleo-environments.

Fabrication, characterization and U(VI) sorption properties of a novel biochar derived from Tribulus terrestris via two different approaches.

Water contamination due to radionuclides is considered a crucial environmental issue. In this study, Tribulus terrestris plant biomass was used as a precursor for obtaining biochar (BC), that was further modified by two different methods using FeCl3 to obtain two different magnetic biochars. Both (one-step biochar, called 1S-BC, and two-steps biochar, called 2S-BC) were studied to investigate their capability for adsorbing/removing uranium (VI) from aqueous solutions. The U(VI) removal efficacy of both biochars was tested for different values of pH, ionic strength, initial concentration of U(VI) and temperature. Experimental adsorption data fitted well to the Freundlich model (achieving as highest value for adsorption capacity KF = 49.56 mg g-1 (mg L-1)-1/n, R2 = 0.99). Thermodynamic studies revealed that adsorption was endothermic, characterized by inner-sphere complexation, and entropy-driven with a relatively increased randomness in the solid-solution interface. X-ray photoelectron spectroscopy (XPS) revealed that U(VI) sorption took place by surface complexation between U(VI) and oxygen containing functional groups on both biochars. Five consecutive regeneration cycles verified an excellent reusability for 1S-BC. The overall results allow to conclude that the FeCl3 modification of the biochar obtained from Tribulus terrestris plant biomass could give an efficient alternative adsorbent for U(VI) removal in a variety of environmental conditions, promoting protection of the environment and human health, as well as facilitating resource utilization and sustainable management of the materials studied.

Utilization of Citrullus lanatus L. seeds to synthesize a novel MnFe2O4-biochar adsorbent for the removal of U(VI) from wastewater: Insights and comparison between modified and raw biochar.

Uranium (U) is a radioactive and highly toxic metal. Its excessive concentrations in the aqueous environments may result in severe and irreversible damage. To fight this hazard, a raw biochar was prepared from Citrullus lanatus L. seeds, then characterized and compared with a MnFe2O4 modified biochar, both tested for U(VI) adsorption from wastewater, which was assayed for the first time in this study. The characterization of the adsorbent materials was performed by means of scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) with elemental mapping, transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), and X-ray diffraction (XRD) techniques. The effects of solution pH, concentration of sorbate and sorbents, temperature, time and ionic strength were assessed as regards their influence on U(VI) adsorption. The experimental adsorption data showed good fit to a pseudo-second-order kinetic model (reaching a value of qe = 15.12 mg g-1, R2 = 0.96 at equilibrium), and to the Langmuir isotherm (achieving a maximum score of qmax = 27.61 mg g-1, R2 = 0.96). The maximum adsorption capacity was found at 318 K. The results of the study indicate that the binding of negatively charged functional groups (carbonyls, hydroxyls, and some carboxylic groups) with MnFe2O4 significantly enhanced U(VI) adsorption. In view of the overall results, it can be concluded that the MnFe2O4 modification of the Citrullus lanatus L. seeds biochar could give an efficient alternative adsorbent for U(VI) removal in a variety of environmental conditions, simultaneously promoting resource utilization and good sustainable management of the materials studied, aiding to protect the environment and human health.