Amidoxime-grafted cotton fibers with anti-microbial sludge for efficient uranium recovery.

Uranium as a nuclear fuel, its source and aftertreatment has been a hot topic of debate for developers. In this paper, amidoxime and guanidino-modified cotton fibers (DC-AO-PHMG) were synthesized by the two-step functionalization approach, which exhibited remarkable antimicrobial and high uranium recovery property. Adsorption tests revealed that DC-AO-PHMG had excellent selectivity and anti-interference properties, the maximum adsorption capacity of 609.75 mg/g. More than 85 % adsorption capacity could still be kept after 10 adsorption-desorption cycles, and it conformed to the pseudo-second-order kinetic model and the Langmuir adsorption isotherm model as a spontaneous heat-absorbing chemical monolayer process. FT-IR, EDS and XPS analyses speculated that the amidoxime and amino synergistically increased the uranium uptake. The inhibitory activities of DC-AO-PHMG against three aquatic bacteria, BEY, BEL (from Yellow River water and lake bottom silt, respectively) and B. subtilis were significantly stronger, and the uranium adsorption was not impacted by the high bacteria content. Most importantly, DC-AO-PHMG removed up to 94 % of uranium in simulated seawater and extracted up to 4.65 mg/g of uranium from Salt Lake water, which demonstrated its great potential in the field of uranium resource recovery.

Microbial etch: A novel construction method of functionalized biochar for enhanced uranium extraction in radioactive wastewater.

Nuclear energy is playing an increasingly important role on the earth, but the nuclear plants leaves a legacy of radioactive waste pollution, especially uranium-containing pollution. Straw biochar with wide sources, large output, low cost, and easy availability, has emerged as a promising material for uranium extraction from radioactive wastewater, but the natural biomass with suboptimal structure and low content of functional groups limits the efficiency. In this work, microbial etch was first came up to regulate the biochar's structure and function. The surface of the biochar becomes rougher and more microporous, and the mineral contents (Ca, P) indirectly increased by microbial etch. The biochar was modified by calcium phosphate and exhibited a remarkable uranium extraction capacity of 590.8 mg g-1 (fitted value). This work provides a cost-effective and sustainable method for preparing functionalized biochar via microbial etch, which has potential for application to uranium extraction from radioactive wastewater.

The effect of extracellular polymeric substances on MICP solidifying rare earth slags and stabilizing Th and U.

Microbially induced carbonate precipitation (MICP) has been used to cure rare earth slags (RES) containing radionuclides (e.g. Th and U) and heavy metals with favorable results. However, the role of microbial extracellular polymeric substances (EPS) in MICP curing RES remains unclear. In this study, the EPS of Lysinibacillus sphaericus K-1 was extracted for the experiments of adsorption, inducing calcium carbonate (CaCO3) precipitation and curing of RES. The role of EPS in in MICP curing RES and stabilizing radionuclides and heavy metals was analyzed by evaluating the concentration and morphological distribution of radionuclides and heavy metals, and the compressive strength of the cured body. The results indicate that the adsorption efficiencies of EPS for Th (IV), U (VI), Cu2+, Pb2+, Zn2+, and Cd2+ were 44.83%, 45.83%, 53.7%, 61.3%, 42.1%, and 77.85%, respectively. The addition of EPS solution resulted in the formation of nanoscale spherical particles on the microorganism surface, which could act as an accumulating skeleton to facilitate the formation of CaCO3. After adding 20 mL of EPS solution during the curing process (Treat group), the maximum unconfined compressive strength (UCS) of the cured body reached 1.922 MPa, which was 12.13% higher than the CK group. The contents of exchangeable Th (IV) and U (VI) in the cured bodies of the Treat group decreased by 3.35% and 4.93%, respectively, compared with the CK group. Therefore, EPS enhances the effect of MICP curing RES and reduces the potential environmental problems that may be caused by radionuclides and heavy metals during the long-term sequestration of RES.

Electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites for persistent uranium recovery at a low potential.

Electrochemical uranium extraction (EUE) from seawater is a very promising strategy, but its practical application is hindered by the high potential for electrochemical system, as well as the low selectivity, efficiency, and poor stability of electrode. Herein, we developed creatively a low potential strategy for persistent uranium recovery by electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites coupled with indirect reduction of uranium, finally achieving high selectivity, efficient and persistent uranium recovery. As-designed titanium dioxide rich in oxygen vacancies (TiO2-VO) electrode displayed an EUE efficiency of ∼99.9 % within 180 min at a low potential of 0.09 V in simulated seawater with uranium of 5∼20 ppm. Moreover, the TiO2-VO electrode also showed high selectivity (89.9 %) to uranium, long-term cycling stability and antifouling activity in natural seawater. The excellent EUE property was attributed to the fact that electrochemistry-assisted in-situ regeneration of oxygen vacancies and Ti(III) active sites enhanced EUE cycling process and achieved persistent uranium recovery. The continuous regeneration of oxygen vacancies not only reduced the adsorption energy of U(VI)O22+ but also serve as a storage and transportation channel for electrons, accelerating electron transfer from Ti(III) to U(VI) at solid-liquid interface and promoting EUE kinetic rate.

Enhanced microbial remediation of uranium tailings through red soil utilization.

Seepage of uranium tailings has become a focus of attention in the uranium mining and metallurgy industry, and in-situ microbial remediation is considered an effective way to treat uranium pollution. However, this method has the drawbacks of easy biomass loss and unstable remediation effect. To overcome these issues, spare red soil around the uranium mine was used to enhance the efficiency and stability of bioremediation. Furthermore, the bioremediation mechanism was revealed by employing XRD, FTIR, XPS, and 16S rRNA. The results showed that red soil, as a barrier material, had the adsorption potential of 8.21-148.00 mg U/kg soil, but the adsorption is accompanied by the release of certain acidic and oxidative substances. During the dynamic microbial remediation, red soil was used as a cover material to neutralize acidity, provide a higher reduction potential (<-200 mV), and increase the retention rate of microbial agent (19.06 mL/d) compared to the remediation group without red soil. In the presence of red soil, the anaerobic system could maintain the uranium concentration in the solution below 0.3 mg/L for more than 70 days. Moreover, the generation of new clay minerals driven by microorganisms was more conducive to the stability of uranium tailings. Through alcohol and amino acid metabolism of microorganisms, a reducing environment with reduced valence states of multiple elements (such as S2-, Fe2+, and U4+) was formed. At the same time, the relative abundance of functional microbial communities in uranium tailings improved in presence of red soil and Desulfovirobo, Desulfocapsa, Desulfosporosinus, and other active microbial communities reconstructed the anaerobic environment. The study provides a new two-in-one solution for treatment of uranium tailings and resource utilization of red soil through in-situ microbial remediation.

Evaluation and health risk assessment of arsenic and potentially toxic elements pollution in groundwater of Majha Belt, Punjab, India.

Concentrations of potentially toxic elements (PTEs) like arsenic, uranium, iron, and nitrate in the groundwater of the Majha Belt (including Tarn Taran, Amritsar, Gurdaspur, and Pathankot districts) in Punjab, India were measured to evaluate the health risks associated with its consumption and daily use. The average concentrations of these elements in some locations exceeded the WHO-recommended values. Arsenic and iron toxicity levels were found to be higher in the Amritsar district, while uranium toxicity was more prevalent in Tarn Taran. The Trace Element Evaluation Index suggests that Amritsar is one of the districts most affected by toxic elements. According to the US Environmental Protection Agency's (USEPA) guidelines, the HQ values of U, Fe, and nitrate were less than one, indicating that there is no non-carcinogenic health risk for adults and children. However, the hazard quotient (HQ) value for arsenic was greater than one, indicating a higher possibility of health risk due to arsenic in the study area. The total hazard index values of 44.10% of samples were greater than four for arsenic, indicating that people in the Majha Belt are at a very high health risk due to the usage of water for drinking and domestic purposes. The cancer risk assessment values for arsenic in children (5.69E + 0) and adults (4.07E + 0) were higher than the accepted limit of USEPA (10-4 to 10-6) in the Majha Belt. The average radiological cancer risk values of U for children and adults were 8.68E-07 and 9.45E-06, respectively, which are well below the permissible limit of 1.67 × 10-4 suggested by the Atomic Energy Regulatory Board of DAE, India. The results of this study confirm that the residents of the Majha Belt who use contaminated groundwater are at a serious risk of exposure to arsenic in the Amritsar district and uranium in Tarn Taran district.

Anchoring chitosan/phytic acid complexes on polypyrrole nanotubes as capacitive deionization electrodes for uranium capture from wastewater.

Capacitive deionization (CDI) technology holds great potential for rapid and efficient uranyl ion removal from wastewater. However, the related electrode materials still have much room for research. Herein, chitosan/phytic acid complexes were anchored on polypyrrole nanotubes (CS/PA-PPy) to fabricate the electrode for the electrosorption of uranyl ions (UO22+). In this system, polypyrrole nanotubes provided specific channels for ion and electron diffusion, and chitosan/phytic acid complexes offered selective sites for UO22+ binding. The results demonstrated that CS/PA-PPy via electrosorption showed faster kinetics and higher uranium uptake than those via physicochemical adsorption. The maximum adsorption capacity toward UO22+ via electrosorption (1.2 V) could reach 799.3 mg g-1, which was higher than most of the reported CDI electrodes. Electrochemical measurements and experimental characterizations showed that the electrosorption of UO22+ by CS/PA-PPy was a synergistic effect of capacitive process and physicochemical adsorption, in which the capacitive mechanism involved the formation of an electric double layer from hollow polypyrrole nanotubes, whereas the coordination of phosphate, amino and hydroxyl groups with UO22+ was attributed to physicochemical adsorption. With the rational design of material, along with its excellent uranium removal performance, this work exhibited a novel and potential composite electrode for uranium capture via CDI from wastewater.

Occurrence and geochemistry of altered radioactive accessory minerals as sources of radionuclide in Mesozoic granite aquifers (Korea).

Accessory minerals in granitic rocks are unlikely significant radionuclide contributions to groundwater due to their remarkable durability. However, accessory minerals incorporating U and Th may suffer structural damages due to the radioactivity and become highly susceptible to alteration. This study investigates geochemistry coupled with textural analysis of the U-Th bearing accessory minerals using a field emission scanning electron microscope and an electron probe micro-analyzer. Altered zircons with numerous open structures related to the radioactive decay show higher contents of U and Th and low analytical totals. Some thorites show high contents of U and non-formula elements due to the hydrothermal alteration in the metamicted thorite. The cerianite including U occurs as micro-veinlet in fracture with trace of Fe and Mn oxides, which indicates secondary phase formation from the decomposed accessory minerals in an oxidizing environment. Some accessory minerals with the high content of U and Th have been found in Mesozoic granite terrain in South Korea, where high concentration levels of radionuclide in groundwater were also reported. The leaching of U may be more likely when the accessory minerals are highly metamicted or altered as found in our samples. The altered zircon and thorite of the study area could be major carriers of radioelement in Mesozoic granitic aquifers where the occurrence of soluble U-minerals has not been reported.

Gamma ray spectrometric analysis and assessment of radiation hazards in soils of Mbeere North region, Kenya.

This study used gamma ray spectrometry to determine the radiological safety of construction soil sampled randomly from Mbeere North region, Kenya. The mean activity concentration of 232Th, 238U, and 40K was 149.7 ± 2.8 Bqkg-1, 88.3 ± 2.4 Bqkg-1, and 490 ± 35 Bqkg-1, respectively. These averages exceed the world average for all the radionuclides. The radionuclides were non-uniformly distributed, with higher concentrations along the slopes and on the feet of the hills. The mean absorbed dose rate, indoor and outdoor annual effective dose, radium equivalent, external hazard index, and internal hazard index were 157.9 ± 4.4 nGh-1, 0.58 ± 0.02 mSvy-1, 0.39 ± 0.01 mSvy-1, 340.7 ± 9.2 Bqkg-1, 0.92 ± 0.02 and 1.14 ± 0.03, respectively. Among the radiation safety indicators, only the average internal hazard index exceeded slightly the acceptable safe limit. Therefore, soils of Mbeere North region are radiologically safe for use in brick making and construction of human habitats.

Leaching behaviour of 226Ra from uranium tailings and adsorption behaviour in geotechnical medias.

The leaching process of uranium tailings is a typical water-rock interaction. The release of 226Ra from uranium tailings depends on the nuclides outside the intrinsic properties of uranium tailings on the one hand, and is influenced by the water medium on the other. In this paper, a uranium tailings repository in southern China was used as a research object, and uranium tailings at different depths were collected by drilling samples and mixed to analyze the 226Ra occurrence states. Static dissolution leaching experiments of 226Ra under different pH conditions, solid-liquid ratio conditions, and ionic strength conditions were carried out, and the adsorption and desorption behaviours of 226Ra in five representative stratigraphic media were investigated. The results show that 226Ra has a strong adsorption capacity in representative strata, with adsorption distribution coefficient Kd values ranging from 1.07E+02 to 1.29E+03 (mL/g) and desorption distribution coefficients ranging from 4.97E+02 to 2.71E+03 (mL/g), but the adsorption is reversible. The 226Ra in uranium tailings exists mainly in the residual and water-soluble states, and the release of 226Ra from uranium tailings under different conditions is mainly from the water-soluble and exchangeable state fractions. Low pH conditions, low solid-liquid ratio conditions and high ionic strength conditions are favourable to the release of 226Ra from uranium tailings, so the release of 226Ra from uranium tailings can be reduced by means of adjusting the pH in the tailings and setting up a water barrier. The results of this research have important guiding significance for the management of existing uranium tailings ponds and the control of 226Ra migration in groundwater, which is conducive to guaranteeing the long-term safety, stability and sustainability of uranium mining sites.

Improving the level of water quality and plant species diversity in the reservoir accumulating natural effluents from the reclaimed uranium-containing industrial waste dump.

Due to the need to achieve the principles of sustainable development and to understand the processes of formation of phytocenoses in areas that were adversely affected by the industrial impact, this study assessed the condition of the Grachevsky uranium mine (Kazakhstan), which underwent conservation procedures about 25 years ago. The purpose is to determine the level of water quality and phytocenosis of the shores of the reservoir accumulating natural effluents from reclaimed dumps and anthropogenic sites of a uranium mine, as well as quality indicators and toxicology. The assessment included a qualitative research method (analysis of documents) to determine agro-climatic conditions and empirical methods of collecting information. The authors studied the intensity of ionizing radiation of the gamma background of the water surface of the reservoir (and sections of the shoreline and territories adjacent to the reservoir), and hydrochemical parameters of the waters of the reservoir, and performed a description of the botanical diversity. The vegetation cover of the sections of the reservoir shore is at different stages of syngenesis and is represented by pioneer groupings, group thicket communities, and diffuse communities. Favorable ecological conditions for the settlement and development of plants develop within the shores of the reservoir. The intensity levels of ionizing radiation do not exceed the maximum permissible levels and practically do not affect the formation of phytocenoses. An anthropogenically modified dry meadow with the participation of plants typical of the steppe zone has been formed on the floodplain terrace. Concerning the indicators of quality and toxicology of this reservoir, the water can be used for household and drinking purposes under the condition of prior water treatment. It can be concluded that a high level of natural purification of the reservoir waters occurred within twenty years after the reclamation of the uranium mine.

Facile and scalable synthesis of functionalized hierarchical porous polymers for efficient uranium adsorption.

Efficient uranium capture from wastewater holds great importance for the environmental remediation and sustainable development of nuclear energy, but it is a tremendous challenge. Herein, a facile and scalable approach is reported to fabricate functionalized hierarchical porous polymers (PPN-3) decorated with high density of phosphate groups for uranium adsorption. The as-constructed hierarchical porous structure could allow rapid diffusion of uranyl ions, while abundant phosphate groups that serve as adsorption sites could provide the high affinity for uranyl. Consequently, PPN-3 shows a high uranium adsorption uptake of 923.06 mg g-1 and reaches adsorption equilibrium within simply 10 min in uranium-spiked aqueous solution. Moreover, PPN-3 affords selective adsorption of uranyl over multiple metal ions and possesses a rapid and high removal rate of U(VI) in real water systems. Furthermore, this study offers direct polymerization strategy for the cost-effective fabrication of phosphate-functionalized porous organic polymers, which may provide promising application potential for uranium extraction.

Open-Framework Vanadate as Efficient Ion Exchanger for Uranyl Removal.

The elimination of uranium from radioactive wastewater is crucial for the safe management and operation of environmental remediation. Here, we present a layered vanadate with high acid/base stability, [Me2NH2]V3O7, as an excellent ion exchanger capturing uranyl from highly complex aqueous solutions. The material possesses an indirect band gap, ferromagnetic characteristic and a flower-like morphology comprising parallel nanosheets. The layered structure of [Me2NH2]V3O7 is predominantly upheld by the H-bond interaction between anionic framework [V3O7]nn- and intercalated [Me2NH2]+. The [Me2NH2]+ within [Me2NH2]V3O7 can be readily exchanged with UO22+. [Me2NH2]V3O7 exhibits high exchange capacity (qm = 176.19 mg/g), fast kinetics (within 15 min), high removal efficiencies (>99%), and good selectivity against an excess of interfering ions. It also displays activity for UO22+ ion exchange over a wide pH range (2.00-7.12). More importantly, [Me2NH2]V3O7 has the capability to effectively remove low-concentration uranium, yielding a residual U concentration of 13 ppb, which falls below the EPA-defined acceptable limit of 30 ppb in typical drinking water. [Me2NH2]V3O7 can also efficiently separate UO22+ from Cs+ or Sr2+ achieving the highest separation factors (SFU/Cs of 589 and SFU/Sr of 227) to date. The BOMD and DFT calculations reveal that the driving force of ion exchange is dominated by the interaction between UO22+ and [V3O7]nn-, whereas the ion exchange rate is influenced by the mobility of UO22+ and [Me2NH2]+. Our experimental findings indicate that [Me2NH2]V3O7 can be considered as a promising uranium scavenger for environmental remediation. Additionally, the simulation results provide valuable mechanistic interpretations for ion exchange and serve as a reference for designing novel ion exchangers.

Novel biocompatible N-rich AIE fluorescent probe for live cell imaging and visual onsite detection of uranium.

A sensitive and biocompatible N-rich probe for rapid visual uranium detection was constructed by grafting two trianiline groups to 2,6-bis(aminomethyl)pyridine. Possessing excellent aggregation-induced emission (AIE) property and the advantages to form multidentate chelate with U selectively, the probe has been applied successfully to visualize uranium in complex environmental water samples and living cells, demonstrating outstanding anti-interference ability against large equivalent of different ions over a wide effective pH range. A large linear range (1.0 × 10-7-9.0 × 10-7 mol/L) and low detection limit (72.6 nmol/L, 17.28 ppb) were achieved for the visual determination of uranium. The recognition mechanism, photophysical properties, analytical performance and cytotoxicity were systematically investigated, demonstrating high potential for fast risk assessment of uranium pollution in field and in vivo.

Single Cell Analysis of Human Colonoids Exposed to Uranium-Bearing Dust.

BACKGROUND: Uranium exposure remains an important environmental legacy and physiological health concern, with hundreds of abandoned uranium mines located in the Southwestern United States largely impacting underserved indigenous communities. The negative effects of heavy metals on barrier permeability and inhibition of intestinal epithelial healing have been described; however, transcriptomic changes within the intestinal epithelial cells and impacts on lineage differentiation are largely unknown. OBJECTIVES: Herein, we sought to determine the molecular and cellular changes that occur in the colon in response to uranium bearing dust (UBD) exposure. METHODS: Human colonoids from three biologically distinct donors were acutely exposed to UBD then digested for single cell RNA sequencing to define the molecular changes that occur to specific identities of colonic epithelial cells. Validation in colonoids was assessed using morphological and imaging techniques. RESULTS: Human colonoids acutely exposed to UBD exhibited disrupted proliferation and hyperplastic differentiation of the secretory lineage cell, enteroendocrine cells (EEC). Single-cell RNA sequencing also showed more EEC subtypes present in UBD-exposed colonoids. DISCUSSION: These findings highlight the significance of crypt-based proliferative cells and secretory cell differentiation using human colonoids to model major colonic responses to uranium-bearing particulate dust exposure. https://doi.org/10.1289/EHP13855.

Absorbed dose rates and biological consequences of discrete alpha-emitting particles embedded in tissue.

This study calculates dose rate in Gy y-1 for individual dust, soil, and sediment particles that contain significant amounts of alpha-emitting uranium or thorium. When inhaled or ingested, these particles deliver radiation dose to organs where they embed. The presented method uses X-ray microscopy to measure alpha emitting elements in environmental microparticles, followed by calculation of dose rates delivered to the targeted volume of tissues that surround embedded microparticles. The example calculations use a real-world, 89% uranium house dust particle.

Gross alpha/beta and radionuclide activity concentrations in soil, plant and some fruits around the Tehran Research Reactor.

Human activities usually have some contamination as effluents from chemical industries and radionuclides from nuclear reactors. For assessing the probable radioactive contamination in vicinity of Tehran Research Reactor, The gross alpha and beta radioactivity concentrations in soil, pine and cedar leaves and some selected fruits (fig, apple, berry and pomegranate) were investigated using an alpha/beta spectrometer during 2021-2022. Also, the concentrations of artificial and natural radionuclides in samples were investigated by the method of gamma spectroscopy. The gross alpha activity concentrations in soil, pine and cedar leaves and some selected fruits samples are from 0.05 to 0.35 Bq/gr and 0.07-0.31 Bq/gr and 0.04-0.18 Bq/gr, respectively. The gross beta activity concentrations in soil, pine and cedar leaves and some selected fruit samples are from 0.73 to 4.25 Bq/gr and 0.21-3.97 Bq/gr and 1.01-2.71 Bq/gr, respectively. Average activities concentration of natural radionuclide 232Th, 238U and 40K in soil, pine and cedar leaves and some selected fruits are 31.89-16.23-582.73 Bq/kg and 1.84-0.99-84.60 Bq/kg and 1.98-1.09-72.08 Bq/kg respectively. From artificial radionuclides, just 137Cs is recognized in soil sample and the range of 137Cs concentration in surface soils was observed to vary in the range 0.85-2.21 (Bq/kg). The result showed that the Tehran Research Reactor activities not have increased the environmental radioactivity and radiation level in the area.

Aneurinibacillus uraniidurans sp. nov., a uranium-resistant bacterium isolated from uranium-contaminated soil.

A novel Gram-positive strain, B1T, was isolated from uranium-contaminated soil. The strain was aerobic, rod-shaped, spore-forming, and motile. The strain was able to grow at 20-45 °C, at pH 6.0-9.0, and in the presence of 0-3 % (w/v) NaCl. The complete genome size of the novel strain was 3 853 322 bp. The genomic DNA G+C content was 45.5 mol%. Phylogenetic analysis based on the 16S rRNA gene sequence showed that strain B1T has the highest similarity to Aneurinibacillus soli CB4T (96. 71 %). However, the novel strain showed an average nucleotide identity value of 89.02 % and a digital DNA-DNA hybridization value of 37.40 % with strain CB4T based on the genome sequences. The major fatty acids were iso-C15 : 0 and C16 : 0. The predominate respiratory quinone was MK7. Diphosphatidylglycerol, phosphatidylmethylethanolamine, phosphatidylethanolamine, phosphatidylglycerol, unidentified phospholipids, an unidentified aminolipid and an unidentified lipid were identified as the major polar lipids. The phylogenetic, phenotypic, and chemotaxonomic analyses showed that strain B1T represents a novel species of the genus Aneurinibacillus, for which the name Aneurinibacillus uraniidurans sp. nov. is proposed. The type strain is B1T (=GDMCC 1.4080T=JCM 36228T). Experiments have shown that strain B1T demonstrates uranium tolerance.

Cinnamic Acid: A Low-Toxicity Natural Bidentate Ligand for Uranium Decorporation.

Uranium accumulation in the kidneys and bones following internal contamination results in severe damage, emphasizing the pressing need for the discovery of actinide decorporation agents with efficient removal of uranium and low toxicity. In this work, cinnamic acid (3-phenyl-2-propenoic acid, CD), a natural aromatic carboxylic acid, is investigated as a potential uranium decorporation ligand. CD demonstrates markedly lower cytotoxicity than that of diethylenetriaminepentaacetic acid (DTPA), an actinide decorporation agent approved by the FDA, and effectively removes approximately 44.5% of uranyl from NRK-52E cells. More importantly, the results of the prompt administration of the CD solution remove 48.2 and 27.3% of uranyl from the kidneys and femurs of mice, respectively. Assessments of serum renal function reveal the potential of CD to ameliorate uranyl-induced renal injury. Furthermore, the single crystal of CD and uranyl compound (C9H7O2)2·UO2 (denoted as UO2-CD) reveals the formation of uranyl dimers as secondary building units. Thermodynamic analysis of the solution shows that CD coordinates with uranyl to form a 2:1 molar ratio complex at a physiological pH of 7.4. Density functional theory (DFT) calculations further show that CD exhibits a significant 7-fold heightened affinity for uranyl binding in comparison to DTPA.

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.