Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

Efficient purification of low-level uranium-containing wastewater by polyamine/amidoxime synergistically reinforced fiber.

The removal and recovery of uranium [U(VI)] from organic containing wastewater has been a challenging in radioactive wastewater purification. Here, we designed a polyamine/amidoxime polyacrylonitrile fiber (PAN-AO-A) with high removal efficiency, excellent selectivity, excellent organic resistance and low cost by combining the anti-organic properties of amidoxime polyacrylonitrile fiber (PAN-AO-A) with the high adsorption capacity of polyamine polyacrylonitrile fiber, which is used to extract U(VI) from low-level uranium-containing wastewater with high ammonia nitrogen and organic content. PAN-AO-A adsorbent with high grafting rate (86.52%), high adsorption capacity (qe = 618.8 mg g-1), and strong resistance to organics and impurity interference is achieved. The adsorption rate of U(VI) in both real organic and laundry wastewater containing uranium is as high as 99.7%, and the partition coefficients (Kd) are 7.61 × 105 mL g-1 and 9.16 × 106 mL g-1, respectively. The saturated adsorption capacity of PAN-AO-A in the continuous system solution can reach up to 505.5 mg g-1, and the concentration of U(VI) in the effluent is as low as 1 µg L-1. XPS analysis and Density functional theory (DFT) studies the coordination form between U(VI) and PAN-AO-A, where the most stable structure is η2-AO(UO2)(CO3)2. The -NH-/-NH2 and -C(NH2)N-OH groups of PAN-AO-A exhibit a synergistic complex effect in the U(VI) adsorption process. PAN-AO-A is a material with profound influence and limitless potential that can be used for wastewater containing U(VI) and organic matter.

Uranium speciation and distribution on the surface of Shewanella putrefaciens in the presence of inorganic phosphate and zero-valent iron under anaerobic conditions.

Shewanella putrefaciens (S. putrefaciens) is one of the main microorganisms in soil bioreactors, which mainly immobilizes uranium through reduction and mineralization processes. However, the effects of elements such as phosphorus and ZVI, which may be present in the actual environment, on the mineralization and reduction processes are still not clearly understood and the environment is mostly in the absence of oxygen. In this study, we ensure that all experiments are performed in an anaerobic glove box, and we elucidate through a combination of macroscopic experimental findings and microscopic characterization that the presence of inorganic phosphates enhances the mineralization of uranyl ions on the surface of S. putrefaciens, while zero-valent iron (ZVI) facilitates the immobilization of uranium by promoting the reduction of uranium by S. putrefaciens. Interestingly, when inorganic phosphates and ZVI co-exist, both the mineralization and reduction of uranium on the bacterial surface are simultaneously enhanced. However, these two substances exhibit a certain degree of antagonism in terms of uranium immobilization by S. putrefaciens. Furthermore, it is found that the influence of pH on the mineralization and reduction of uranyl ions is far more significant than that of inorganic phosphates and ZVI. This study contributes to a better understanding of the environmental fate of uranium in real-world settings and provides valuable theoretical support for the bioremediation and risk assessment of uranium contamination.

Surface biomineralization of uranium onto Shewanella putrefaciens with or without extracellular polymeric substances.

The influence of extracellular polymeric substances (EPS) on the interaction between uranium [U(VI)] and Shewanella putrefaciens (S. putrefaciens), especially the U(VI) biomineralization process occurring on whole cells and cell components of S. putrefaciens was investigated in this study. The removal efficiency of U(VI) by S. putrefaciens was decreased by 22% after extraction of EPS. Proteins were identified as the main components of EPS by EEM analysis and were determined to play a major role in the biosorption of uranium. SEM-EDS results showed that U(VI) was distributed around the whole cell as 500-nanometer schistose structures, which consisted primarily of U and P. However, similar uranium lamellar crystal were wrapped only on the surface of EPS-free S. putrefaciens cells. FTIR and XPS analysis indicated that phosphorus- and nitrogen-containing groups played important roles in complexing U (VI). XRD and U LIII-edge EXAFS analyses demonstrated that the schistose structure consisted of hydrogen uranyl phosphate [H2(UO2)2(PO4)2•8H2O]. Our study provides new insight into the mechanisms of induced uranium crystallization by EPS and cell wall membranes of living bacterial cells under aerobic conditions.

Mutual effects of Shewanella putrefaciens-montmorillonite and their impact on uranium immobilization.

This study investigated the immobilization behavior of U(VI) by the mixture of Shewanella putrefaciens (S. putrefaciens) and montmorillonite with batch experiment. The relevant mechanisms were discussed based on the experimental results and characterizations. It was found that the immobilization of U(VI) by S. putrefaciens-montmorillonite was inhibited at pH < 7.0 and enhanced at pH > 7.0. The inhibition effect was due to the aggregation and coverage between S. putrefaciens and montmorillonite, whereas the association of microbial dissolvable organic matters (DOM) on montmorillonite could promote immobilization of U(VI). The evidences of X-photoelectron spectroscopy (XPS) and density functional theory (DFT) simulation confirmed that the carboxyl-, hydroxyl-, nitrogen-based DOM do have the ability to interacted with U(VI). This work highlights a comprehensive and overlook perspective to understand the immobilization behavior of U(VI) in environmental organo-minerals.

Efficient extraction of U(VI) from uranium enrichment process wastewater by amine-aminophosphonate-modified polyacrylonitrile fibers.

The enrichment and recovery of U(VI) from low-level radioactive wastewater in the process of uranium enrichment is important for the sustainable development of nuclear energy and environmental protection. Herein, a novel amine-aminophosphonate bifunctionalized polyacrylonitrile fiber (AAP-PAN), was prepared for the extraction of U(VI) from simulated and real uranium-containing process wastewater. The AAP-PAN fiber demonstrated a maximum adsorption capacity of 313.6 mg g-1 at pH = 6.0 and 318 K in the batch experiments. During the dynamic column experiment, over 99.99% removal of U(VI) could be achieved by the fiber using multi-ion simulated solution and real wastewater with an excellent saturation adsorption capacity of 132.0 mg g-1 and 72.5 mg g-1, respectively. It also exhibited an outstanding reusability for at least 5 cycles of adsorption process. The mechanism for U(VI) removal was studied by Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy analysis in the assist of simulation calculation. It suggested that the amine and aminophosphonate groups can easily bind uranyl ions due to U(VI) is more likely to combine with oxygen atoms of CO and PO, respectively.

Nano zero valent iron encapsulated in graphene oxide for reducing uranium.

Nano zero-valent iron (Fe0) has been widely used to remove Uranium (U(VI)). In order to enhance the performance of Fe0 toward U(VI) removal, the Fe0 was assembled into graphene oxide (GO) sheets via 3-aminopropyl triethoxysilane (APTES) as Fe0/APTES-GO composites. The Fe0/APTES-GO composites were triumphantly prepared, characterized and analyzed by means of Scanning Electron Microscope (SEM), Transmission Electron Microscope (TEM) together with Energy Dispersive Spectrometer (EDS), X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR) and X-ray Photoelectron Spectroscopy (XPS). SEM and TEM-EDS results manifested that Fe0 particles were encapsulated into rolled-up GO, which greatly improved the stability of Fe0. Batch experiment showed that only a small amount of Fe2+ was leached in the first two leaching cycles of Fe0/APTES-GO composites. The removal capacity of Fe0/APTES-GO composites was up to 1357.99 mg/g at pH = 4.1 and T = 50 °C, which was mainly attributed to the reducing activity of Fe0 and an abundance of functional groups (i.e., -COOH, C-OH and -OH) on the Fe0/APTES-GO composites. The electrostatic potential (ESP) from the calculation also supported that U(VI) tended to be reduced at the back side of the GO-Fe0 cluster.

[Biosorption and Biomineralization of Uranium(VI) from Aqueous Solutions by Landoltia Punctata].

The biosorption and biomineralization characteristics of uranium by the duckweed Landoltia punctata was investigated in aqueous solutions enriched with 1 to 250 mg · L(-1) of U(VI) supplied as uranyl nitrate [UO2(NO3)2 · 6H2O]. The maximum uranium removal for the plant cultivar occurred at pH 4~5 of solution and their uranium removal efficiencies exceeded 90% after 24 h. In kinetics studies, the dried powder of duckweed can finished nearly 80% adsorption within 5 min, the batch adsorption equilibrium can be reached within 24 h for the living and dried powder of duckweed, Both for the living and dried powder of duckweed, the experimental data were well fitted by the pseudo-second-order rate model with the degree of fitting (r) higher than 0.99. The adsorption isotherms could be better described by the Freundlich model than the Langmuir model. In addition, Fourier transform infrared spectroscopy (FTIR) revealed that the surface of Landoltia punctata possess many active groups such as hydroxyl, carboxyl, phosphate and amide groups, the hydroxyl, amino groups involved in adsorption of U(VI) by living and dried powder of Landoltia punctata, and the phosphate groups also participated in the adsorption behavior of U(VI) by the living Landoltia punctata. The living Landoltia punctata reduction part of U(VI) to U(IV) was observed by XPS analysis. SEM and energy dispersive X-ray spectroscopy (EDS) of duckweed from 10~200 mg · L(-1) uranium treatments indeed showed root surface of living Landoltia punctata formed a significant portion of U precipitates with nanometer sized schistose structures that consisted primarily U and P, not containing C. Inorganic phosphate was released by the root cells of Landoltia punctata during the experiments providing ligands for formation of insoluble U(VI) and U(IV) phosphates. The distinct uranium peaks in the EDS spectra of the cluster on the root surface can be observed after biosorption and the uranium and phosphorus mass ratio of the cluster spot was measured to be 82.5% and 8.76% of the total component weight, respectively, and the atomic percentage of 30.89% and 25.19%, respectively. It is worth noting that the phosphorus mass ratio and the atomic rate of the control group is only 0.24% and 0.11%, respectively. But there was no similar crystals observed on the surface of dried powder of Landoltia punctata after biosorption. The present work suggests that living and dried powder of Landoltia punctata can remove more than 90% U(VI) from solution simultaneously precipitated together with phosphate by the living Landoltia punctata, and the dried powder of Landoltia punctata adsorption U(VI) is mainly through the effect of electrostatic attraction, ion exchange and complexation coordination, etc. Here, for the first time, the presence of U immobilization mechanisms within one aquatic plant is reported using Landoltia punctata.

[Biosorption of Radionuclide Uranium by Deinococcus radiodurans].

As a biological adsorbent, Living Deinococcus radiodurans was used for removing radionuclide uranium in the aqueous solution. The effect factors on biosorption of radionuclide uranium were researched in the present paper, including solution pH values and initial uranium concentration. Meanwhile, the biosorption mechanism was researched by the method of FTIR and SEM/EDS. The results show that the optimum conditions for biosorption are as follows: pH = 5, co = 100 mg · L(-1) and the maximum biosorption capacity is up to 240 mgU · g(-1). According to the SEM results and EDXS analysis, it is indicated that the cell surface is attached by lots of sheet uranium crystals, and the main biosorpiton way of uranium is the ion exchange or surface complexation. Comparing FTIR spectra and FTIR fitting spectra before and after biosorption, we can find that the whole spectra has a certain change, particularly active groups (such as amide groups of the protein, hydroxy, carboxyl and phosphate group) are involved in the biosorption process. Then, there is a new peak at 906 cm(-1) and it is a stretching vibration peak of UO2(2+). Obviously, it is possible that as an anti radiation microorganism, Deinococcus radiodurans could be used for removing radionuclide uranium in radiation environment.

[Characteristics of U (VI) biosorption by biological adsorbent of platanus leaves].

The platanus leaves were used as adsorbent to study uranium removal efficiency from aqueous solution on the basis of adsorption kinetics and isotherm equations. Static adsorption affected by initial pH values and contact time was analyzed, and surface characteristics of platanus leaves and uranium removal mechanism were investigated with the help of SEM, FTIR, XRD and XRF. The adsorption process fits pseudo-second-order kinetic model and Freundlich isotherm equation, and the maximum adsorption capacity for uranium was 19.68 mg x g(-1). Results showed that hydroxyl groups, amides II belt and carboxyl active functional groups were important for uranium removal. Structure characteristic adsorption band of cellulose was found in XRD spectra, uranium was detected, and also Ca and Na elements of the content increased. Mg element content relative decrease was found on platanus leaves after adsorption by XRF, and it proved the reaction feasibility. Speculation for the behavior of uraniu adsorption by platanus leaves was both physical adsorption and chemical adsorption, exhibiting joint action of electrostatic attraction, redox reaction, chelating ligand and ion exchange.

Screening of plant species for phytoremediation of uranium, thorium, barium, nickel, strontium and lead contaminated soils from a uranium mill tailings repository in South China.

The concentrations of uranium, thorium, barium, nickel, strontium and lead in the samples of the tailings and plant species collected from a uranium mill tailings repository in South China were analyzed. Then, the removal capability of a plant for a target element was assessed. It was found that Phragmites australis had the greatest removal capabilities for uranium (820 µg), thorium (103 µg) and lead (1,870 µg). Miscanthus floridulus had the greatest removal capabilities for barium (3,730 µg) and nickel (667 µg), and Parthenocissus quinquefolia had the greatest removal capability for strontium (3,920 µg). In this study, a novel coefficient, termed as phytoremediation factor (PF), was proposed, for the first time, to assess the potential of a plant to be used in phytoremediation of a target element contaminated soil. Phragmites australis has the highest PFs for uranium (16.6), thorium (8.68), barium (10.0) and lead (10.5). Miscanthus floridulus has the highest PF for Ni (25.0). Broussonetia papyrifera and Parthenocissus quinquefolia have the relatively high PFs for strontium (28.1 and 25.4, respectively). On the basis of the definition for a hyperaccumulator, only Cyperus iria and Parthenocissus quinquefolia satisfied the criteria for hyperaccumulator of uranium (36.4 µg/g) and strontium (190 µg/g), and could be the candidates for phytoremediation of uranium and strontium contaminated soils. The results show that the PF has advantage over the hyperaccumulator in reflecting the removal capabilities of a plant for a target element, and is more adequate for assessing the potential of a plant to be used in phytoremediation than conventional method.