Research on the Properties of Wasteforms after Direct Involvement of Uranium-Containing Silica Gel in Glass Network Formation.

Uranium-containing silica gel (UCSG) is a secondary waste generated during the advanced treatment of nuclear wastewater. In order to reduce the growing storage pressure for UCSG, from the perspective of building a borosilicate glass network, UCSG was used to replace SiO2 in the glass-cured formula to directly achieve the immobilization of UCSG. SEM-EDS results showed that uranium was uniformly distributed in the matrix, and the maximum solid solubility of UCSG (two components: silica gel and uranyl ions) in the formula was as high as 55 wt %. At the same time, TG-MS proved that silica gel lost OH groups (down about 4.61 wt %) and formed Si-O-Si bond by condensation. FT-IR and XPS proved a change in the number of Si-O-Si bond, and new Si-O-B and Si-O-Al bond appeared on the spectrum. This was evidence that silica gel could self-involved participate in the construction of glass networks. EPR analysis obtained the changes in the coordination environment of U atom, the U atom decreased spin electrons number in the glass than in uranyl crystals. The glass also has good physical properties (hardness: 6.51 ± 0.23 GPa; density: 2.3977 ± 0.0056 g/cm3) and chemical durability (normalized leaching rate: LRU = 2.34 × 10-4 ± 2.05 × 10-6 g·m2·days-1 after 42 days), this research provided tactics for simple treatment of uranium-containing silica gel in one step.

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.

Bismuth Coordinates with Iodine Atoms to Form Chemical Bonds for Existing Stabilization in Boron Glass.

Stabilizing radioactive iodine in boron glass for disposal was the ultimate goal of this study. In this study, bismuth was used near a monument. Thermogravimetric analysis showed that bismuth could remarkably stabilize iodine atoms in boron glass (only 3.74% of the mass was lost at 850 °C). Scanning electron microscopy-energy dispersive spectrometry images showed that most of the AgI was uniformly immobilized in the glass network. X-ray photoelectron spectrometry and NMR results confirmed the change in the coordination number of boron in the samples. The density functional theory calculation helped to understand the reason for the stable presence of iodine in boron glass. Iodine atoms were difficult to bond directly with boron atoms but tended to bond with bismuth atoms. From the spatial distribution of the structural molecular orbitals, it was observed that the bismuth atom releases electrons when stimulated, and the iodine atom needs to gain an electron to reach stability. At a low treatment temperature of 550 °C, the maximum density of the immobilized sample containing bismuth is 2.42 g·cm-3, and its iodine leaching rate at day 7 can be as low as 3.77 × 10-6 g·m-2·d-1. This study provides a way to improve the properties of boron glass microscopically in the future.

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.

Macroscopic and Microscopic Investigation of U(VI) and Eu(III) Adsorption on Carbonaceous Nanofibers.

The adsorption mechanism of U(VI) and Eu(III) on carbonaceous nanofibers (CNFs) was investigated using batch, IR, XPS, XANES, and EXAFS techniques. The pH-dependent adsorption indicated that the adsorption of U(VI) on the CNFs was significantly higher than the adsorption of Eu(III) at pH < 7.0. The maximum adsorption capacity of the CNFs calculated from the Langmuir model at pH 4.5 and 298 K for U(VI) and Eu(III) were 125 and 91 mg/g, respectively. The CNFs displayed good recyclability and recoverability by regeneration experiments. Based on XPS and XANES analyses, the enrichment of U(VI) and Eu(III) was attributed to the abundant adsorption sites (e.g., -OH and -COOH groups) of the CNFs. IR analysis further demonstrated that -COOH groups were more responsible for U(VI) adsorption. In addition, the remarkable reducing agents of the R-CH2OH groups were responsible for the highly efficient adsorption of U(VI) on the CNFs. The adsorption mechanism of U(VI) on the CNFs at pH 4.5 was shifted from inner- to outer-sphere surface complexation with increasing initial concentration, whereas the surface (co)precipitate (i.e., schoepite) was observed at pH 7.0 by EXAFS spectra. The findings presented herein play an important role in the removal of radionuclides on inexpensive and available carbon-based nanoparticles in environmental cleanup applications.

Adsorption and desorption of U(VI) on functionalized graphene oxides: a combined experimental and theoretical study.

The adsorption and desorption of U(VI) on graphene oxides (GOs), carboxylated GOs (HOOC-GOs), and reduced GOs (rGOs) were investigated by batch experiments, EXAFS technique, and computational theoretical calculations. Isothermal adsorptions showed that the adsorption capacities of U(VI) were GOs > HOOC-GOs > rGOs, whereas the desorbed amounts of U(VI) were rGOs > GOs > HOOC-GOs by desorption kinetics. According to EXAFS analysis, inner-sphere surface complexation dominated the adsorption of U(VI) on GOs and HOOC-GOs at pH 4.0, whereas outer-sphere surface complexation of U(VI) on rGO was observed at pH 4.0, which was consistent with surface complexation modeling. Based on the theoretical calculations, the binding energy of [G(···)UO2](2+) (8.1 kcal/mol) was significantly lower than those of [HOOC-GOs(···)UO2](2+) (12.1 kcal/mol) and [GOs-O(···)UO2](2+) (10.2 kcal/mol), suggesting the physisorption of UO2(2+) on rGOs. Such high binding energy of [GOs-COO(···)UO2](+) (50.5 kcal/mol) revealed that the desorption of U(VI) from the -COOH groups was much more difficult. This paper highlights the effect of the hydroxyl, epoxy, and carboxyl groups on the adsorption and desorption of U(VI), which plays an important role in designing GOs for the preconcentration and removal of radionuclides in environmental pollution cleanup applications.

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.

Homogenizing microwave pyrolysis of oily sludge using nano-Fe3O4: volatile gas product analysis.

To improve the homogeneity of heating, the magnetic absorbing material Fe3O4 is considered to use in microwave pyrolysis of oily sludge. Therefore, the effect of Fe3O4 on the microwave pyrolysis of oily sludge is investigated based on gas volatile products. Thermogravimetric mass spectrometry result certifies that Fe3O4 will increase the weight-loss ratio from 13.0% to 14.1%. Also, the characteristic peak intensity of CO in gas products decreases from 5.41 × 10-10 A/g to 1.95 × 10-10 A/g, while H2O increases from 3.57 × 10-10 A/g to 7.32 × 10-10 A/g and CO2 increases from 6.87 × 10-10 A/g to 8.92 × 10-10 A/g. This is caused by the esterification of alcohols and esters and the reduction of Fe3O4 by CO. Based on the decrease in activation energy and enthalpy values of Stage II and IV, it infers that Fe3O4 catalyzes the pyrolysis process of oily sludge to some extent. Similarly, gas chromatography-mass spectrometry results show that Fe3O4 can make the types of gas products increase. Especially, the number of molecular species increases from 5 to 46 under 200-300 °C. Finally, a simple molecular dynamics simulation model is conducted, and the results are in agreement with the experimental results. This study shows that Fe3O4 improves the pyrolysis homogeneity and the pyrolysis efficiency also improves.

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.

Design anion regulated layered double hydroxide and explore its theoretical mechanism of immobilizing uranium.

It is momentous to comprehensively understand the anion's effect during the formation of Mg-Al layered double hydroxide (LDH), especially relating to the long-term disposal of uranium-containing (UO22+) residue. In this research, the CO32-, PO43- and SO42- anions were inserted into the LDH's interlayer driven by its reconstructive memory effect. The UO22+ removal capacity increased in order (typically SO42- < PO43- < CO32-). This was further confirmed by the bond length of U-S, U-P and U-C data acquired by theoretical calculation. The SEM-EDS showed anion-regulated LDH materials got fleecy and facilitated the insertion of anions. The increased average pore size and volume of calcined LDH provided convenient access for anions to easily enter interlayer. XRD results showed inserted interlayer anions could increase the interlayer spacing and expose more active sites, which was conducive to the removal of UO22+. The FTIR combined with theoretical calculation results certified anions could grasp UO22+. XPS results gave a compelling evidence that the amount of anion insertion was proportional to UO22+ removal capacity. In short, the anions could significantly improve LDH to the removal of UO22+ by the mechanism of surface and interlayer complexation. What was discovered can better evaluate the environmental behavior of UO22+ influenced by anion factors.

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.

Retraction: Simultaneous sorption and reduction of U(vi) on magnetite-reduced graphene oxide composites investigated by macroscopic, spectroscopic and modeling techniques.

[This retracts the article DOI: 10.1039/C5RA10451C.].

Retraction: Determination of chemical affinity of graphene oxide nanosheets with radionuclides investigated by macroscopic, spectroscopic and modeling techniques.

Retraction of 'Determination of chemical affinity of graphene oxide nanosheets with radionuclides investigated by macroscopic, spectroscopic and modeling techniques' by Congcong Ding et al., Dalton Trans., 2014, 43, 3888-3896.

Retraction: Tuning the chemistry of graphene oxides by a sonochemical approach: application of adsorption properties.

[This retracts the article DOI: 10.1039/C5RA02021B.].

Competitive sorption of Pb(II), Cu(II) and Ni(II) on carbonaceous nanofibers: A spectroscopic and modeling approach.

The competitive sorption of Pb(II), Cu(II) and Ni(II) on the uniform carbonaceous nanofibers (CNFs) was investigated in binary/ternary-metal systems. The pH-dependent sorption of Pb(II), Cu(II) and Ni(II) on CNFs was independent of ionic strength, indicating that inner-sphere surface complexation dominated sorption Pb(II), Cu(II) and Ni(II) on CNFs. The maximum sorption capacities of Pb(II), Cu(II) and Ni(II) on CNFs in single-metal systems at a pH 5.5±0.2 and 25±1°C were 3.84 (795.65mg/g), 3.21 (204.00mg/g) and 2.67 (156.70mg/g)mmol/g, respectively. In equimolar binary/ternary-metal systems, Pb(II) exhibited greater inhibition of the sorption of Cu(II) and Ni(II), demonstrating the stronger affinity of CNFs for Pb(II). The competitive sorption of heavy metals in ternary-metal systems was predicted quite well by surface complexation modeling derived from single-metal data. According to FTIR, XPS and EXAFS analyses, Pb(II), Cu(II) and Ni(II) were specifically adsorbed on CNFs via covalent bonding. These observations should provide an essential start in simultaneous removal of multiple heavy metals from aquatic environments by CNFs, and open the doorways for the application of CNFs.

Novel fungus-Fe3O4 bio-nanocomposites as high performance adsorbents for the removal of radionuclides.

The bio-nanocomposites of fungus-Fe3O4 were successfully synthesized using a low-cost self-assembly technique. SEM images showed uniform decoration of nano-Fe3O4 particles on fungus surface. The FTIR analysis indicated that nano-Fe3O4 was combined to the fungus surface by chemical bonds. The sorption ability of fungus-Fe3O4 toward Sr(II), Th(IV) and U(VI) was evaluated by batch techniques. Radionuclide sorption on fungus-Fe3O4 was independent of ionic strength, indicating that inner-sphere surface complexion dominated their sorption. XPS analysis indicated that the inner-sphere radionuclide complexes were formed by mainly bonding with oxygen-containing functional groups (i.e., alcohol, acetal and carboxyl) of fungus-Fe3O4. The maximum sorption capacities of fungus-Fe3O4 calculated from Langmuir isotherm model were 100.9, 223.9 and 280.8 mg/g for Sr(II) and U(VI) at pH 5.0, and Th(IV) at pH 3.0, respectively, at 303 K. Fungus-Fe3O4 also exhibited excellent regeneration performance for the preconcentration of radionuclides. The calculated thermodynamic parameters showed that the sorption of radionuclides on fungus-Fe3O4 was a spontaneous and endothermic process. The findings herein highlight the novel synthesis method of fungus-Fe3O4 and its high sorption ability for radionuclides.

Simultaneous adsorption and reduction of U(VI) on reduced graphene oxide-supported nanoscale zerovalent iron.

The reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) composites were synthesized by chemical deposition method and were characterized by SEM, high resolution TEM, Raman and potentiometric acid-base titrations. The characteristic results showed that the nZVI nanoparticles can be uniformly dispersed on the surface of rGO. The removal of U(VI) on nZVI/rGO composites as a function of contact time, pH and U(VI) initial concentration was investigated by batch technique. The removal kinetics of U(VI) on nZVI and nZVI/rGO were well simulated by a pseudo-first-order kinetic model and pseudo-second-order kinetic model, respectively. The presence of rGO on nZVI nanoparticles increased the reaction rate and removal capacity of U(VI) significantly, which was attributed to the chemisorbed OH(-) groups of rGO and the massive enrichment of Fe(2+) on rGO surface by XPS analysis. The XRD analysis revealed that the presence of rGO retarded the transformation of iron corrosion products from magnetite/maghemite to lepidocrocite. According to the fitting of EXAFS spectra, the UC (at ∼2.9Å) and UFe (at ∼3.2Å) shells were observed, indicating the formation of inner-sphere surface complexes on nZVI/rGO composites. Therefore, the nZVI/rGO composites can be suitable as efficient materials for the in-situ remediation of uranium-contaminated groundwater in the environmental pollution management.