Magnetic hierarchical titanium ferrocyanide for the highly efficient and selective removal of radioactive cesium from water.

Selective adsorption is the most suitable technique for eliminating trace amounts of 137Cs from various volumes of 137Cs-contaminated water, including seawater. Although various metal ferrocyanide (MFC)-functionalized magnetic adsorbents have been developed for the selective removal of 137Cs and magnetic recovery of adsorbents, their adsorption capacity for Cs remains low. Here, magnetic hierarchical titanium ferrocyanide (mh-TiFC) was synthesized for the first time for enhanced Cs adsorption. Hierarchical TiFC, comprising 2-dimensional TiFC flakes, was synthesized on SiO2-coated magnetic Fe3O4 particles using a sacrificial TiO2 shell as a source of Ti4+ via a reaction with ferrocyanide under acidic conditions. The resultant mh-TiFC exhibited the highest maximum adsorption capacity (434.8 mg g-1) and enhanced Cs selectivity with an excellent Kd value (6,850,000 mL g-1) compared to those of previously reported magnetic Cs adsorbents. This enhancement was attributed to the hierarchical structure, which reduced intracrystalline diffusion and increased the surface area available for direct Cs adsorption. Additionally, mh-TiFC (0.1 g L-1) demonstrated an excellent removal efficiency of 137Cs exceeding 99.85% for groundwater and seawater containing approximately 22 ppt 137Cs. Therefore, mh-TiFC offers promising applications for the treatment of 137Cs-contaminated water.

Post-substitution of magnesium at CaI of nano-hydroxyapatite surface for highly efficient and selective removal of radioactive 90Sr from groundwater.

We have modified the ion-exchange affinity of nano-Hydroxyapatite (Ca5(PO4)3OH, HAP) surface for the rapid and selective adsorption of 90Sr from groundwater. The modification was achieved by the post-substitution of cations (Na+, Mg2+, Cu2+, Ba2+, Fe3+, and Al3+) for parent Ca2+ within surface structure of HAP. The diffraction patterns of modified HAP showed a slight shift of the (002) peak between 25° and 27° 2θ depending the ionic radius of the substituted cation. Magnesium substituted HAP, Mg-HAP, exhibited the highest removal efficiency (>95%) for 10 ppm of Sr2+, which is attributable to the higher ion-exchange affinity of substituted Mg2+ than parent Ca2+ toward Sr2+. The results of various analyses revealed that Mg substitution dominantly occurred at the CaI site of HAP, which enabled the Mg-HAP to adsorb Sr2+ at both of CaI and CaII sites whereas bare HAP could adsorb Sr2+ mainly at CaII site. Adsorption isotherms and the kinetics of Mg-HAP for Sr2+ were evaluated using a bi-Langmuir isotherm and a pseudo-second-order kinetic model, which demonstrated the Mg-HAP exhibited the highest adsorption capacity (64.69 mg/g) and fastest adsorption kinetics (0.161-1.714 g/(mg·min)) than previously modified HAPs. In the presence of competing cations at circumneutral pHs, the enhanced performance of the Mg-HAP led to a greater than 97% reduction of 90Sr (initial radioactivity = 9500 Bq/L) within 1 h. The distribution coefficient of Mg-HAP was 1.3-6.6 × 103 mL/g while that of bare HAP was 1.2-6.6 × 102 mL/g. The findings in the present study highlight that the ion-exchange affinity of CaI and CaII sites on HAP surface plays a key-role in 90Sr uptake. The proposed modification method can simply increase the affinity of HAP surface, therefore, this work can further improve the deployment of an in situ remediation technology for 90Sr contaminated groundwater, i.e., Mg-HAP-based permeable reactive barrier.

Stabilizing decontamination foam using surface-modified silica nanoparticles containing chemical reagent: foam stability, structures, and dispersion properties.

The stabilization of decontamination foams containing a chemical reagent is a crucial requirement for their use in the decontamination of nuclear power plants. We have investigated the effects on decontamination foam stability of adding silica nanoparticles (NPs) modified with various functional groups, namely propyl (-CH3), amine (-NH2), and thiol (-SH) groups. The surface properties of these silica NPs were characterized with ATR-FTIR, solid NMR, and TGA analyses. We also established that the agglomeration in such foams of the amine-modified silica NPs is weaker than that of the other modified silica NPs due to their thorough dispersion in the liquid film. Further, the foam containing amine-modified silica NPs was found to be stable for 60 min at a pH of 2, i.e. under decontamination conditions. The bubble structure analysis showed that this decontamination foam has a bubble count that is approximately 5-8 times higher than the foams containing NPs modified with the other functional groups, which indicates that the decontamination foam with amine-modified silica NPs has the best foam structure of the three investigated foams. The well-dispersed and smaller amine-modified silica NPs enhance the foam stability by providing a barrier between the gas bubbles and delaying their coalescence. In contrast, the thiol- and propyl-modified silica NPs form aggregates with large diameters that reduce the maximum capillary pressure of coalescence and hence decrease the foam stability.

Cs desorption behavior during hydrothermal treatment of illite with oxalic acid.

The desorption of radioactive cesium (Cs) in soil is influenced by the clay mineral type, adsorption site, and concentration of Cs. In this study, experiments to detect desorption of non-radioactive and radioactive Cs from illite using oxalic acid were performed for 2 days at 70 °C in hydrothermal conditions. The results showed that the 133Cs removal efficiency by oxalic acid and inorganic acid treatment was similar at high concentration (22.86 mmol/kg) of non-radioactive 133Cs. In the radioactive 137Cs experiment, the removal efficiency by oxalic acid was higher than that by inorganic acid at low concentration (0.79 × 10-6 mmol/kg) of radioactive 137Cs. Based on the illite hypothetical frayed edge site (FES) concentration of 0.612 mmol/kg, the results suggested that 137Cs was preferentially adsorbed to FES on illite. The 137Cs at low concentration was difficult to remove because it was irreversible adsorption to FES, while the non-radioactive Cs at high concentration was mainly adsorbed to planar sites, and so was easy to desorb by ion exchange. Based on the results of NMR, FTIR, and XPS analyses, we concluded that the higher efficiency of 137Cs removal at low concentration by oxalic acid treatment than by treatment with inorganic acid was because of chelation effects associated with the complexation of oxalic acid (ligands) and metal ions in irreversible site (FES).

Immobilization of uranium(VI) in a cementitious matrix with nanoscale zerovalent iron (NZVI).

We developed a novel solidification and stabilization process using a nanoscale zerovalent iron (NZVI)-cement system for reductive immobilization of hexavalent uranium (U(VI)) in a soil-cement matrix. The NZVI suspension without cement demonstrated high removal efficiency (100% in 2 h) and fast removal kinetics (53.7 Lm-2d-1), which surpassed those of other Fe-containing minerals (i.e., green rust, mackinawite, magnetite, and pyrite). Significant removal of aqueous U(VI) was observed in NZVI-cement slurries and minimal adsorbed U was desorbed by a bicarbonate/carbonate (CARB) solution. Surface analysis using scanning electron microscopy and X-ray photoelectron spectroscopy revealed U distributed homogeneously on the surface of the NZVI-cement and transformed considerably from U(VI) to reduced U species by coupled oxidation of Fe(0)/Fe(II) to Fe(III). Furthermore, the increase in pH and NZVI concentration, and presence of humic acid resulted in the enhanced U(VI) reduction in NZVI-cement slurries. The NZVI-cement system was tested with a soil matrix, resulting in successful immobilization of aqueous U(VI) in both batch and column experiments. Moreover, the U(VI) removed in the NZVI-cement system was not leached out by the CARB solution during long-term experiments. The results suggest an NZVI-cement system could represent a promising remediation alternative for effective and stable immobilization of U(VI) in contaminated sites.

Molecular Identification of Cr(VI) Removal Mechanism on Vivianite Surface.

Experimental and theoretical studies were conducted to identify the molecular-scale reaction mechanism for Cr(VI) removal by a ferrous phosphate mineral, vivianite. The surface-normalized rate constant for Cr(VI) removal in a vivianite suspension at pH 7 was higher than those obtained for other Fe(II)-containing minerals (i.e., magnetite and pyrite). The highest rate constant was obtained at pH 5, which was 35- and 264-times higher than those obtained at pH 7 and 9, respectively, indicating the dramatic acceleration of removal kinetics with decreasing pH of suspension. The X-ray photoelectron spectroscopy (XPS) and X-ray absorption near-edge structure (XANES) spectroscopy revealed that Cr(VI) removal involved reduction of Cr(VI) to Cr(III) coupled with oxidation of Fe(II) to Fe(III) on the vivianite surface. In addition, the density functional theory (DFT)-optimized structure of the Cr(VI)-vivianite complex was consistent with that obtained from extended X-ray absorption fine structure (EXAFS) spectroscopy and revealed the transformation of vivianite to amorphous Fe(III) phosphate. We also demonstrated that both Cr(VI) species, HCrO4̅ and CrO42-, can effectively bind to the vivianite surface, particularly on the Fe sites having 6 neighboring Fe molecules with 4 H2O and 2 PO4 moieties. Our results show that Cr(VI) is readily reduced to Cr(III) by vivianite via adsorption and inner-sphere complexation, suggesting that in anoxic iron-phosphate-enriched environments, vivianite may significantly influence the fate and transport of Cr(VI).

Synergistic effect of nano-sized mackinawite with cyano-cobalamin in cement slurries for reductive dechlorination of tetrachloroethylene.

Experiments were conducted to investigate the reductive dechlorination of tetrachloroethylene (PCE) by nano-Mackinawite (nFeS) with cyano-cobalamin (Cbl(III)) in cement slurries. Almost complete degradation of PCE by nFeS-Cbl(III) was observed in cement slurries in 5 h and its degradation kinetics (k(obs-PCE)=0.57 h(-1)) was 6-times faster than that of nFeS-Cbl(III) without the cement slurries. PCE was finally transformed to non-chlorinated organic compounds such as ethylene, acetylene, and C3-C4 hydrocarbons by nFeS-Cbl(III) in cement slurries. X-ray photoelectron spectroscopy and PCE degradation by cement components (SiO2, Al2O3, and CaO) revealed that both the reduced Co species in Cbl(III) and the presence of Ca in cement played an important role for the enhanced reductive dechlorination of PCE. The increase in the concentration of Cbl(III) (0.005-0.1 mM), cement ratio (0.05-0.2), and suspension pH (11.5-13.5) accelerated the PCE degradation kinetics by providing more favorable environments for the production of reactive Ca species and reduction of Co species. We also observed that the degradation efficiency of PCE by nFeS-Cbl(III)-cement lasted even at high concentration of PCE. The experimental results obtained from this study could provide fundamental knowledge of redox interactions among nFeS, Cbl(III), and cement, which could significantly enhance reductive dechlorination of chlorinated organics in contaminated natural and engineered environments.

Effect of promoter and noble metals and suspension pH on catalytic nitrate reduction by bimetallic nanoscale Fe(0) catalysts.

Experiments were conducted to investigate the effect of experimental factors (types of promotor and noble metals, H2 injection, and suspension pH) on catalytic nitrate reduction by bimetallic catalysts supported by nanoscale zero-valent iron (NZVI). NZVI without H2 injection showed 71% of nitrate reduction in 1 h. Cu/NZVI showed the almost complete nitrate reduction (96%) in 1 h, while 67% of nitrate was reduced by Ni/NZVI. The presence of noble metals (Pd and Pt) on Cu/NZVI without H2 injection resulted in the decrease of removal efficiency to 89% and 84%, respectively, due probably to the electron loss of NZVI for formation of metallic Pd and Pt. H2 injection into Cu-Pd/NZVI suspension significantly improved both catalytic nitrate reduction (>97% in 30 min) and N2 selectivity (18%), indicating that adsorbed H on active Pd sites played an important role for the enhanced nitrate reduction and N2 selectivity. The rapid passivation of NZVI surface resulted in a dramatic decrease in nitrate reduction (79-28%) with an increase in N2 selectivity (8-66%) as the suspension pH increased from 8 to 10.