Fabrication of nanofibrous PbO2 electrode embedded with Pt for decomposition of organic chelating agents.

A new fabrication method of nanofibrous metal oxide electrode comprising Pt nanofiber (Pt-NF) covered with PbO2 on a Ti substrate was proposed. Pt-NF was obtained by performing sputtering deposition of Pt on the surface of electrospun poly(vinyl alcohol) (PVA) nanofiber on a Ti substrate, in which PVA was then removed by calcination (Ti/Pt-NF). Subsequently, by introducing PbO2 to the Ti/Pt-NF using the electrodeposition method, a nanofibrous Ti/Pt-NF/PbO2 electrode was finally obtained. Because the Ti substrate was covered by nanofibrous Pt, it had no environmental exposure and thus, was not oxidized during calcination. The crystal structure of the PbO2 mainly consisted of ß-form rather than α-form; the ß-form was suitable for electrochemical decomposition and remained stable even after 20 h of use. The nanofibrous Ti/Pt-NF/PbO2 electrodes showed 10% lower anode potential, 1.6 times higher current density at water decomposition potential, lower electrical resistance in the ion charge transfer resistance, and 2.27 times higher electrochemically active surface area than those of a planar-type Ti/Pt/PbO2 electrode, and demonstrated excellent electrochemical performance. As a result, compared with the planar electrode, the Ti/Pt-NF/PbO2 electrode showed more effective electrochemical decomposition toward nitrilotriacetic acid (80%) and ethylenediaminetetraacetic acid (83%), which are commonly used as chelating agents in nuclear decontamination.

Selective adsorption of sodium dodecylbenzenesulfonate from a Cs ion mixture by electrospun mesoporous silica nanofibers.

Sodium dodecylbenzenesulfonate (SDBS) is commonly used to remove radioactive nuclides such as Cs ions during decontamination of shut-down nuclear power plants. Potential environmental problems still remain because of the incomplete removal of large amounts of SDBS from radioactive liquid waste. For the first time, mesoporous silica nanofibers (MSFs) were fabricated for an efficient SDBS separation. MSFs were prepared by electrospinning using tetraethyl orthosilicate, a surfactant, and a template polymer; the product had a large surface area, a high pore volume, and a uniform pore size distribution. The internal pores or external surface were modified with quaternary ammonium salt, providing affinity to water and an electrostatic interaction with SDBS. The MSF-based adsorbent had excellent adsorption ability for SDBS (158.98 mg/g) over conventional adsorbents. In addition, the MSF-based adsorbent could selectively adsorb SDBS from a mixed solution of SDBS and Cs ions. Judging from the Freundlich pseuso second-order kinetic adsorption, the adsorption isotherm indicated that the SDBS adsorption was a kind of multilayer physisorption.

Cesium ion-exchange resin using sodium dodecylbenzenesulfonate for binding to Prussian blue.

Radioactive Cs ions are extremely harmful to the human body, causing cancers and other diseases. Treatments were performed on radioactive Cs present in wastewater after use in industrial or medical fields. Prussian blue (PB) has been widely used for the removal of Cs ions from water but its colloidal structure hinders reuse, making it problematic for practical use. To solve this problem, we used a commercial macroporous polymer resin as a PB matrix. To provide an efficient anchor for PB, the surface of the polymer resin was decorated with sodium dodecylbenzenesulfonate to produce a negatively charged surface. The successful chemical binding between the polymer resin and PB prevented leakage of the latter during adsorption and crosslinked structure of the matrix provided regeneration of the adsorbent. The adsorbent maintained its removal efficiency after five repeats of the regeneration process. The PB-based, Cs ion-exchange resin showed excellent selectivity toward Cs ions and good reusability, maintaining its high adsorption capacity.

Desorption of cesium from hydrobiotite by hydrogen peroxide with divalent cations.

In this study, hydrogen peroxide (H2O2) was used to enhance the cation-exchange treatment for Cs+ desorption from clay minerals. Among various investigated clay minerals, hydrobiotite (HBT), which has interstratified layers of vermiculite and biotite, exhibited the highest Cs+ sorption capacity and the most favorable H2O2 activation because of its high Fe content. In X-ray diffraction analysis, HBT treated with H2O2 and 0.1 M Mg2+ showed substantial changes in its basal spacing, indicating expansion of the interlayer region induced by treatment of H2O2 and strongly hydrated divalent cations. In addition, more than 80% of the Cs+ was readily desorbed from HBT with 35% H2O2 solution and 0.1 M Mg2+ at room temperature. After three cycles under the same treatment conditions (35% H2O2 solution and 0.1 M Mg2+), approximately 99% removal of radioactive Cs+ was achieved. These results suggested that H2O2 treatment with solvated Mg2+ enhanced Cs+ desorption from HBT by altering the interlayer region through intercalation of hydrated divalent cations in conjunction with the H2O2 decomposition reaction.

Adsorption of Ethylenediaminetetraacetic Acid on a Gel-Type Ion-Exchange Resin for Purification of Liquid Waste Containing Cs Ions.

Because of its excellent chelating property, ethylenediaminetetraacetic acid (EDTA) is used as a complex agent, not only for heavy metals, but also for radioactive isotopes during the decontamination of nuclear facilities. The removal of EDTA was investigated by adsorption with commercially available, gel-type, anion-exchange resins (AERs), which are based on cross-linked polystyrene with positive tertiary amine groups. Because of the positive charge on AERs, they could adsorb EDTA effectively even in a solution mixed with ions of cesium (Cs) via electrostatic attraction. Because EDTA adsorption by cation-exchange resins (CERs) was not possible, it was concluded that the negative charges on CERs do not contribute to the interaction with EDTA. The maximum adsorption capacity (qmax) of AER (2 g/L) for EDTA removal, calculated by the Langmuir isotherm model was 0.47 mmol/g for initial EDTA concentrations in the range of 0.01⁻1 mM in the EDTA/Cs mixed solution. The Langmuir isotherm model was found to be suitable for EDTA adsorption on AERs, indicative of monolayer adsorption. The results clearly suggested that the AERs could efficiently remove EDTA, regardless of the presence of nuclides, such as Cs ions in the aqueous solution.

A remotely steerable Janus micromotor adsorbent for the active remediation of Cs-contaminated water.

We report the development of magnetically steerable self-propelled micromotors that selectively remove radioactive Cs from contaminated water. Mesoporous silica microspheres were functionalized with the highly Cs-selective copper ferrocyanide, and half of the adsorptive particle surface was then coated with ferromagnetic Ni and catalytic Pt layers to fabricate Janus micromotors. The micromotor adsorbent displayed random propulsion in an H2O2 solution via catalytic bubble evolution from the Pt surface, and the micromotor adsorbent self-propulsion resulted in an 8-fold higher Cs removal compared to the stationary adsorbent within one hour. The ferromagnetism of the Ni layer allowed the micromotor adsorbent to be magnetically and remotely steerable, and the propulsion speed under a magnetic field was ˜11-fold greater than it was in the absence of the magnetophoretic force. The adsorption of Cs by the self-propelling micromotor adsorbent and the subsequent magnetic recovery of the adsorbent enabled the successful removal of radioactive 137Cs from aqueous solutions. More than 98% of the radioactive 137Cs ions were removed from solution, even in the presence of competing ions, such as Na+ (1000 ppm).

Enhanced surface decontamination of radioactive Cs by self-generated, strippable hydrogels based on reversible cross-linking.

A self-generated, strippable hydrogel containing adsorbents was developed to remove the radioactive cesium from surfaces by adsorption for wide-area surface decontamination. Two aqueous polymeric solutions of polyvinyl alcohol (PVA) and phenylboronic-acid-grafted alginate (PBA-Alg) were easily applied to surfaces and subsequently self-generated a hydrogel based on the PBA-diol ester bond. Compared to the strippable coating and chemical gels, the PBA-diol ester bond-based hydrogel was easily peeled off the surfaces without a drying step due to its high elasticity, which is more practical and time saving. The resulting hydrogel displayed high 137Cs removal efficiencies of 91.61% for painted cement, 97.505% for aluminum, 94.05% for stainless steel, and 53.5% for cement, which was 2.3 times higher than that of Decongel due to the presence of the adsorbent in the hydrogel having an excellent Cs distribution coefficient (3.34 × 104 mL/g). Moreover, the volume of radioactive waste generated after the surface decontamination could be reduced by a simple magnetic separation of the adsorbent from the used hydrogel, which can reduce the waste disposal cost. Therefore, our hydrogel system has great potential as a new, cost-effective surface decontaminant in various nuclear industry fields including wide-area environmental remediation after a nuclear accident or terrorist attack.

Chemically bound Prussian blue in sodium alginate hydrogel for enhanced removal of Cs ions.

A new approach for efficient removal of radioactive 137Cs was developed using a sodium alginate hydrogel beads-based adsorbent containing chemically bound Prussian blue (PB). Sodium alginate was crosslinked with Fe (III) ions to form hydrogel beads, in which Fe (III) had a dual function; it served as a crosslinking agent and also led to PB formation via reaction with hexacyanoferrate. Fe (III) ions, an unusual crosslinking agent for sodium alginate gel, led to stable, homogeneous distribution of PB inside the beads. The amount of embedded PB in the composite beads was more than two times larger than in the conventional sodium alginate-PB composite beads, resulting in an adsorption capacity for Cs ions that was two to five times higher, mainly because of a higher PB contents and because of the microporosity of the sodium alginate hydrogel.

Removal of Sodium Dodecylbenzenesulfonate by Macroporous Adsorbent Resins.

Among the surfactants used for removal of radioactive nuclides generated from nuclear decontamination, sodium dodecylbenzenesulfonate (SDBS) is frequently used. A potential environmental problem of incomplete elimination of SDBS from radioactive liquid wastes (RLWs), which contain a high concentration of SDBS and radioactive nuclides, still remains. Removal of SDBS was evaluated by adsorption using commercially available, macroporous polymer-based adsorbents, HP20 and HP2MGL, which are styrene (St)- and methyl methacrylate (MMA)-based crosslinked resin beads, respectively. The effect of the macroporosity and chemical structure of the macroporous adsorbent resins (MARs) on the adsorption behavior was investigated. HP20 did not have any functionality for adsorbing SDBS, but it showed effective adsorption toward SDBS (less than 20 min to reach 90% adsorption), because of the hydrophobic interaction between the phenyl groups in the St unit in HP20 and in the SDBS. The removal of SDBS from a mixed solution of SDBS and Cs ions was investigated to elucidate the adsorption process in an imitation of the sort of RLWs. This investigation suggests that MARs can potentially be used for the removal of SDBS not only from a SDBS solution but also from a mixed solution of SDBS and Cs ions.

Eco-friendly one-pot synthesis of Prussian blue-embedded magnetic hydrogel beads for the removal of cesium from water.

A simple one-step approach to fabricating Prussian blue-embedded magnetic hydrogel beads (PB-MHBs) was fabricated for the effective magnetic removal of radioactive cesium (137Cs) from water. Through the simple dropwise addition of a mixed aqueous solution of iron salts, commercial PB and polyvinyl alcohol (PVA) to an ammonium hydroxide (NH4OH) solution, the formation of hydrogel beads and the encapsulation of PB in beads were achieved in one pot through the gelation of PVA with in situ-formed iron oxide nanoparticles as the cross-linker. The obtained PB-MHBs, with 43.77 weight % of PB, were stable without releasing PB for up to 2 weeks and could be effectively separated from aqueous solutions by an external magnetic field, which is convenient for the large-scale treatment of Cs-contaminated water. Detailed Cs adsorption studies revealed that the adsorption isotherms and kinetics could be effectively described by the Langmuir isotherm model and the pseudo-second-order model, respectively. Most importantly, the PB-MHBs exhibited excellent selectivity for 137Cs in 137Cs-contaminated simulated groundwater (55 Bq/g) with a high removal efficiency (>99.5%), and the effective removal of 137Cs from real seawater by these PB-MHBs demonstrated the excellent potential of this material for practical application in the decontamination of 137Cs-contaminated seawater.

Sodium-copper hexacyanoferrate-functionalized magnetic nanoclusters for the highly efficient magnetic removal of radioactive caesium from seawater.

Sodium-copper hexacyanoferrate (NaCuHCF)-functionalized magnetic nanoadsorbents were fabricated for the highly efficient magnetic removal of radioactive caesium from seawater. The magnetic nanoclusters (MNCs), composed of many individual Fe3O4 nanoparticles, were covalently coated with polyethyleneimine (PEI) to functionalize the MNC surfaces with NaCuHCF. After simple immobilization of Cu and Na ferrocyanide on the NC surface, the resulting NaCuHCF-functionalized MNCs showed good magnetic properties and a significant adsorption capacity for Cs+ with a high content of NaCuHCF (36.04%). The adsorption kinetics and isotherms were well fit to a pseudo-second-order model and Langmuir isotherm, respectively. The sorption of 97.35% Cs by the NaCuHCF-PEI-MNCs completed in less than 5 min, and the maximum adsorption capacity of the adsorbent was 166.67 mg/g. The NaCuHCF-PEI-MNCs selectively adsorbed Cs even in the presence of various competing ions, such as Na, K, Mg, and Ca, and the Cs removal mechanism was revealed as ion exchange between Cs in solution and Na in the NaCuHCF-PEI-MNCs. In radioactive tests, our adsorbent displayed excellent removal performance in real seawater with a high removal efficiency exceeding 99.73%, a decontamination factor exceeding 372, and a high stability in water over a wide pH range from 4 to 10 with negligible leaching of Fe.

Enhanced desorption of Cs from clays by a polymeric cation-exchange agent.

We report on a new approach to increase the removal of cesium from contaminated clays based on the intercalation of a cationic polyelectrolyte into the clay interlayers. A highly charged cationic polyelectrolyte, polyethyleneimine (PEI), was shown to intercalate into the negatively charged interlayers and readily replaced Cs ions adsorbed on the interlayers of montmorillonite. The polycation desorbed significantly more Cs strongly bound to the clay than did single cations. Moreover, additional NH4+ treatment following the PEI treatment enhanced desorption of Cs ions that were less accessible by the bulky polyelectrolyte. This synergistic effect of PEI with NH4+ yielded efficient desorption (95%) of an extremely low concentration of radioactive 137Cs in the clay, which is very difficult to remove by simple cation-exchange methods due to the increased stability of the binding of Cs to the clay at low Cs concentrations.

Removal of cesium ions from clays by cationic surfactant intercalation.

We propose a new approach to remediate cesium-contaminated clays based on intercalation of the cationic surfactant dodecyltrimethylammonium bromide (DTAB) into clay interlayers. Intercalation of DTAB was found to occur very rapidly and involved exchanging interlayer cations. The reaction yielded efficient cesium desorption (∼97%), including of a large amount of otherwise non-desorbable cesium ions by cation exchange with ammonium ions. In addition, the intercalation of DTAB afforded an expansion of the interlayers, and an enhanced desorption of Cs by cation exchange with ammonium ions even at low concentrations of DTAB. Finally, the residual intercalated surfactants were easily removed by a decomposition reaction with hydrogen peroxide in the presence of Cu2+/Fe2+ catalysts.

Colorimetric detection and removal of radioactive Co ions using sodium alginate-based composite beads.

We demonstrate a simple method for the visual determination and removal of Co ions using a bead-shaped, capturing probe based on hybridized sodium alginate. For Co ions, the designed protocol consisted of three main constituents: an azopyridine-based Co ion-probe for visual detection; sodium alginate as an adsorbent for the Co ion and a bead construct for removal and structure; silica as a linker for the probe and the alginate, leading to a robust structure. When the composite beads were exposed to Co ions, the yellow color of the beads turned to intensive violet and the color intensity was associated with the Co ion concentration. The color variation was quantified using red-green-blue (RGB) color values that were obtained with a scanner and evaluated with Photoshop. The technique achieved both visual recognition with obvious color change of the beads and efficient removal of the radioactive 60Co ion. The sensing and removal of any radioactive isotope could be achieved with an appropriate sensing probe, to provide a simple and universal platform for remediation.

Copper Ferrocyanide-Functionalized Magnetic Adsorbents Using Polyethyleneimine Coated Fe3O4 Nanoparticles for the Removal of Radioactive Cesium.

Copper ferrocyanide-functionalized magnetic nano-adsorbents were successfully synthesized by electrostatic coating of citric acid coated Fe3O4 nanoparticles with polyethyleneimine, and immobilizing copper and ferrocyanide on the surfaces of polyethyleneimine-coated nanoparticles. Radioactive cesium (Cs) adsorption tests were conducted to investigate the effectiveness of the copper ferrocyanide-functionalized magnetic nano-adsorbents toward the removal of radioactive Cs.

Copper Ferrocyanide-Functionalized Magnetic Nanoparticles for the Selective Removal of Radioactive Cesium.

Copper ferrocyanide-functionalized magnetite nanoparticles (Cu-FC-MNPs) were successfully synthesized by immobilizing copper and ferrocyanide on the surfaces of [1-(2 amino-ethyl)-3-aminopropyl] trimethoxysilane-modified magnetite nanoparticles. Radioactive cesium (Cs) adsorption tests were conducted to investigate the effectiveness of the Cu-FC-MNPS toward the removal of radioactive Cs. The Cu-FC-MNPs showed excellent separation properties using an external magnet in an aqueous solution.

Succinate Functionalization of Hyperbranched Polyglycerol-Coated Magnetic Nanoparticles as a Draw Solute During Forward Osmosis.

Hyperbranched polyglycerol-coated magnetic nanoparticles (SHPG-MNPs) were functionalized with succinate groups to form a draw solute for use in a forward osmosis (FO). After the one-step synthesis of hyperbranched polyglycerol-coated magnetic nanoparticles (HPG-MNPs), the polyglycerol groups on the surfaces of the HPG-MNPs were functionalized with succinic anhydride moieties. The resulting SHPG-MNPs showed no change of size and magnetic property compared with HPG-MNPs and displayed excellent dispersibility in water up to the concentration of 400 g/L. SHPG-MNPs solution showed higher osmotic pressure than that of HPG-MNPs solution due to the presence of surface carboxyl groups in SHPG-MNPs and could draw water from a feed solution across an FO membrane without any reverse draw solute leakage during FO process. Moreover, the water flux remained nearly constant over several SHPG-MNP darw solute regeneration cycles applied to the ultrafiltration (UF) process. The SHPG-MNPs demonstrate strong potential for use as a draw solute in FO processes.

Removal of Radioactive Cesium Using Prussian Blue Magnetic Nanoparticles.

Radioactive cesium (137Cs) has inevitably become a human concern due to exposure from nuclear power plants and nuclear accident releases. Many efforts have been focused on removing cesium and the remediation of the contaminated environment. In this study, we elucidated the ability of Prussian blue-coated magnetic nanoparticles to eliminate cesium from radioactive contaminated waste. Thus, the obtained Prussian blue-coated magnetic nanoparticles were then characterized and examined for their physical and radioactive cesium adsorption properties. This Prussian blue-coated magnetic nanoparticle-based cesium magnetic sorbent can offer great potential for use in in situ remediation.

Volatility and leachability of heavy metals and radionuclides in thermally treated HEPA filter media generated from nuclear facilities.

The purpose of the present study was to apply thermal treatments to reduce the volume of HEPA filter media and to investigate the volatility and leachability of heavy metals and radionuclides during thermal treatment. HEPA filter media were transformed to glassy bulk material by thermal treatment at 900°C for 2h. The most abundant heavy metal in the HEPA filter media was Zn, followed by Sr, Pb and Cr, and the main radionuclide was Cs-137. The volatility tests showed that the heavy metals and radionuclides in radioactive HEPA filter media were not volatilized during the thermal treatment. PCT tests indicated that the leachability of heavy metals and radionuclides was relatively low compared to those of other glasses. XRD results showed that Zn and Cs reacted with HEPA filter media and were transformed into crystalline willemite (ZnO·SiO(2)) and pollucite (Cs(2)OAl(2)O(3)4SiO(2)), which are not volatile or leachable. The proposed technique for the volume reduction and transformation of radioactive HEPA filter media into glassy bulk material is a simple and energy efficient procedure without additives that can be performed at relatively low temperature compared with conventional vitrification process.

Effects of the different conditions of uranyl and hydrogen peroxide solutions on the behavior of the uranium peroxide precipitation.

The dynamic precipitation characteristics of UO(4) in different solution conditions (pH, ionic strength, uranium and H(2)O(2) concentrations) were characterized by measuring changes in the absorbance of the precipitation solution and by monitoring the change of particle size in a circulating particle size analyzer. The precipitation solution conditions affected the precipitation characteristics such as the induction time, precipitation rate, overall precipitation time, and particle size in a complex manner. With increases in both pH and ionic strength, the induction time was prolonged, and the individual particle size decreased, but the individual particles tended to grow by aggregation to form larger precipitates. The uranium concentration and the ionic strength of the solution affected the induction time and precipitation rate to the greatest extent.