Bio-Inspired Preparation of Clay-Hexacyanoferrate Composite Hydrogels as Super Adsorbents for Cs.

A facile and low-cost fabrication route, inspired by the adhesive proteins secreted by mussels, has been developed to prepare a clay-based composite hydrogel (DHG(Cu)) containing hexacyanoferrate (HCF) nanoparticles for the selective removal of Cs+ from contaminated water. Initially, montmorillonite was exfoliated prior to coating with a thin layer of polydopamine (PDOPA) via the self-polymerization of dopamine. Mixing the composite (D-clay) with the HCF precursor, followed by the addition of copper ions, led to the self-assembly of the polymer-coated exfoliated clay nanosheets into a three-dimensional network and in situ growth of KCuHCF nanoparticles embedded within the gel structure. Analytical characterization verified the fabrication route and KCuHCF immobilization by a copper-ligand complexation. Rheology testing revealed the composite hydrogel to be elastic under low strain and exhibited reversible, self-healing behavior following high strain deformation, providing a good retention of KCuHCF nanoparticles in the membrane. The adsorbent DHG(Cu) showed a superior Cs+ adsorption capacity (∼173 mg/g), with the performance maintained over a wide pH range, and an excellent selectivity for Cs+ when dispersed in seawater at low concentrations of 0.2 ppm. On the basis of its excellent mechanico-chemical properties, the fabricated hydrogel was tested as a membrane in column filtration, showing excellent removal of Cs+ from Milli-Q water and seawater, with the performance only limited by the fluid residence time. For comparison, the study also considered other composite hydrogels, which were fabricated as intermediates of DHG(Cu) or fabricated with Fe3+ as the cross-linker and reactant for HCF nanoparticle synthesis.

Taguchi L16 optimization approach for simultaneous removal of Cs+ and Sr2+ ions by a novel scavenger.

This study targeted to investigate the efficacy of a novel nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite scavenger for simultaneous elimination of Cs+ and Sr2+ ions from binary aqueous systems. Fractal analysis is introduced to assign a fractal dimension and other fractal characteristics necessary for the surface characterization in terms of fractal dimension (Ds) and pre-exponential coefficient (C), which, in theory, are independent tool and sole for each surface. It is found that the Ds value of nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type Y (NAASMS-ZY) is higher than that of nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type X (NAASMS-ZX) and nano 2-naphtyl amine6:6-azulene sodium methanesulfonate di sulphonic acid-impregnated zeolite of type A (NAASMS-ZA) which accordingly, suggests the irregularity of NAASMS-ZY surface and thus demonstrates a large surface area. To increase the scavenge efficacy, effecting parameters on scavenge process were investigated and optimized via the use of adopting Taguchi L16 design of experiments approach. It is found that, the initial metal ions concentration is the most powerful variable, and its value of contribution percentage is up to 33% and 31% for Cs+ and Sr2+, respectively. The kinetic curves and sorption isotherms at 298, 303 and 313 K were obtained, which well fitted to hyperbolic and Langmuir equations, respectively. Thermodynamic parameters demonstrated that the scavenge process was endothermic for both the concerned ions. Our results showed that the novel synthesized NAASMS-ZY is an effective nano-scavenger for cesium and strontium decontamination.

Development of a carbamate-conjugated catechol ligand and its application to Cs extraction from contaminated soil by using supercritical CO2.

Extraction of radioactive Cs from contaminated soil is a crucial aspect of remediation after nuclear accidents. For this purpose, we have developed a new type of ligand, carbamate-conjugated catechol, to assist in metal extraction by using supercritical CO2 (SCCO2). The synthesis process for this ligand is relatively simple, and the carbamate-conjugated catechol ligand dissolves well in SCCO2. The measured ligand distribution coefficient increased according to a power law with an exponent of 1.7 as the ligand concentration increased, indicating that approximately two ligand molecules are needed to extract one Cs ion. The roles of additives (ligand, co-ligand, and water) were limited when they were used separately, but the combination of these additives was important. We tested 27 combinations of these three additives for extracting Cs from artificially contaminated sea sand. A quantitative analysis indicated that the ligand had the strongest influence on Cs extraction, followed by water, and the co-ligand. The carbamate-conjugated catechol ligand was then used for Cs extraction from artificially contaminated real soil. Three types of soil were prepared: coarse soil (particle size = 0.5-1 mm), medium soil (particle size = 0.2-0.5 mm), and fine soil (particle size < 0.2 mm). The Cs fractions extracted from the coarse, medium, and fine soils were measured to be 95%, 91% and 70% of the Cs fraction extracted from sea sand, respectively, which indicates the existence of a surface area effect. Additionally, we suspect that Cs undergoes chemical interaction on the surface of real soil.

Removal of radioactive cesium from an aqueous solution via bioaccumulation by microalgae and magnetic separation.

We evaluated the potential sequestration of cesium (Cs+) by microalgae under heterotrophic growth conditions in an attempt to ultimately develop a system for treatment of radioactive wastewater. Thus, we examined the effects of initial Cs+ concentration (100-500 µM), pH (5-9), K+ and Na+ concentrations (0-20 mg/L), and different organic carbon sources (acetate, glycerol, glucose) on Cs+ removal. Our initial comparison of nine microalgae indicated that Desmodesmus armatus SCK had removed the most Cs+ under various environmental conditions. Addition of organic substrates significantly enhanced Cs+ uptake by D. armatus, even in the presence of a competitive cation (K+). We also applied magnetic nanoparticles coated with a cationic polymer (polyethylenimine) to separate 137Cs-containing microalgal biomass under a magnetic field. Our technique of combining bioaccumulation and magnetic separation successfully removed more than 90% of the radioactive 137Cs from an aqueous medium. These results clearly demonstrate that the method described here is a promising bioremediation technique for treatment of radioactive liquid waste.

Surface modification of poly(vinyl alcohol) sponge by acrylic acid to immobilize Prussian blue for selective adsorption of aqueous cesium.

Prussian blue (PB) is known to be an effective cesium adsorbent, but the direct application of PB is limited by the difficulty of its recovery from solution. In this study, PB was immobilized on a porous support media, poly(vinyl alcohol) (PVA) sponge, for use as a selective material for cesium adsorption. The commercially available PVA sponge was functionalized by the addition of poly(acrylic acid) (PAA) (i.e., PAA-PVA) to enhance the PB immobilization, which increased both PB loading and binding strength. The AA functionalization changed the major functional groups from hydroxyl to carboxylic, as confirmed by Fourier-transform infrared spectroscopy. PB was further synthesized in the PAA-PVA using layer-by-layer (LBL) assembly, which contributed to more stable PB formation, and reduced detachment of PB during washing. The prepared adsorbent, PAA-L@PVA-PB, was tested for cesium adsorption capability. Cesium adsorption was equilibrated within three hours, and the maximum cesium adsorption capacity was 4.082 mg/g, which was 5.7 times higher than Pure-L@PVA-PB. The observed decrease in solution pH during cesium adsorption inhibited overall cesium uptake, however, this was minimized by buffering. The prepared PAA-L@PVA-PB was used as a column filling material and its potential use as a countermeasure for removing radioactive cesium from a contaminated water stream was demonstrated.

Separation of cesium from wastewater with copper hexacyanoferrate film in an electrochemical system driven by microbial fuel cells.

A electrochemical adsorption system driven by microbial fuel cell (MFC-adsorption) was developed based on copper(II) hexacyanoferrate(III) (CuHCF) film for cesium (Cs) removal from wastewater. Cs uptake and elution can be simply controlled by regulating the redox states of the CuHCF films. Chemical oxygen demand (COD) removal showed little difference as MFC was connected to adsorption system. Meanwhile, power density and coulombic efficiency of MFC were dramatically reduced. The efficiencies of Cs adsorption and desorption were undesirable. MFC-adsorption technology used for actual nuclear wastewater treatment still has far to go.

Effective removal of cesium from wastewater solutions using an innovative low-cost adsorbent developed from sewage sludge molten slag.

This study investigates the effective removal of cesium (Cs) from aqueous solution using sewage sludge molten (SSM) slag that has undergone the surface modification with alkali (NaOH) hydrothermal treatment. The raw and modified slags were characterised systematically using the BET method, the FESEM, the XRF, the XRD spectroscopy and the CEC analysis to understand the physicochemical changes of the materials, and its sensitivity to Cs ions adsorption. Batch adsorption experiments were carried out to investigate the effects of adsorbent dose, contact time, solution pH, different initial Cs concentrations, temperature and the effect of competitive ions on Cs adsorption. The adsorption isotherm, kinetic and thermodynamic studies were also evaluated based on the experimental results. A higher Cs removal efficiency of almost 100% (for 20-100 mg/L of initial concentration) was achieved by the modified SSM slag, and the maximum adsorption capacity was found to be 52.36 mg/g. Several types of synthetic zeolites such as zeolite X, zeolite Y, zeolite A, and sodalite were formed on surface of the modified slag through the modification process which might be enhanced the Cs adsorption capacity. Kinetic parameters were fitted by the pseudo-second order model. The adsorption isotherms data of modified slag were well-fitted to the Langmuir (R2 = 0.989) and Freundlich isotherms (R2 = 0.988). The thermodynamic studies indicated that the adsorption process by the modified slag was spontaneous and exothermic. In the competitive ions effect, the modified slag effectively captured the Cs ion in the presence of Na+ and K+, especially at their lower concentrations. Moreover, the modified slag was reused for several cycles after the successful elution process with an appropriate eluting agent (0.5 M H2SO4), without deterioration of its original performance. Therefore, the SSM modified slag could be effectively used as a low-cost potential adsorbent for high Cs adsorption from wastewater.

Removal of Cs+ from aqueous solutions by perlite.

Perlite is an abundant mineral that requires minimum processing before use either as raw or expanded perlite, resulting in a low-cost, natural porous material. The application of materials for the removal of radioactive cesium from liquid effluents and contaminated waters is currently of great interest. Perlite has been evaluated in the last years for the sorption of a variety of metals, but it had not been investigated before for removal of Cs+ from contaminated waters. The present work examines the use of perlites from a deposit in Salta, Argentina, for removal of Cs+ from aqueous solutions. The mineral was characterized by means of powder X-ray diffraction, thermal analysis, analysis of specific area, and scanning electron microscopy. The effect of solution pH, presence of concomitant ions, contact time, Cs+ initial concentration, perlite dose, and basic or acidic treatment of the sorbent were studied by batch experiments. Removal increased at high pHs and after treatment with NaOH. Sorption of Cs+ by perlite presented a rapid rise in the first 80 min of contact. The selected material (from Pava mine) yielded removal efficiencies of 84 and 89% before and after treatment with NaOH, respectively, for a dose of 30 g perlite/L and initial cation concentration of 10 mg/L. Our results demonstrate that perlite is a material capable of removing Cs+ from aqueous solutions, even when applied at low doses. These findings are relevant in the context of removal of radioactive Cs isotopes from nuclear effluents and in case of contamination of environmental waters.

Porous 3D Prussian blue/cellulose aerogel as a decorporation agent for removal of ingested cesium from the gastrointestinal tract.

In the present study, we successfully synthesized a porous three-dimensional Prussian blue-cellulose aerogel (PB-CA) composite and used it as a decorporation agent for the selective removal of ingested cesium ions (Cs+) from the gastrointestinal (GI) tract. The safety of the PB-CA composite was evaluated through an in vitro cytotoxicity study using macrophage-like THP-1 cells and Caco-2 intestinal epithelial cells. The results revealed that the PB-CA composite was not cytotoxic. An adsorption study to examine the efficiency of the decorporation agent was conducted using a simulated intestinal fluid (SIF). The adsorption isotherm was fitted to the Langmuir model with a maximum Cs+ adsorption capacity of 13.70 mg/g in SIF that followed pseudo-second-order kinetics. The PB-CA composite showed excellent stability in SIF with a maximum Cs+ removal efficiency of 99.43%. The promising safety toxicology profile, remarkable Cs+ adsorption efficacy, and excellent stability of the composite demonstrated its great potential for use as an orally administered drug for the decorporation of Cs+ from the GI tract.

Demand driven salt clean-up in a molten salt fast reactor - Defining a priority list.

The PUREX technology based on aqueous processes is currently the leading reprocessing technology in nuclear energy systems. It seems to be the most developed and established process for light water reactor fuel and the use of solid fuel. However, demand driven development of the nuclear system opens the way to liquid fuelled reactors, and disruptive technology development through the application of an integrated fuel cycle with a direct link to reactor operation. The possibilities of this new concept for innovative reprocessing technology development are analysed, the boundary conditions are discussed, and the economic as well as the neutron physical optimization parameters of the process are elucidated. Reactor physical knowledge of the influence of different elements on the neutron economy of the reactor is required. Using an innovative study approach, an element priority list for the salt clean-up is developed, which indicates that separation of Neodymium and Caesium is desirable, as they contribute almost 50% to the loss of criticality. Separating Zirconium and Samarium in addition from the fuel salt would remove nearly 80% of the loss of criticality due to fission products. The theoretical study is followed by a qualitative discussion of the different, demand driven optimization strategies which could satisfy the conflicting interests of sustainable reactor operation, efficient chemical processing for the salt clean-up, and the related economic as well as chemical engineering consequences. A new, innovative approach of balancing the throughput through salt processing based on a low number of separation process steps is developed. Next steps for the development of an economically viable salt clean-up process are identified.

Assessment of the bioavailability and depuration of uranium, cesium and thorium in snails (Cantareus aspersus) using kinetics models.

Uranium ore waste has led to soil contamination that may affect both environmental and soil health. To analyze the risk of metal transfer, metal bioavailability must be estimated by measuring biological parameters. Kinetic studies allow taking into account the dynamic mechanisms of bioavailability, as well as the steady state concentration in organisms necessary to take into account for relevant risk assessment. In this way, this work aims to model the snail accumulation and excretion kinetics of uranium (U), cesium (Cs) and thorium (Th). Results indicate an absence of Cs and Th accumulation showing the low bioavailability of these two elements and a strong uranium accumulation in snails related to the levels of soil contamination. During the depuration phase, most of the uranium ingested was excreted by the snails. After removing the source of uranium by soil remediation, continued snails excretion of accumulated uranium would lead to the return of their initial internal concentration, thus the potential trophic transfer of this hazardous element would stop.

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.

Evaluation of the adsorptive behavior of cesium and strontium on hydroxyapatite and zeolite for decontamination of radioactive substances.

Removal of radioactive substances, such as cesium (Cs) and strontium (Sr), has become an emerging issue after the Fukushima Daiichi Nuclear Power Plant Disaster. To assess the possibility that hydroxyapatite (HA) and zeolites can be used for removal of radioactive substances, the adsorption capacities of Cs and Sr on the HA and a zeolite were investigated. The influence of Fe ions on Cs and Sr adsorption on the HA and the zeolite was also evaluated, because Fe ions are the most effective inhibitor of Cs adsorption on the zeolite.In the Cs adsorption process on the HA and the zeolite, the zeolite showed a higher adsorption ratio than the HA, and the maximum sorption capacity of the zeolite was calculated as 196 mg/g, whereas the HA showed a higher Sr adsorption ratio than the zeolite. The maximum sorption capacity of Sr on the HA was 123 mg/g. Under coexistence with Fe, Cs adsorption on the zeolite decreased with increasing Fe concentration, reaching 2.0 ± 0.8% at 0.1 M Fe concentration. In contrast, Cs adsorption on the zeolite was improved by adding the HA. In the case of coexistence of the HA, the Cs adsorption on the mixture of the HA and the zeolite was 52.4% ± 3.6 % at 0.1 M Fe concentration, although Cs adsorption on the HA alone was quite low. In the Fe adsorption processes of the HA and the zeolite, the HA exhibited a maximum sorption capacity of 256 mg/g, which was much higher than that of the zeolite (111 mg/g). The high affinity of Fe on the HA contributes to the improvement of the deteriorated Cs adsorption on the zeolite due to Fe ions.

Hydrogels Containing Prussian Blue Nanoparticles Toward Removal of Radioactive Cesium Ions.

Recent reports have demonstrated the practical application of Prussian blue (PB) nanoparticles toward environmental clean-up of radionuclide 173Cs. Herein, we prepared a large amount of PB nanoparticles by mixing both iron(III) chloride and sodium ferrocyanide hydrate as starting precursors. The obtained PB nanoparticles show a high surface area (440 m2. g-1) and consequently an excellent uptake ability of Cs ions from aqueous solutions. The uptake ability of Cs ions into poly(N-isopropylacrylamide (PNIPA) hydrogel is drastically increased up to 156.7 m2. g-1 after incorporating our PB nanoparticles, compared to 30.2 m2 . g-1 after using commercially available PB. Thus, our PB-containing PNIPA hydrogel can be considered as an excellent candidate for the removal of Cs ions from aqueous solutions, which will be useful for the remediation of the nuclear waste.

Copper Ferrocyanide Functionalized Core-Shell Magnetic Silica Composites for the Selective Removal of Cesium Ions from Radioactive Liquid Waste.

The copper ferrocyanide functionalized core-shell magnetic silica composite (mag@silica-CuFC) was prepared and was found to be easily separated from aqueous solutions by using magnetic field. The synthesized mag@silica-CuFC composite has a high sorption ability of Cs owing to its strong affinity for Cs as well as the high surface area of the supports. Cs sorption on the mag@silica-CuFC composite quickly reached the sorption equilibrium after 2 h of contact time. The effect of the presence of salts with a high concentration of up to 3.5 wt% on the efficiency of Cs sorption onto the composites was also studied. The maximum sorption ability was found to be maintained in the presence of up to 3.5 wt% of NaCl in the solution. Considering these results, the mag@silica-CuFC composite has great potential for use as an effective sorbent for the selective removal of radioactive Cs ions.

Facile synthesis of pectin-stabilized magnetic graphene oxide Prussian blue nanocomposites for selective cesium removal from aqueous solution.

This work focused on the development of pectin-stabilized magnetic graphene oxide Prussian blue (PSMGPB) nanocomposites for removal of cesium from wastewater. The PSMGPB nanocomposite showed an improved adsorption capacity of 1.609mmol/g for cesium, compared with magnetic graphene oxide Prussian blue, magnetic pectin Prussian blue, and magnetic Prussian blue nanocomposites, which exhibited adsorption capacities of 1.230, 0.901, and 0.330mmol/g, respectively. Increased adsorption capacity of PSMGPB nanocomposites was attributed to the pectin-stabilized separation of graphene oxide sheets and enhanced distribution of magnetites on the graphene oxide surface. Scanning electron microscopy images showed the effective separation of graphene oxide sheets due to the incorporation of pectin. The optimum temperature and pH for adsorption were 30°C and 7.0, respectively. A thermodynamic study indicated the spontaneous and the exothermic nature of cesium adsorption. Based on non-linear regression, the Langmuir isotherm fitted the experimental data better than the Freundlich and Tempkin models.

Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions.

Poly(vinyl alcohol) and alginate cross-linked matrix with immobilized Prussian blue and ion exchange resin for cesium removal from waters.

Cesium (Cs) removal from contaminated water bodies is an emerging issue after the disaster at the Fukushima Daiichi Nuclear Power Plant. The Prussian blue (PB) is an effective Cs adsorbent but will release hexacyanoferrate fragments from the adsorbent matrix during adsorption. Alginate is an affordable biopolymer for PB particles immobilization. This study synthesized poly(vinyl alcohol) (PVA) and alginate cross-linked matrix for immobilization of PB nano-sized particles and a surface-modified styrene-ethyl styrene divinyl benzene resin and tested their swelling stability and Cs adsorption performance in fresh water and in seawater. The PVA-alginate granules have high structural stability in both fresh water and seawater, with the Cs adsorption capability higher for the former than the latter. The adopted resin effectively remove released PB fragments from the tested granules. The transport and reaction parameters for the granules and for the sand filter bed were estimated.

Selective removal of cesium and strontium using porous frameworks from high level nuclear waste.

Efficient and cost-effective removal of radioactive (137)Cs and (90)Sr found in spent fuel is an important step for safe, long-term storage of nuclear waste. Solid-state materials such as resins and titanosilicate zeolites have been assessed for the removal of Cs and Sr from aqueous solutions, but there is room for improvement in terms of capacity and selectivity. Herein, we report the Cs(+) and Sr(2+) exchange potential of an ultra stable MOF, namely, MIL-101-SO3H, as a function of different contact times, concentrations, pH levels, and in the presence of competing ions. Our preliminary results suggest that MOFs with suitable ion exchange groups can be promising alternate materials for cesium and strontium removal.

Carbon dioxide utilization via carbonate-promoted C-H carboxylation.

Using carbon dioxide (CO2) as a feedstock for commodity synthesis is an attractive means of reducing greenhouse gas emissions and a possible stepping-stone towards renewable synthetic fuels. A major impediment to synthesizing compounds from CO2 is the difficulty of forming carbon-carbon (C-C) bonds efficiently: although CO2 reacts readily with carbon-centred nucleophiles, generating these intermediates requires high-energy reagents (such as highly reducing metals or strong organic bases), carbon-heteroatom bonds or relatively acidic carbon-hydrogen (C-H) bonds. These requirements negate the environmental benefit of using CO2 as a substrate and limit the chemistry to low-volume targets. Here we show that intermediate-temperature (200 to 350 degrees Celsius) molten salts containing caesium or potassium cations enable carbonate ions (CO3(2-)) to deprotonate very weakly acidic C-H bonds (pKa > 40), generating carbon-centred nucleophiles that react with CO2 to form carboxylates. To illustrate a potential application, we use C-H carboxylation followed by protonation to convert 2-furoic acid into furan-2,5-dicarboxylic acid (FDCA)--a highly desirable bio-based feedstock with numerous applications, including the synthesis of polyethylene furandicarboxylate (PEF), which is a potential large-scale substitute for petroleum-derived polyethylene terephthalate (PET). Since 2-furoic acid can readily be made from lignocellulose, CO3(2-)-promoted C-H carboxylation thus reveals a way to transform inedible biomass and CO2 into a valuable feedstock chemical. Our results provide a new strategy for using CO2 in the synthesis of multi-carbon compounds.