Durga Parajuli

Dealing with the aftermath of Fukushima Daiichi nuclear accident: decontamination of radioactive cesium enriched ash.

Environmental radioactivity, mainly in the Tohoku and Kanto areas, due to the long living radioisotopes of cesium is an obstacle to speedy recovery from the impacts of the Fukushima Daiichi Nuclear Power Plant accident. Although incineration of the contaminated wastes is encouraged, safe disposal of the Cs enriched ash is the big challenge. To address this issue, safe incineration of contaminated wastes while restricting the release of volatile Cs to the atmosphere was studied. Detailed study on effective removal of Cs from ash samples generated from wood bark, household garbage, and municipal sewage sludge was performed. For wood ash and garbage ash, washing only with water at ambient conditions removed radioactivity due to (134)Cs and (137)Cs, retaining most of the components other than the alkali metals with the residue. However, removing Cs from sludge ash needed acid treatment at high temperature. This difference in Cs solubility is due to the presence of soil particle originated clay minerals in the sludge ash. Because only removing the contaminated vegetation is found to sharply decrease the environmental radioactivity, volume reduction of contaminated biomass by incineration makes great sense. In addition, need for a long-term leachate monitoring system in the landfill can be avoided by washing the ash with water. Once the Cs in solids is extracted to the solution, it can be loaded to Cs selective adsorbents such as Prussian blue and safely stored in a small volume.

Historical Pigment Exhibiting Ammonia Gas Capture beyond Standard Adsorbents with Adsorption Sites of Two Kinds

Prussian blue is a historical pigment synthesized for the first time at the beginning of 18th century. Here we demonstrate that the historical pigment exhibits surprising adsorption properties of gaseous ammonia. Prussian blue shows 12.5 mmol/g of ammonia capacity at 0.1 MPa, whereas standard ammonia adsorbents show only 5.08-11.3 mmol/g. Dense adsorption was also observed for trace contamination in atmosphere. Results also show higher adsorption by Prussian blue analogues with the optimization of chemical composition. The respective capacities of cobalt hexacyanocobaltate (CoHCC) and copper hexacyanoferrate (CuHCF) were raised to 21.9 and 20.2 mmol/g, the highest value among the recyclable adsorbents. Also, CoHCC showed repeated adsorption in vacuum. CuHCF showed regeneration by acid washing. The chemical state of the adsorbed ammonia depends on the presence of the water in atmosphere: NH3, which was stored as in the dehydrated case, was converted into NH4(+) in the hydrated case.

Efficient synthesis of size-controlled open-framework nanoparticles fabricated with a micro-mixer: route to the improvement of Cs adsorption performance

We demonstrated an efficient method for size-controlled nanoparticles of the open framework coordination polymer potassium copper hexacyanoferrate (KCuHCF) using only aqueous solutions of the raw materials and a Y-type micro-mixer. Despite the high viscosity of the synthesized NP slurry, the micro-mixer provides continuous synthesis without clogging for a few hours with a high flow rate of 100 mL min−1, i.e. a linear velocity of 94 m s−1. The crystallite size, evaluated by the Scherrer equation using X-ray diffraction measurements, can be controlled by changing the flow rate. With the highest flow rate of 100 mL min−1, the smallest NPs with a size of ∼11 nm were obtained, less than half of the NP size obtained using the batch method. By downsizing the nanoparticles (NPs) using the micro-mixer synthesis, the Cs adsorption performance of potassium copper hexacyanoferrate (KCuHCF) was drastically improved. The KCuHCF with the smallest primary particles showed the fastest Cs adsorption: 1.4 times in the saturated capacity, 3.9 times in the distribution coefficient, and 7.7 times in the rate constant for the pseudo-second order adsorption theory, compared with the batch-synthesized sample.

Application of Prussian blue nanoparticles for the radioactive Cs decontamination in Fukushima region.

Cs decontamination efficiencies of the composites of iron hexacyanoferrate nanoparticles were investigated in comparison with commercial Prussian blue and natural zeolite. In pure water solution, the adsorption rate varied with sizes. In ash extract, where Cs adsorbing ability of zeolite was sharply dropped due to its poor selectivity, the impact of coexisting ions was negligible for FeHCF. FeHCF-n11, having the finest primary and secondary particle size, resulted the highest distribution coefficient, which was comparable to the high efficiency analogues, CoHCF or NiHCF. This observation suggested the possibility of preparing the high performance FeHCF by particle size and composition adjustment. FeHCF nanoparticle in bead form was tested for the removal of radioactive Cs in pilot scale. Due to larger secondary particle size, pronounced effect of solution temperature on the Cs adsorption kinetics on FeHCF bead was observed. Adjusting the mass of the adsorbent for the given solution temperature is recommended for achieving high decontamination rate.

Improved adsorption properties of granulated copper hexacyanoferrate with multi-scale porous networks

Designed porous copper hexacyanoferrate micro-capsule beads (CuHCF-MCB) were prepared using freeze-drying (FD). Multi-scale porous networks composed of Angstrom, nanometer, and micrometer sizes were obtained in the desired shapes using a simple drying process. They provide special benefits such as fast kinetics and high capacity. The Cs adsorption equilibrium and kinetics fit the pseudo-second-order kinetic model well. The adsorption rate of FD-CuHCF-MCB was improved to about 15 times higher than that of the heat-drying process because of the highly multi-scale porous structure of FD-CuHCF-MCB, which facilitated solution flow and rapid ion-diffusion inside the MCB.

High-capacity and selective ammonium removal from water using sodium cobalt hexacyanoferrate

A new NH4+ adsorbent with high capacity and selectivity, sodium cobalt(II) hexacyanoferrate(II) (NaCoHCF, NayCo(II) [Fe2+(CN)6]x·zH2O), was prepared. The adsorption performance was investigated by varying the mixing ratio of [Fe(CN)6]4− to Co2+ during synthesis, Rmix. The ammonia capacity was found to be proportional to Rmix, indicating that the NH4+ capacity can be increased by increasing the Na+-ion content in NaCoHCF. To conduct a detailed study, we prepared homogeneous nanoparticles by flow synthesis using a micromixer with Rmix = 1.00. Even on the addition of a saline solution (NaCl) with an Na+-ion concentration of 9350 mg L−1, the capacity was maintained: qmax = 4.28 mol kg−1. Using Markham–Benton analysis, the selectivity factor, defined by the ratio of equilibrium constants for NH4+ to that for Na+, was calculated to be α = 96.2, and 4.36 mol kg−1 was found to be the maximum capacity. The high selectivity of NaCoHCF results in good NH4+-adsorption performance, even from seawater. In comparison with other adsorbents under the same conditions and even for a NH4Cl solution, NaCoHCF showed the highest capacity. Moreover, the coexisting Na+ caused no interference with the adsorption of ammonium by NaCoHCF, whereas the other adsorbents adsorbed ammonia only slightly from the saline solution. We also found that the pores for NH4+ adsorption changed their sizes and shapes after adsorption.