Hiroki Mukai

Speciation of Radioactive Soil Particles in the Fukushima Contaminated Area by IP Autoradiography and Microanalyses

Radioactive soil particles several tens of micrometers in size were collected from litter soil in the radiation contaminated area by the Fukushima nuclear plant accident and characterized using electron and X-ray microanalyses. The radioactive particles were discriminated by autoradiography using imaging plates (IP) on which microgrids were formed by laser ablation in order to find the particles under microscopy. Fifty radioactive particles were identified and classified into three types from their morphology and chemical composition, namely: (1) aggregates of clay minerals, (2) organic matter containing clay mineral particulates, and (3) weathered biotite originating from local granite. With respect to the second type, dissolution of the organic matter did not reduce the radiation, suggesting that the radionuclides were also fixed by the clay minerals. The weathered biotite grains have a plate-like shape with well-developed cleavages inside the grains, and kaolin group minerals and goethite filling the cleavage spaces. The reduction of the radiation intensity was measured before and after the trimming of the plate edges using a focused ion beam (FIB), to examine whether radioactive cesium primarily sorbed at frayed edges. The radiation was attenuated in proportion to the volume decrease by the edge trimming, implying that radioactive cesium was sorbed uniformly in the porous weathered biotite.

Cesium adsorption/desorption behavior of clay minerals considering actual contamination conditions in Fukushima.

Cesium adsorption/desorption experiments for various clay minerals, considering actual contamination conditions in Fukushima, were conducted using the 137Cs radioisotope and an autoradiography using imaging plates (IPs). A 50 μl solution containing 0.185 ~ 1.85 Bq of 137Cs (10−11 ~ 10−9 molL−1 of 137Cs) was dropped onto a substrate where various mineral particles were arranged. It was found that partially-vermiculitized biotite, which is termed “weathered biotite” (WB) in this study, from Fukushima sorbed 137Cs far more than the other clay minerals (fresh biotite, illite, smectite, kaolinite, halloysite, allophane, imogolite) on the same substrate. When WB was absent on the substrate, the amount of 137Cs sorbed to the other clay minerals was considerably increased, implying that selective sorption to WB caused depletion of radiocesium in the solution and less sorption to the coexisting minerals. Cs-sorption to WB continued for about one day, whereas that to ferruginous smectite was completed within one hour. The sorbed 137Cs in WB was hardly leached with hydrochloric acid at pH 1, particularly in samples with a longer sorption time. The presence/absence of WB sorbing radiocesium is a key factor affecting the dynamics and fate of radiocesium in Fukushima.

Nucleation and growth of aragonite crystals at the growth front of nacres in pearl oyster, Pinctada fucata

The growth front of nacreous layer, which lies just above the outer prismatic layer, is one of the crucial areas to comprehend the formation of nacreous aragonite. The crystallographic properties of aragonite crystals at the growth front in pearl oyster, Pinctada fucata, were investigated using scanning electron microscopy with electron back-scattered diffraction, and transmission electron microscopy with focused ion beam sample preparation technique. Nano-sized aragonite crystals nucleate with random crystallographic orientation inside the dimples on the surface of the organic matrix that covers the outer prismatic columns. The dimples are filled with horn-like aragonite crystals, which enlarge from the bottom to the upper surface to form hemispheric domes. The domes grow concentrically and coalesce together to become the initial nacreous layer. The c-axes of aragonite at the top surface of the domes are preferentially oriented perpendicular to the surface. The horn-like aragonite and its crystallographic orientation are probably attained by geometrical selection with the fastest growth rate of aragonite along the c-axis, until organic sheets are continuously formed and interrupt the crystal growth of aragonite. The further crystal growth along the shell thickness is attained via mineral bridges through discontinuity or holes in the organic sheets. These results indicate that the crystal growth of aragonite at the growth front results from not only biotic process but also inorganic ones such as geometrical selection and mineral bridges.

Quantitative XRD analysis of {110} twin density in biotic aragonites.

{110} Twin densities in biotic aragonite have been estimated quantitatively from the peak widths of specific reflections in powder X-ray diffraction (XRD) patterns, as well as direct confirmation of the twins using transmission electron microscopy (TEM). Influence of the twin density on the peak widths in the XRD pattern was simulated using DIFFaX program, regarding (110) twin as interstratification of two types of aragonite unit layers with mirrored relationship. The simulation suggested that the twin density can be estimated from the difference of the peak widths between 111 and 021, or between 221 and 211 reflections. Biotic aragonite in the crossed-lamellar microstructure (three species) and nacreous microstructure (four species) of molluscan shells, fish otoliths (two species), and a coral were investigated. The XRD analyses indicated that aragonite crystals in the crossed-lamellar microstructure of the three species contain high density of the twins, which is consistent with the TEM examination. On the other hand, aragonite in the nacre of the four species showed almost no difference of the peak widths between the paired reflections, indicating low twin densities. The results for the fish otoliths were varied between the species. Such variation of the twin density in biotic aragonites may reflect different schemes of crystal growth in biomineralization.

Formation and Geological Sequestration of Uranium Nanoparticles in Deep Granitic Aquifer

The stimulation of bacterial activities that convert hexavalent uranium, U(VI), to tetravalent uranium, U(IV), appears to be feasible for cost-effective remediation of contaminated aquifers. However, U(VI) reduction typically results in the precipitation of U(IV) particles less than 5 nanometers in diameter, except for environmental conditions enriched with iron. Because these tiny particles are mobile and susceptible to oxidative dissolution after the termination of nutrient injection, in situ bioremediation remains to be impractical. Here we show that U(IV) nanoparticles of coffinite (U(SiO4)1−x(OH)4x) formed in fracture-filling calcium carbonate in a granitic aquifer. In situ U-Pb isotope dating demonstrates that U(IV) nanoparticles have been sequestered in the calcium carbonate for at least 1 million years. As the microbiologically induced precipitation of calcium carbonate in aquifer systems worldwide is extremely common, we anticipate simultaneous stimulation of microbial activities for precipitation reactions of calcium carbonate and U(IV) nanoparticles, which leads to long-term sequestration of uranium and other radionuclides in contaminated aquifers and deep geological repositories.

Cesium desorption behavior of weathered biotite in Fukushima considering the actual radioactive contamination level of soils

For the better understanding of radioactive contamination in Fukushima Prefecture at present and in future, Cs desorption experiments have been conducted mainly using weathered biotite (WB) collected from Fukushima Prefecture and considering the actual contamination level (∼10-10 wt%) of radiocesium in Fukushima Prefecture. In the experiments, 137Cs sorbed to WB by immersing in 137Cs solution for one day was mostly desorbed by solutions of 1 M NaNO3, 1 M LiNO3, 10-1 M HCl, and 10-1 M HNO3, although it was barely desorbed by 1 M KNO3, 1 M CsNO3, 1 M NH4NO3, and natural seawater. X-ray diffraction analysis of WB after immersing in these solutions suggested that the collapse of the hydrated interlayers in WB suppressed the desorption of Cs. On the other hand, 137Cs was barely desorbed from WB even by the treatments with solutions of NaNO3 and LiNO3 if the duration for the sorption was longer than approximately two weeks, as well as radioactive WB collected from actual contaminated soils in Fukushima Prefecture. This result implies that Cs sorbed in WB became more strongly fixed with time. Probably removal of radiocesium sorbed in weathered granitic soil at Fukushima Prefecture is difficult by any electrolyte solutions, as more than seven years have passed since the accident.