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Radioactive iodine (129I) is of great concern owing to its high mobility in the environment and long-term radiotoxicity. However, there is a lack of effective techniques for removing iodate (IO3−) from aqueous solution. This study aims to develop a new technique for removing radioactive iodate from contaminated solution by using barite (BaSO4). We examined the coprecipitation mechanism of iodate by barite at the molecular level to determine the optimum conditions for iodate removal. Results showed that iodate was effectively removed from the aqueous solution by coprecipitation even in the presence of competitive anions. Based on comparison of our method with previous techniques, the iodate removal efficiency by barite was determined to be about two orders of magnitude greater than that by hydrotalcite-like layered double hydroxide at 10 mmol L−1 Cl−. Extended X-ray absorption fine structure analysis indicated that the incorporated iodate was strongly bound to the crystal lattice of barite by substituting the sulfate site in the structure when the iodine concentration was low. The charge compensation problem from the IO3− substitution in the SO42− site was achieved by the substitution of Na+−IO3− pairs at the nearest Ba2+ site. Given the high removal efficiency and strong binding of iodate to barite, coprecipitation with barite is a promising tool for removing radioactive iodate from various aqueous solutions contaminated with iodate.

In an electron double-slit experiment, an optically zero propagation distance condition (infocus imaging condition), in which the double-slit position was imaged just on the detector plane (image plane), was realized in a 1.2 MV field-emission transmission electron microscope. Interference fringes composed of dot images were controlled by using two electron biprisms. Using a V-shaped double slit, we observed the interference features under the pre-interference condition, interference condition and post-interference condition of electron waves. We conclude that it is possible to observe the interference fringes only when the path information of the individual electrons is not available.

We have succeeded in operating a transition-edge sensor (TES) spectrometer and evaluating its performance at the SPring-8 synchrotron x-ray light source. The TES spectrometer consists of a 240 pixel National Institute of Standards and Technology (NIST) TES system, and 220 pixels are operated simultaneously with an energy resolution of 4 eV at 6 keV at a rate of ∼1 c/s pixel-1. The tolerance for high count rates is evaluated in terms of energy resolution and live time fraction, leading to an empirical compromise of ∼2 × 103 c/s (all pixels) with an energy resolution of 5 eV at 6 keV. By utilizing the TES's wideband spectroscopic capability, simultaneous multi-element analysis is demonstrated for a standard sample. We conducted x-ray absorption near-edge structure (XANES) analysis in fluorescence mode using the TES spectrometer. The excellent energy resolution of the TES enabled us to detect weak fluorescence lines from dilute samples and trace elements that have previously been difficult to resolve due to the nearly overlapping emission lines of other dominant elements. The neighboring lines of As Kα and Pb Lα2 of the standard sample were clearly resolved, and the XANES of Pb Lα2 was obtained. Moreover, the x-ray spectrum from the small amount of Fe in aerosols was distinguished from the spectrum of a blank target, which helps us to understand the targets and the environment. These results are the first important step for the application of high resolution TES-based spectroscopy at hard x-ray synchrotron facilities.

River water and sediments collected from the Erdenet, Gavil, and Khangal Rivers, near the Erdenet Cu–Mo mine were analyzed for their rare earth elements (REE) and yttrium (YREE) contents. Surface water samples were also collected from the tailing pond and ash pond of the mine, as well as in the seepage from the ash pond, where a part of the effluent flows into the Khangal river. The major chemical compositions of river and surface waters were found to vary slightly with water flow. The river water is Ca–HCO3-dominated in the upstream of the Erdenet and Gavil Rivers and ash pond; Ca–SO4-dominated in the tailing pond and seepage from the ash pond; and Ca–HCO3–SO4-dominated downstream of the Erdenet and Khangal Rivers. Both river and surface water exhibited a significant diatom content and the dissolved organic matter mainly comprise of fulvic acid-like materials, protein-like materials and microbial materials. The concentrations of YREE in river and surface waters ranged from 4.6 to 14.9 ng/L, whereas those of the sediments and rocks were 10–43 mg/kg and 25–34 mg/kg, respectively. Shale-normalized YREE patterns of river and surface waters, irrespective of water type, were characterized by enrichments in the middle REE (MREE) and heavy REE (HREE) relative to the light REE (LREE), exceptionally positive La anomalies, and super-chondritic Y/Ho ratios. The predominant REE species were REE(CO3)2−, REECO3+, and REESO4+ in the Ca–SO4-rich water. The HREE enrichment in both river and surface waters resulted in stronger complexation with carbonate ions and fulvic-acid like materials with increasing atomic number and preferential sorption of LREE onto sediments in neutral to slightly alkaline pH water. The YREE patterns of sediments showed MREE enrichment. Total YREE contents in the river sediments were correlated with Fe2O3, P2O5 and loss on ignition (LOI), suggesting the MREE enrichment fractionated by precipitation of authigenic MREE-enriched minerals such as phosphate, Fe (oxy)hydroxides and organic matter. With the exception of La, there were significant correlations among neighboring YREE concentrations, indicating that most YREEs were fractionated by the same geochemical processes, such as aqueous complexation and sorption onto the sediment surfaces. The concentrations of La did not correlate with those of the other YREE, suggesting that the La anomaly was probably induced by a biogenic activity such as diatom blooming and/or anthropogenic processes. Our results provide better understanding of REE behavior because of (bio)geochemical and anthropogenic contamination in terrestrial water systems.

This paper reports the concentration, speciation and isotope ratio (129I/127I) of iodine from both groundwater and host rocks in the Horonobe area, northern Hokkaido, Japan, to clarify the origin and migration of iodine in sedimentary rocks. Cretaceous to Quaternary sedimentary rocks deposited nearly horizontally in Tenpoku Basin and in the Horonobe area were uplifted above sea level during active tectonics to form folds and faults in the Quaternary. Samples were collected from the Pliocene Koetoi and late Miocene Wakkanai formations (Fms), which include diatomaceous and siliceous mudstones. The iodine concentration in groundwater, up to 270 μmol/L, is significantly higher than that of seawater, with the iodine enrichment factor relative to seawater reaching 800–1500. The iodine concentration in the rocks decreases from the Koetoi to Wakkanai Fms, suggesting that iodine was released into the water from the rocks of deeper formations. The iodine concentration in the rocks is sufficiently high for forming iodine-rich groundwater as found in this area. X-ray absorption near edge structure (XANES) analysis shows that iodine exists as organic iodine and iodide (I−) in host rocks, whereas it exists mainly as I− in groundwater. The isotope ratio is nearly constant for iodine in the groundwater, at [0.11–0.23] × 10−12, and it is higher for iodine in rocks, at [0.29–1.1] × 10−12, giving iodine ages of 42–60 Ma and 7–38 Ma, respectively. Some iodine in groundwater must have originated from Paleogene and even late Cretaceous Fms, which are also considered as possible sources of oil and gas, in view of the old iodine ages of the groundwater. The iodine ages of the rocks are older than the depositional ages, implying that the rocks adsorbed some iodine from groundwater, which was sourced from greater depths. The iodine concentration in groundwater decreases with decreasing chlorine concentration due to mixing of iodine-rich connate water and meteoric water. A likely scenario is that iodine-rich brine formed during the long-term basin evolution from the Cretaceous to Quaternary and that this brine was diluted by mixing with meteoric water during uplifting and denudation of the area.

The cerium (Ce) anomaly observed in rare earth element (REE) patterns has been used to estimate the redox state of paleo-marine environments. Cerium is unique because it forms tetravalent cations under oxic conditions, in contrast to the other REEs that occur in a trivalent state. This characteristic leads to anomalously high or low Ce concentrations relative to neighboring REEs. However, the use of Ce anomaly as a paleo-redox proxy is not well calibrated. This study shows that coupling of the Ce anomaly and Ce stable isotope ratio (δ142Ce) is more quantitative redox proxy to distinguish suboxic and oxic redox conditions. Our results revealed a progressive enrichment in heavy Ce isotopes in consecutive formations of iron (Fe) and manganese (Mn) precipitate from hot spring water without any associated change in REE patterns. The δ142Ce values of Mn precipitates were approximately 0.35‰ heavier than those of the Fe precipitates, which was consistent with experiment-based predictions. The δ142Ce values of marine ferromanganese deposits with three different formation processes were hydrogenetic (+0.25‰) > diagenetic (+0.10‰) ⩾ hydrothermal (+0.05‰), which also reflects redox conditions of their formation environment. These observations suggest that the Ce stable isotope ratios yield more quantitative information regarding redox state than REE patterns alone. We thus suggest that this novel proxy can be successfully utilized to reconstruct marine redox states, particularly from slightly oxic to highly oxic conditions such as the Great Oxidation Event (GOE).

Information transfer of a 1-MV field-emission transmission electron microscope (TEM) was improved by reducing mechanical vibrations and improving the stability of an acceleration voltage. The resulting mechanical stability was estimated from lattice fringes with an obtained spacing of 19.6 pm under achromatic conditions. This value corresponds to a vibration amplitude of

The metastability of monohydrocalcite (CaCO3·H2O: MHC) suggests high reactivity to dissolved trace elements. Using kinetic and isotherm sorption experiments with different reaction times (24h, 48h), As(V) sorption on MHC was examined to elucidate As(V) uptake by MHC. Although the MHC was transformed to aragonite with time, the MHC in higher As(V) loading conditions was able to persist longer than in lower loading conditions. Actually, As(V) uptake was negligible for samples in which the MHC remained. However, remarkable uptake of As(V) was observed for samples in which a complete transformation of MHC to aragonite occurred. Results of kinetic study confirmed that the timing of the MHC transformation coincided perfectly with that of As(V) removal from the solution. XAFS measurements showed that the local structure of As after the MHC transformation was almost identical to that of As in the As(V) coprecipitated aragonite. Sorption behavior of As(V) during the transformation is explainable theoretically by the substitution of As(V) into the aragonite structure. The distribution coefficient and (apparent) maximum sorption capacity of As(V) sorption on MHC after 48h at low-to-moderate As(V) concentrations are 500L/kg and 25μmol/g, respectively, which are much higher than those of simple adsorption of As(V) on calcite.

Neuroendocrine tumors of the thyroid gland are generally considered to derive from parafollicular endocrine cells (C cells) and are generally referred to as medullary thyroid carcinomas (MTC). Calcitonin secretion is almost always detected in MTC and a prerequisite for both clinical and pathological diagnosis. Thyroid neuroendocrine tumors without any apparent calcitonin secretion reflect a diagnostic dilemma because non-calcitonin-producing MTCs have virtually not been characterized. Here, we report a case of primary thyroid neuroendocrine tumors lacking calcitonin secretion or expression. The tumor cells expressed cytokeratins, chromogranin A, and synaptophysin, all of which were consistent with epithelial and neuroendocrine differentiation. Thyroid transcription factor-1 paired box gene 8, and carcinoembryonic antigen were also immunohistochemically detected, consistent with its thyroid origin. However, the tumor was negative for calcitonin both by immunohistochemistry and in situ hybridization, hence, not meeting the definition of MTC. Despite the loss of calcitonin expression, immunoreactivity for the calcitonin-gene-related peptide was detected in the tumor. Somatic gene mutations of RET, H-RAS, K-RAS, or BRAF were not detected in this case. A limited number of calcitonin non-producing thyroid neuroendocrine tumors are available in the scientific literature available in English, and its etiology and clinical manifestations remain largely unknown. Our case, along with the rare, previously reported cases, suggests that calcitonin non-producing neuroendocrine tumors of the thyroid gland are most likely derived from C cells, but should be differentiated from ordinary MTCs.

The input history of 236U to the surface water of the Japan Sea was reconstructed through measurement of the 236U/238U atom ratio in annual bands of a coral skeleton which was collected at Iki Island in the Tsushima Strait, the main entrance to the Japan Sea. The 236U/238U atom ratios and concentrations of U isotopes were measured for the period 1935–2010 using AMS and ICP-MS. The 236U/238U atom ratios revealed three prominent peaks: 4.51 × 10−9 in 1955, 6.15 × 10−9 in 1959 and 4.14 × 10−9 in 1963; thereafter the isotope ratios gradually decreased over the next several decades, attaining a value of ca.1.3 × 10−9 for the present day. A simplified depth profile model for 236U in the Japan Sea, using the reconstructed 236U value for the surface water together with observed depth profiles for 236U in the water column in 2010, yielded diffusion coefficients of 3.4–5.6 cm2/s for 6 sampling points. The diffusion coefficient values obtained for the northern stations were relatively large, and fitting uncertainty was also larger for stations in the northern region. It may be presumed that the distribution of 236U in the water columns have been influenced not only by diffusion but also by subduction of the surface water in the Japan Sea.

The rare earth elements (REEs) are widely used as tracers in studies of various geochemical systems. Their behavior in natural systems such as groundwater and river water is strongly influenced by organic complexation. The behavior of REE during the maturation of organic compounds (e.g., during decarboxylation reaction) is not well understood, and thus forms the topic of this study. In this study, the behavior of REEs during the maturation of organic matters was examined by heating experiments and analysis of crude oil. Heating increased the release of REEs from humic acid, and was associated with a decreased concentration of carboxyl groups in the humic acid. Ternary heating experiments (humic acid + REE + slate) led to the re-adsorption of released REEs to the slate. Carbon-13 nuclear magnetic resonance spectroscopy (13C NMR) did not show peaks corresponding to carboxyl groups in the natural crude oils examined here, meaning that the oils are more highly mature than other oils containing carboxyl groups. The abundances of REEs in the oils without carboxyl groups (this study) were about three orders of magnitude lower than those previously found in oils with carboxyl groups, suggesting that the carboxyl group is important to REE retention in crude oil. These findings suggest that a considerable amount of REEs is released during the early stage of diagenesis, or during decarboxylation, and is likely to be subsequently adsorbed to the petroleum source rock. The variation in the Y/Ho ratio among oils suggests the occurrence of a secondary distribution to the oil-hosting rock. Other metallic elements that behave similarly to REEs, such as Ca, Al, and Fe, can also be released from the organic phase, whereas those that behave differently from the REEs may be retained.

We herein investigated the mechanisms underlying the contact leaching process in pyrite bioleaching by Acidithiobacillus ferrooxidans using scanning transmission X-ray microscopy (STXM)-based C and Fe near edge X-ray absorption fine structure (NEXAFS) analyses. The C NEXAFS analysis directly showed that attached A. ferrooxidans produces polysaccharide-abundant extracellular polymeric substances (EPS) at the cell-pyrite interface. Furthermore, by combining the C and Fe NEXAFS results, we detected significant amounts of Fe(II), in addition to Fe(III), in the interfacial EPS at the cell-pyrite interface. A probable explanation for the Fe(II) in detected EPS is the leaching of Fe(II) from the pyrite. The detection of Fe(II) also indicates that Fe(III) resulting from pyrite oxidation may effectively function as an oxidizing agent for pyrite at the cell-pyrite interface. Thus, our results imply that a key role of Fe(III) in EPS, in addition to its previously described role in the electrostatic attachment of the cell to pyrite, is enhancing pyrite dissolution.

A significant amount of scandium (Sc) has been found in the laterites developed over ultramafic and mafic rocks, but much less knowledge is available regarding Sc speciation in laterites. The geochemistry of Sc is unique compared with other rare earth elements (REE), however, the controls of their different partitioning behaviors are still poorly understood. In this study, the distribution and speciation of Sc and yttrium (Y) in the Philippine nickel (Ni) laterites were determined by a combination of sequential extraction, synchrotron-based micro-focused X-ray fluorescence (μ-XRF) and X-ray absorption fine structure (XAFS) techniques, to clarify different geochemical behaviors between Sc and other REE in Ni laterites. Here we demonstrate that Sc can be structurally incorporated into goethite in Ni laterites apart from the adsorption on the goethite surface, while Y is mainly adsorbed on goethite via the bidentate-binuclear inner-sphere complexation. The striking disparity regarding the speciation could result from ionic radius of Sc3+ and Y3+ (REE3+) with respect to Fe3+ in iron (oxyhydr)oxides, which is likely responsible for the relatively lower mobilization and (re)distribution of Sc than other REE in Ni laterites. Our study firstly reports disparate chemical speciation of Sc and Y in Ni laterites and provides molecular-scale insights into the control of different solubility and partitioning behaviors of Sc and other REE.

Internal radiation exposure from neutron-induced radioisotopes environmentally activated following atomic bombing or nuclear accidents should be considered for a complete picture of pathologic effects on survivors. Inhaled hot particles expose neighboring tissues to locally ultra-high doses of &beta, rays and can cause pathologic damage. 55MnO2 powder was activated by a nuclear reactor to make 56MnO2 which emits &beta, rays. Internal exposures were compared with external &gamma, rays. Male Wistar rats were administered activated powder by inhalation. Lung samples were observed by histological staining at six hours, three days, 14 days, two months, six months and eight months after the exposure. Synchrotron radiation - X-ray fluorescence - X-ray absorption near-edge structure (SR&ndash, XRF&ndash, XANES) was utilized for the chemical analysis of the activated 56Mn embedded in lung tissues. 56Mn beta energy spectrum around the particles was calculated to assess the local dose rate and accumulated dose. Hot particles located in the bronchiole and in damaged alveolar tissue were identified as accumulations of Mn and iron. Histological changes showed evidence of emphysema, hemorrhage and severe inflammation from six hours through eight months. Apoptosis was observed in the bronchiole epithelium. Our study shows early event damage from the locally ultra-high internal dose leads to pathogenesis. The trigger of emphysema and hemorrhage was likely early event damage to blood vessels integral to alveolar walls.

Calcium (Ca) species in aerosols collected in Higashi–Hiroshima in southwestern Japan were determined by X-ray absorption near-edge structure (XANES) analysis, and their size distributions and seasonal variation were investigated. Calcium K-edge XANES results showed that gypsum (CaSO4⋅2H2O) and calcium oxalate (CaC2O4⋅2H2O) were the major Ca species that were formed by reactions of mineral particles in the atmosphere. These species exhibit similar hygroscopicity to that of calcite (CaCO3), which is an original Ca species in mineral particles. In addition, high hygroscopic Ca species, such as calcium nitrate [Ca(NO3)2⋅4H2O] and calcium chloride (CaCl2⋅2H2O) were considered minor Ca species. Moreover, the formation of CaSO4⋅2H2O by the reaction of mineral particles suppresses the formation of hygroscopic sulfate aerosol species, such as ammonium sulfate [(NH4)2SO4], reducing the number of cloud condensation nuclei (CCN). Sulfur K-edge XANES also confirmed that CaSO4⋅2H2O was a major species of sulfate in coarse particles. By contrast, high hygroscopic sulfate, such as (NH4)2SO4, was major species in fine particle. In addition, CaSO4⋅2H2O fraction to total sulfate increased during the sampling period, which was affected by a dust event. Consequently, the amount of hygroscopic sulfate in fine particles was decreased by the reaction, forming CaSO4⋅2H2O in coarse particles in the presence of mineral dust. Although these facts have been indicated mostly by modeling and laboratory studies, the present research suggested that the reaction of CaCO3 to form CaSO4⋅2H2O will reduce the amount of hygroscopic sulfate aerosols based on natural sample measurement in terms of the speciation of Ca and sulfate in aerosols using XANES spectroscopy.

A novel Mg/Al/Bi ternary mixed metal oxide (MMO) was successfully prepared by a simple coprecipitation and calcination process. The Mg/Al/Bi MMO (molar ratio = 3:0.4:0.6) presented synergistically enhanced adsorption efficiency for iodide in water with porous structure. Kinetic adsorption results indicated good agreement with pseudo first-order-kinetic model (R = 0.998) and the maximum adsorption capacity calculated by Langmuir isotherm of Mg/Al/Bi MMO was 202.2 mg/g, which is higher than that of Mg/Al layered double oxide (LDO) (161.0 mg/g) and bismuth oxide (57.5 mg/g). In addition, the Mg/Al/Bi MMO showed good adsorption efficiency under neutral condition (pH 7), by which the material exhibits relatively strong resistance to the presence of co-existing anions in water due to the ion selectivity. Extended X-ray absorption fine structure (EXAFS) spectra revealed that the enhanced adsorption of iodide by Mg/Al/Bi MMO can be induced by selective Bi-O-IBformation, which is stable waste form for its treatment. Consequently, it is clear that the novel Mg/Al/Bi MMO is a potentially attractive material in terms of selective uptake of iodide with forming stable chemical complex in radioactive contaminants.

Rivers and ponds near the Erdenet mine, one of the world&rsquo, s largest copper-molybdenum mines, exhibit high concentrations of molybdenum (Mo). This study evaluates the distribution and chemical speciation of Mo in surface sediments from ponds and rivers in Erdenet city to elucidate the mobility and solubility of Mo in the surface aquatic environments in the area. The waters and sediments were collected in two shallow ponds connected to the tailing pond and from three rivers flowing through Erdenet city. The distribution and chemical speciation of Mo in the sediments were examined using five-step sequential extraction and X-ray absorption fine structure (XAFS) analyses. The XAFS spectra of the sediments showed that large amounts of Mo in the sediments are molybdate or polymeric molybdate, weakly adsorbed onto ferrihydrite. Sequential extraction consistently showed a large amount of Mo distributed in the labile fractions. Results suggest that the surface sediments from ponds and rivers play a role as secondary contamination sources of Mo rather than as sinks of Mo in the area.

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.

Clarification of the morphology of bulk heterojunction (BHJ) is indispensable for true comprehension of the organic solar cells. Here, we performed scanning transmission X-ray microscopy (STXM) for a poly-(9,9-dioctylfluorene-co-bithiophene) (F8T2)/[6,6]-phenyl C71-butyric acid methyl ester (PC71BM) blend film annealed at various temperatures (Tan). We found that the fullerene concentration within the polymer-rich domain decreases with Tan while the domain size (∼230 nm) is essentially unchanged. We will discuss the interrelation between the film morphology and the photovoltaic performance.

The present study focused on the enhanced removal of As(III) by the simultaneous photooxidation and removal process using TiO2 nanoparticles supported layered double hydroxide (TiO2/LDH). The TiO2/LDH nanocomposites were synthesized using a flocculation method, and nanosized (30–50 nm) TiO2 particles were well-distributed on the LDH surface. The XPS and DLS data revealed that the TiO2/LDH nanocomposites were both chemically and physically stable in the aquatic system. The optimum ratio of TiO2 was 20 wt.% and the calcination process of LDH enhanced the removal capacity of As(III) by the reconstruction process. In the kinetic removal experiment, UV irradiation improved the removal rate of As(III), based on the continuous conversion of As(III) to As(V), and that the removal rate was faster under alkaline conditions than acidic and neutral conditions due to the abundance of oxidants and negative charged As(III) species (pKa: 9.2). The main mechanism of As(III) photooxidation is the direct oxidation by h vb + , which is generated by supported TiO2 nanoparticles. X-ray near edge structure results also confirmed that the As(III) was completely oxidized to As(V). Consequently, the simultaneous photooxidation and removal process of As(III) by TiO2/LDH nanocomposites may be the effective removal option in As(III) contaminated water.

Electron holographic vector field electron tomography visualized three-dimensional (3D) magnetic vortices in stacked ferromagnetic discs in a nanoscale pillar. A special holder with two sample rotation axes, both without missing wedges, was used to reduce artifacts in the reconstructed 3D magnetic vectors. A 1 MV holography electron microscope was used to precisely measure the magnetic phase shifts. Comparison of the observed 3D magnetic field vector distributions in the magnetic vortex cores with the results of micromagnetic simulations based on the Landau-Lifshitz-Gilbert equation showed that the proposed technique is well suited for direct 3D visualization of the spin configurations in magnetic materials and spintronics devices.

The occurrence of (137)Cs in size fractionated samples in river water from the Abukuma River system, (the Kuchibuto and Abukuma Rivers, five sampling events for three sites) was studied from June 2011--approximately some three months after the Fukushima Dai-ichi Nuclear Power Plant (FDNPP) accident until December 2012. The total concentration of (137)Cs (mBq/L) in river water was generally high at the upper stream site in the Yamakiya District within the evacuation/off-limits zone. The (137)Cs concentration was about 1Bq/L for the first sampling campaign (June 2011) at all sites, but then decreased substantially to about one-tenth of that by the time of a second sampling campaign (November or December 2011). The (137)Cs in the

Copyright © 2015 by The Geochemical Society of Japan. tool to estimate sedimentary environment at the time of deposition of sediments (Chaudhuri and Cullers, 1979; Nath et al., 1997). In particular, the cerium (Ce) anomaly is a decent redox indicator of the depositional environment and has been widely employed in geochemical studies (Shimizu and Masuda, 1977; Palmer, 1985; Wang et al., 1986). To develop REE pattern as a geochemical tool for sediments or sedimentary rocks, the host phases of REEs within the sediments or sedimentary rocks should Transfer of rare earth elements (REE) from manganese oxides to phosphates during early diagenesis in pelagic sediments inferred from REE patterns, X-ray absorption spectroscopy, and chemical leaching method

This study examined the radiocesium (RCs) interception potential (RIP), cation exchange capacity (CEC), total organic carbon (TOC) content, and adsorption species in soils and minerals by using extended X-ray absorption fine structure (EXAFS) spectroscopy. The RIP related to Cs(+) adsorption by frayed-edge site (FES) has often been used to measure the mobility and bioavailability of RCs in the environment. This study found that the presence of organic matter (OM) can reduce RIP to a certain extent. The adsorption amount (=Q(T)) in soil was obviously correlated to RIP at a small [Cs(+)] region, whereas a linear relationship between Q(T) and CEC was observed at a large [Cs(+)] region. Both the inner-sphere (IS) and outer-sphere (OS) complexes of Cs(+) were observed through EXAFS at a molecular scale. The linear correlation between log (RIP/CEC) and the ratio of the coordination number (CN) of IS (=CNIS) and OS (=CNOS) complexes noted as CNIS/(CNIS + CNOS) suggested that the ratio of CN is very sensitive to Cs(+) adsorption species with variable RIP and CEC. The adsorption species of Cs(+) in soil was mainly dependent on the clay mineral content of soil. RIP was affected not only by FES but also by other strong adsorption sites, such as the interlayers and cavities identified as the IS complex in EXAFS analysis. Findings indicated that the EXAFS approach is a powerful and efficient tool to explore the behavior of Cs(+) in a given environment.

Manganese (Mn) carbonate nodules, which differ from seafloor Mn nodules mainly composed of MnO 2 , are occasionally embedded in the form of a lens shape in the Jurassic accretionary complexes, such as the Mino Belt in Japan. The interpretation of the formation process of Mn carbonate is still controversial, particularly concerning whether the Mn carbonate was formed primarily or secondarily. In this study, a fresh Mn carbonate nodule incorporated into the red siliceous mudstone was collected for geochemical and sedimentological analysis. The optical observation of thin sections indicates that the Mn carbonate nodules are composed of abraded grains of rhodochrosite spherule with radiolarians and are sedimentary embedded in siliceous mudstone. Microfossil radiolarians from the Mn carbonate nodules and the host red siliceous mudstone are dated as the Bajocian, but the radiolarians in the nodules are somewhat older than those in the host red siliceous mudstone. Geochemical analysis using the X-ray absorption near-edge structure on Ce indicates the dominance of trivalent Ce at present, despite the observation of a positive Ce anomaly in the PAAS-normalized REE pattern of Mn carbonate. The REE adsorption experiment on synthesized MnCO 3 does not show any distinctive positive Ce anomaly, and a thermodynamic calculation suggests the possible coexistence of rhodochrosite and spontaneous oxidation of Ce. A leaching experiment that can selectively decompose the carbonate phase demonstrated no Ce anomaly in the carbonate phase of the Mn carbonate and a poor contribution to the bulk REE concentration. The carbon isotope data of Mn carbonate nodule implied the dominance of inorganic marine carbonate origin with small contribution of organic decomposition. The most plausible account of all of the observational and geochemical results is that the rhodochrosite grains were primarily formed on the depositional site and subsequently transferred to a different site, where siliceous mudstone was deposited.

Iron isotope ratios (δ56/54Fe) of various anthropogenic materials produced by combustion processes were analyzed. It was revealed that particles emitted through combustion processes, such as fine a...

© 2016 The Chemical Society of Japan. Particle surfaces of mineral aerosols are important reaction sites in the atmosphere. Previous studies suggested that calcite in aerosols, which are emitted during dust periods, neutralizes sulfuric acid. In this study, depth-dependent X-ray absorption fine structure spectroscopy for individual particles was employed to determine calcium (Ca) species at particle surface and in the bulk ofindividual particles, using an X-ray microbeam measured in the conversion electron yield and fluorescence yield modes, which is a powerful method to understand chemical processes at aerosol surfaces.

Adsorption of radiocesium (RCs) on particulate matters in aquatic environment is important to understand its mobility and bioavailability. We here focused on factors controlling partition of RCs on particulate matters and sediments in Kuchibuto (Fukushima) and Pripyat (Chernobyl) Rivers, though RCs level in water was much smaller than WHO guideline. Moreover, Cs speciation and organic matter-clay mineral interaction were studied: (i) extended X-ray absorption fine structure showed that the contribution of outer-sphere complex of Cs on particulate matters is larger in Chernobyl than in Fukushima and (ii) scanning transmission X-ray microscope revealed larger association of humic substances and clay minerals in Chernobyl partly due to high [Ca2+] in the Pripyat River. Consequently, RCs is more soluble in the Pripyat River due to weaker interaction of RCs with clay minerals caused by the inhibition effect of the adsorbed humic substances. In contrast, particulate matters and sediments in the Kuchibuto River display high adsorption affinity with lesser inhibition effect of adsorbed humic substances. This difference is possibly governed by the geology and soil type of provenances surrounding both catchments (Fukushima: weathered granite; Chernobyl: peat wetland and carbonate platform) which leads to high concentrations of organic matter and Ca2+ in the Pripyat River.

The sediments of Majuro Atoll, Marshall Islands, consist of bioclastic materials, including foraminifera and coral debris. The sedimentary depth profiles of elements showed that various elements including zinc (Zn) and copper (Cu) were enriched in the upper layers of the islands of Majuro Atoll. Carbon-14 dating revealed that the sedimentation of the upper layer was completed before 1670 and 542 cal BP in Laura and Calalen, respectively. The enriched elements could be categorized by their origins: (a) terrestrial elements transported as dust (aluminum (Al) and rare earth elements (REEs)); (b) anthropogenic elements (Zn and Cu); and (c) elements supplied by seabirds (phosphorus (P)). From the results of the total amount of Al supplied to sediments for ca. 2000 years, Al in Majuro Atoll was suggested to be airborne origin. The enrichment factors of the elements normalized to Al concentration of continental crust showed that REEs were also transported as dust, while Zn and Cu were mainly of anthropogenic origin. The speciation analysis by X-ray absorption near-edge structure (XANES) showed the presence of Zn–Cu alloys originated from industrial products. It was also revealed that Zn was enriched in the surface due to anthropogenic emission after urbanization on Majuro Atoll and fixed by carbonate and phosphate at the upper layer, which inhibits migration of Zn into the deeper layer and its release to the groundwater and costal water. Hence, the fixation of heavy metals at the surface prevents their exposure to aquatic organisms and residents via fresh groundwater in the island.

Although environmental changes and evolution of life are potentially recorded via microbial carbonates, including laminated stromatolites and clotted thrombolites, factors controlling their fabric are still a matter of controversy. Herein, we report that the exopolymer properties of different cyanobacterial taxa primarily control the microbial carbonates fabrics in modern examples. This study shows that the calcite encrustation of filamentous Phormidium sp. secreting acidic exopolymers forms the laminated fabric of stromatolites, whereas the encrustation of coccoid Coelosphaeriopsis sp. secreting acidic exopolymers and poor calcification of filamentous Leptolyngbya sp. secreting non-acidic exopolymers form peloids and fenestral structures, respectively, i.e. the clotted fabric of thrombolites. Based on these findings, we suggest that the rise and decline of cyanobacteria possessing different exopolymer properties caused the expansion of thrombolites around the Proterozoic/Cambrian boundary.

Non-spherical heterogeneous radiocesium-bearing particles were found on masks worn during cleaning work in residences near the Fukushima Dai-ichi Nuclear Power Plant (FDNPP), from which residents had evacuated. Three slightly larger (6.6-12 μm) non-spherical radiocesium-bearing particles were found in a residence in Futaba Town, a straight distance of 2.11 km west-northwest from the FDNPP. These were collected on October 25, 2016, 5 years and 7 months after the Fukushima Dai-ichi nuclear disaster and were presumed to originate from the Plant's Unit 2 based on the measured radioactivity ratio of 134Cs/137Cs. The main elemental composition was similar to particles already reported in other studies. However, this is the first time that such particles had a clearly heterogeneous distribution.

Field, petrographic, geochemical, and K–Ar and U–Pb age data were used to elucidate the internal structure of the Cretaceous Hobenzan pluton, SW Japan, and the processes which generated that structure. The pluton is elongated E–W with dimensions of about 6.5 × 2.0 km (13 km2), and was emplaced at ~ 95 Ma as a pluton in accretionary complexes. The pluton contains an early tonalite, but most of the body consists of later granitoids that show a continuous differentiation series from biotite–hornblende granodiorite (GD) to hornblende–biotite granite (HBG) and biotite granite (BG). The contacts between the GD and HBG are gradational. The pluton provides an exceptional cross-sectional view of a simple cooling magma body. The GD shows no vertical variations in modal and chemical compositions, whereas the HBG displays differentiation from the lowermost exposure to the top of the pluton. Initial Sr isotope ratios (SrI) in the HBG increase from the lower part to the top of the pluton. The granitoids show continuous compositional variations from 65 to 79 wt.% SiO2 (anhydrous basis), and magmatic differentiation was dominantly controlled by crystal fractionation of hornblende and plagioclase. Field, elemental and Sr–Nd isotope data are consistent with limited operation of assimilation with pelitic rocks and fractional crystallization (AFC), in which assimilation increased with higher degrees of differentiation. The Hobenzan pluton retains a history of granitoid magma evolution in a subvolcanic magma reservoir. The GD formed as a rigid sponge, and melt fraction increases inwards from the walls, forming the HBG mush by fractional crystallization, coupled with small degrees of assimilation of adjacent schists. A more evolved and enriched low-density melt segregated from the mushy cumulate of the HBG by incomplete crystal–melt separation, and moved upwards with the assistance of gas-driven filter pressing, as indicated by the presence of miarolitic cavities, thus forming the BG at the roof of the pluton.

This study used laboratorial estimations and determined the distribution coefficient (Kd) of 137Cs in river sediments sampled from the Abukuma River and the Kuchibuto River to investigate the particle size dependence of RCs distribution. Results show that the Kd patterns of 137Cs (particle size-dependence of Kd) were not only related to the particle size of large particles (low clay mineral content) but also to the clay mineral content of small particles (high clay mineral content) and particularly cation concentration in aqueous phase. By contrast, the Kd patterns of stable Cs (133Cs) exhibited no obvious particle size dependence. Adsorption species of Cs that was added to the river sediments at various particle sizes was almost the same at the molecular scale as determined by the extended X-ray absorption fine structure. Our findings indicate that river sediments have high fixation ability to 137Cs. Nevertheless, adsorbed 137Cs can be extracted from sediments in the water phase when salinity becomes high, such as that in seawater. The distribution patterns of 137Cs at various particle sizes can slowly down the equilibrium of the adsorption of 137Cs during the transportation of river sediments, and then the behavior of 137Cs should eventually be similar to that of stable Cs in the river system. Therefore, the particle size of sediments is an important factor in the distribution of RCs at the early stage of its deposition. In the end, RCs adsorbed on the sediments will be equilibrated with the stable Cs during its transportation in the river system. Controlling factors such as the mineralogy of sediments could possibly make the distribution patterns of RCs similar to that of stable Cs in the long run.

Two active hydrothermal fields, Jade and Hakurei fields have been discovered within the Izena Hole, a rectangular 6 km × 3 km shape depression located in the middle Okinawa Trough back arc basin. In both fields, intense hydrothermal activity is represented by venting of high-temperature fluid (>300°C) and occurrence of sulfide/sulfate ore deposits. We collected hydrothermal fluids during dive expeditions of ROV Hyper Dolphin conducted in 2003, 2010 and 2011, in order to analyze both elemental and gas species. The geochemistry of high temperature hydrothermal fluids collected from the Jade and Hakurei fields is very similar to each other with exceptions in minor gas composition. Little temporal variation was observed in geochemistry of the high-temperature hydrothermal fluid of the Jade field over two decades, since a previous study carried out in 1989. These results suggest that these fluids are derived from a common fluid reservoir where fluid chemistry is basically controlled by fluid-mineral equilibria and gas species are dominantly contributed from the same magma. Venting of low temperature fluid (about 104°C) was discovered in the distal part of the Jade field, which was named as the Biwako vent. Chemical composition of the Biwako vent fluid was distinctive from that of the high temperature fluid in the proximal part of the Jade field, and could not be explained by simple dilution or cooling. This intra-field chemical diversity could be caused by phase separation and segregation during fluid upwelling, based on relationships in concentrations of Cl and major cations. On the other hand, the chemical diversity recognized in minor gas composition between the Jade and Hakurei fields is in accordance with results from previous plume survey. Difference in concentrations of minor gases such as H2 is attributed to contribution from thermal degradation of organic matter in the sediment, during fluid upwelling., 論文

An acidic (pH 5.2) firing range soil, FDR26 in New Jersey, with Pb content of 6,017 mg kg−1, was amended by adding 2.5 wt% fish bone grains. The leaching test, toxicity characteristic leaching procedure (TCLP), and spectroscopic technique, non-destructive X-ray absorption near edge structure (LCF-XANES), were employed to determine the leaching behavior and Pb speciation prior to and after the TCLP test. The TCLP-Pb was 209 mg L−1 after the standard 18 h of tumbling and was increased to 288 mg L−1 after an extended tumbling time of 96 h. The XANES of TCLP residue confirmed the existence of extractable Pb species following the 18 h extraction. TCLP-Pb was also reduced to 1.4 mg L−1 after phosphate addition followed by 28 days of curing. LCF-XANES results revealed the transformation of metallic Pb into insoluble pyromorphite precipitates during the leaching test. The acidic extraction solution significantly increased the dissolution of phosphate source and Pb species, and resulted in improved Pb immobilization.

The relationship between cesium (Cs) adsorption on clay minerals with various expandabilities and Cs mobility in environment was investigated using sequential extraction, batch adsorption, X-ray diffraction (XRD), generalized adsorption model (GAM), and Cs LIII-edge extended X-ray absorption fine structure (EXAFS) analyses with molecular simulations using the density functional theory (DFT). In particular, the difference between the affinities of illite (non-expansion) and vermiculite (intermediate expansion) for Cs and the effect of humic acid (HA) addition on the Cs/clay mineral system were highlighted in this study. These two factors affect Cs mobility and bioavailability in surface soil and sediments. The batch adsorption results showed that Cs adsorption was inhibited to some extent in the ternary clay + HA + Cs system because of (i) the blocked access of Cs to the frayed edge site (FES) and type II site [inner–sphere (IS) complex in GAM] by HA, and (ii) the reduced availability of the interlayer site in vermiculite. EXAFS analysis further confirmed that the adsorbed Cs in clay minerals was drastically changed by the sequential addition of HA. In addition, the dominant IS complex in the illite + Cs and illite + Cs + HA systems (in which HA was added after Cs adsorption on illite) can be converted to the outer–sphere (OS) complex largely in the illite + HA + Cs system (in which HA was added prior to Cs adsorption). These results are consistent with the sequential extraction and GAM results. The IS complex of dehydrated Cs+ mainly formed at the FES and interlayer site on illite (non-expansion) without resulting in any illite structural changes. However, on vermiculite (intermediate expansion), the dehydrated Cs+ can be adsorbed as an IS complex associated with the siloxane group of the di-trigonal cavity in the tetrahedral SiO4 sheet. This adsorption is accompanied by collapse of the layer, which can be easily coated by HA molecules to prevent Cs fixation. However, a nearly complete OS complex was observed at the planar site of montmorillonite (large expansion). These processes were confirmed by sequential extraction, batch adsorption, XRD, and EXAFS, which clearly showed that Cs mobility in soil highly depends on clay mineral expandability, natural organic matter (NOM), and the coupling of both effects. The atomic-scale information given by EXAFS is consistent with the distribution data from adsorption experiments, GAM, sequential extraction, and DFT. These results can be used as a basis for a clearer understanding of Cs behavior in natural systems.

This essay will shed light on the reasons why Brazilian football player Zico has become the ‘God of Soccer’ in Japan by discussing Zico’s unique character and actions and the social condition surrounding him, as well as the role played by the image of a hero held by the Japanese. The study uses the existing literature on Zico’s tenure in Japan along with Zico’s own writings and anecdotes to reflect upon his legacies from various angles. While it emphasizes the ability of an interpreter in constructing Zico’s image, it also encapsulates the key moments and images Zico elicited in Japan, including his brilliant style of play, his memorable hat-trick in his opening J-League match and his figure as a father of Japanese football. The essay will try to show that Zico’s emphasis on the importance of family, as in building a ‘Zico Family’, as well as his strong sense of obligation, professionalism and integrity contributed to creating his image as a legendary human being in Japan.

We collected fluvial suspended sediments in Fukushima after the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident and analyzed the 137Cs concentration in bulk and size-fractioned samples to investigate the particle-size-dependent distribution of radiocesium. The 137Cs concentration in bulk suspended sediments decreased from August to December 2011, possibly reflecting a decrease of radiocesium concentration in its source materials. Smaller particles had higher radiocesium concentrations, reflecting larger specific surface areas. Silt- and sand-size fractions occupied more than 95 % of the total 137Cs in the suspended sediments. The contribution of clay-size fractions, which had the highest 137Cs concentration, was quite small because of their low frequency. A line of the data showed that the particle size distribution of radiocesium was essential to evaluate the migration and distribution of radiocesium in river systems where radiocesium is mainly present as particulate form after the FDNPP accident.

Tellurium, an element of growing economic importance, is extremely enriched in marine ferromanganese oxides. We investigated the mechanism of this enrichment using a combination of spectroscopic analysis and adsorption/coprecipitation experiments. X-ray Absorption Near-Edge Structure (XANES) analysis showed that in adsorption/coprecipitation systems, Te(IV) was oxidized on δ-MnO 2 and not oxidized on ferrihydrite. Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that both Te(IV) and Te(VI) were adsorbed on the surface of δ-MnO 2 and ferrihydrite via formation of inner-sphere complexes. In addition, Te(VI) can be structurally incorporated into the linkage of Fe octahedra through a coprecipitation process because of its molecular geometry that is similar to the Fe octahedron. The largest distribution coefficient obtained in the adsorption/coprecipitation experiments was for the Te(VI)/ferrihydrite coprecipitation system, and it was comparable to those calculated from the distribution between natural ferromanganese oxides and seawater. Our XAFS and micro-focused X-ray fluorescence (μ-XRF) mapping of natural ferromanganese oxides showed that Te was structurally incorporated as Te(VI) in Fe (oxyhydr)oxide phases. We conclude that the main process for the enrichment of Te in ferromanganese oxides is structural incorporation of Te(VI) into Fe (oxyhydr)oxide phases through coprecipitation. This mechanism can explain the unique degree of enrichment of Te compared with other oxyanions, which are mainly enriched via adsorption on the surface of the solid structures. In particular, the great contrast in the distributions of Te and Se is caused by their oxidized species: (i) the similar geometry of the Te(VI) molecule to Fe octahedron, and (ii) quite soluble nature of Se(VI). Coexisting Mn oxide phases may promote structural incorporation of Te(VI) by oxidation of Te(IV), although the surface oxidation itself may not work as the critical enrichment process as in the case of some cations. This enrichment mechanism also means that ferromanganese oxides mainly scavenge dominant Te(VI) species from seawater and do not affect its species distribution in seawater, as described in a previous model. The variation in Te abundances and the correlation of Te concentration with the growth rate of natural ferromanganese oxides are consistent with the coprecipitation mechanism.

Black-colored road dusts were collected in high-radiation areas in Fukushima Prefecture. Measurement of (236)U and Pu isotopes and (134,137)Cs in samples was performed to confirm whether refractory elements, such as U and Pu, from the fuel core were discharged and to ascertain the extent of fractionation between volatile and refractory elements. The concentrations of (134,137)Cs in all samples were exceptionally high, ranging from 0.43 to 17.7 MBq/kg, respectively. (239+240)Pu was detected at low levels, ranging from 0.15 to 1.14 Bq/kg, and with high (238)Pu/(239+240)Pu activity ratios of 1.64-2.64. (236)U was successfully determined in the range of (0.28 to 6.74) × 10(-4) Bq/kg. The observed activity ratios for (236)U/(239+240)Pu were in reasonable agreement with those calculated for the fuel core inventories, indicating that trace amounts of U from the fuel cores were released together with Pu isotopes but without large fractionation. The quantities of U and (239+240)Pu emitted to the atmosphere were estimated as 3.9 × 10(6) Bq (150 g) and 2.3 × 10(9) Bq (580 mg), respectively. With regard to U, this is the first report to give a quantitative estimation of the amount discharged. Appreciable fractionation between volatile and refractory radionuclides associated with the dispersal/deposition processes with distance from the Fukushima Dai-ichi Nuclear Power Plant was found.