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We performed micro-X-ray fluorescence imaging of frozen-hydrated sections of a root of Pteris vittata for the first time, to the best of our knowledge, to reveal the mechanism of arsenic (As) uptake. The As distribution was successfully visualized in cross sections of different parts of the root, which showed that (i) the major pathway of As uptake changes from symplastic to apoplastic transport in the direction of root growth, and (ii) As and K have different mobilities around the stele before xylem loading, despite their similar distributions outside the stele in the cross sections. These data can reasonably explain As reduction, axially observed around the root tip in the direction of root growth and radially observed in the endodermis in the cross sections, as a consequence of the incorporation of As into the cells or symplast of the root. In addition, previous observations of As species in the midrib can be reconciled by ascribing a reduction capacity to the root cells, which implies that As reduction mechanisms at the cellular level may be an important control on the peculiar root-to-shoot transport of As in P. vittata.

The striking sub-cellular distribution of cadmium (Cd) and zinc (Zn) in the Cd and Zn hyperaccumulator Arabidopsis halleri ssp. gemmifera was revealed by microbeam X-ray microfluorescence analysis (μ-XRF) using high-energy synchrotron radiation. Plants were grown in hydroponics with various Cd and Zn concentrations. The concentration of Cd in the aerial portions of the plants increased with increasing Zn exposure and the transportation efficiency of Cd from the root to the shoot was affected by both the Cd and Zn concentrations in the nutrient solution. The μ-XRF imaging clearly showed that Cd and Zn were preferentially accumulated in trichomes on the leaf, while the distribution of Cd in the leaf was changed by Zn treatment. It was observed that Cd treated with a higher Zn concentration (20 μM Cd + 100 μM Zn) was distributed in the mesophyll tissue at high concentrations. In addition, μ-XRF imaging clarified that the distribution of Zn inside the leaf was different from that of Cd at a cellular level. Zn was primarily distributed in the mesophyll tissue of the leaf blade. In contrast, Cd was localized in the vascular bundle of the main vein. That is, Zn was transported to mesophyll tissue from the vascular bundle more efficiently than Cd. As seen above, we were able to study the difference of the distribution of Cd and Zn, which are congeners and behave similarly, inside the plant body at the cellular level in detail by high-energy μ-XRF.

Synchrotron μ-XRF and autoradiography complementally revealed the different behavior of arsenic and phosphorus in Pteris vittata L. at a high spatial resolution in its living state. We found that P...

Synchrotron radiation (SR) X-ray microbeam analyses revealed the detailed chemical nature of radioactive aerosol microparticles emitted during the Fukushima Daiichi Nuclear Power Plant (FDNPP) accident, resulting in better understanding of what occurred in the plant during the early stages of the accident. Three spherical microparticles (∼2 μm, diameter) containing radioactive Cs were found in aerosol samples collected on March 14th and 15th, 2011, in Tsukuba, 172 km southwest of the FDNPP. SR-μ-X-ray fluorescence analysis detected the following 10 heavy elements in all three particles: Fe, Zn, Rb, Zr, Mo, Sn, Sb, Te, Cs, and Ba. In addition, U was found for the first time in two of the particles, further confirmed by U L-edge X-ray absorption near-edge structure (XANES) spectra, implying that U fuel and its fission products were contained in these particles along with radioactive Cs. These results strongly suggest that the FDNPP was damaged sufficiently to emit U fuel and fission products outside the containment vessel as aerosol particles. SR-μ-XANES spectra of Fe, Zn, Mo, and Sn K-edges for the individual particles revealed that they were present at high oxidation states, i.e., Fe(3+), Zn(2+), Mo(6+), and Sn(4+) in the glass matrix, confirmed by SR-μ-X-ray diffraction analysis. These radioactive materials in a glassy state may remain in the environment longer than those emitted as water-soluble radioactive Cs aerosol particles.

Gynura pseudochina (L.) DC. is a zinc (Zn)/cadmium (Cd) hyperaccumulative plant. The aim of this study was to examine the tolerance of G. pseudochina (L.) DC. for Zn and/or Cd accumulation and protein expression. An in vitro tissue culture system was used to control the environment and effects of the microorganisms. Treatments with higher Zn and Cd concentrations increased chlorosis and the accumulation of metals in the root and shoot. Cd treatment at low levels induced the growth of the plant, and the translocation factor was high. A dual treatment with Cd and Zn decreased the metals’ toxicity and demonstrated the plant’s proclivity to accumulate Cd. The SDS–PAGE and FT-IR analyses showed the effect of the metals’ toxicity on protein expression and secondary structure. Moreover, using XAFS techniques, it was demonstrated that treatment with a high Zn concentration (100 mg l −1 ) resulted in tetrahedral coordination with mixed S/O ligation in the protein extract as compared with Zn O coordination in the protein extract from the control plant cultured in the presence of trace levels of Zn (0.04 mg l −1 ). This research suggested that G. pseudochina (L.) DC. had properties to tolerate a high Zn and Cd concentration, related to the sulphur proteins.

Cobalt-blue colorant was first used in the 18th Dynasty in the New Kingdom of Egypt. The source of this cobalt was cobaltiferous alum from the Western Oases of Egypt. The use of this alum, especially in glass, was suddenly limited at the end of the 18th Dynasty. There is little evidence of the production of cobalt-blue glass in the Ramesside Period (the 19th–20th Dynasties) in the New Kingdom of Egypt. In this study, we brought a portable X-ray fluorescence spectrometer to two archaeological sites located in the Memphite region and used it for onsite analyses of Ramesside cobalt blue-colored glasses and faiences. This method revealed that the compositional characteristics of the cobalt-blue colorant in these Ramesside glasses and faiences is different from the colorant derived from cobaltiferous alum used in the 18th Dynasty, based on the comparison of transition metal composition and alumina content with those of the cobalt blue-colored artifacts from the 18th Dynasty. This result suggests that a new cobalt source other than cobaltiferous alum from the Western Oases was utilized in Egypt during the Ramesside Period.

Carbon-coated Na2FePO4F and Na2Fe0.5Mn0.5PO4F are successfully prepared by a simple solid-state method with ascorbic acid as carbon source. Crystal structure of Na2Fe0.5Mn0.5PO4F is found to be isostructural with Na2MnPO4F by an X-ray diffraction method, which has a three dimensional fluorophosphate framework. Scanning/transmission electron microscopy and Raman spectroscopy reveal that the addition of ascorbic acid effectively suppresses the particle growth of the samples, forming the nano-sized carbon coated materials. Electrode performance of Na2FePO4F is compared with that of Na2Fe0.5Mn0.5PO4F. The carbon-coated Na2FePO4F prepared with 2 wt% ascorbic acid delivers discharge capacity of 100–110 mAh g−1 at a rate of 1/20 C (6.2 mA g−1) with well-defined voltage plateaus at 3.06 and 2.91 V vs. Na metal. In contrast, Na2Fe0.5Mn0.5PO4F is less electrochemically active. The higher content of carbon by the adding ascorbic acid (6 wt%) and ball-milling treatment are necessary to achieve high reversible capacity. A well-optimized Na2Fe0.5Mn0.5PO4F sample delivers the discharge capacity of 110 mAh g−1 at a rate of 1/20 C (6.2 mA g−1), and it is first demonstrated that average operating voltage is higher than that of Na2FePO4F based on the possible Mn2+/Mn3+ redox couple centered at 3.53 V.

Soil and water contamination with chromium is an issue of recent concern in Thailand due to increases in industrial activity. Gynura pseudochina (L.) DC., a chromium tolerance plant, could be employed to address this problem via phytoremediation. To understand the tolerance mechanism, this study investigated the speciation and distribution of chromium accumulated in G. pseudochina (L.) DC. using AAS, XAFS, μ-XANES, μ-XRF imaging and EPR. The plants were separately treated with K2Cr2O7 and Cr2(SO4)3 in a hydroponic system. μ-XRF imaging clarified the distributions of Cr, Fe, Zn, Ca, Cl, K and S within the samples. In G. pseudochina (L.) DC. treated with Cr(VI) solution, the Cr was mainly distributed in the vascular bundle and periderm of the tuber, the stem xylem, the vein and the epidermis, including the trichome of the leaf tissues. This Cr distribution corresponded to those of Cu, Fe and Zn. In G. pseudochina (L.) DC. treated with Cr(III) solution, the Cr was distributed in the periderm of the tuber, the stem cortex, and the epidermis and parenchyma of the leaf tissues. μ-XANES and XAFS indicated that highly toxic Cr(VI) was reduced to the intermediate Cr(V) and accumulated as less toxic Cr(III), and EXAFS spectra showed that the reduced Cr(III) was bound to oxygen ligands. The coordination number (N) and the interatomic distance (R) to the first shell were approximately 3–4 (N) and 2 A (R), respectively. EPR spectra of the plant samples treated with Cr(VI) revealed the presence of Cr(V) and Cr(III). Thus, Cr(III) and Cr(VI) were taken up into the vascular system and transported from the roots to the leaves. Cr(III) was distributed via the symplast system to the ground tissue and accumulated mainly in the stem cortex. Cr(VI) was transported to the xylem via the apoplast system, and the adsorption of Cr(VI) and its reduction to Cr(V) and Cr(III) occurred on oxygen ligands in the lignocellulosic structure of the xylem and vein.

Carbon-coated Na2FePO4F is synthesized by a simple solid-state method with ascorbic acid as carbon source. Structural characterization of Na2FePO4F by synchrotron X-ray diffraction, scanning/transmission electron microscopy, and Raman spectroscopy reveals that ascorbic acid effectively suppresses the particle growth of Na2FePO4F, forming the nano-sized carbon coated materials. Electrode performance of Na2FePO4F for rechargeable sodium batteries is also examined. The carbon-coated Na2FePO4F sample (1.3 wt% carbon) delivers initial discharge capacity of 110 mAh g-1 at a rate of 1/20 C (6.2 mA g-1) with well-defined voltage plateaus at 3.06 and 2.91 V vs. Na metal. The sample also shows acceptable capacity retention and rate capability as the positive electrode materials for rechargeable Na batteries, which is operable at room temperature. Keywords: Na battery, Sodium insertion

Trees that accumulate metals are important plants for restoring contaminated soil because of their high biomass. We examined the cadmium (Cd) tolerance and growth rate of six willow (Salix) species common in Japan. To characterize in detail the localization of Cd and its ligands, synchrotron radiation-based micro X-ray fluorescence analysis was used. This revealed the accumulation of cadmium at the tips of the serrations in leaves, and the phellogen and/or the phelloderm under the stem surface. micro-X-ray absorption near edge structure spectra of Cd in all the accumulation sites were similar to that of the Cd ion coordinated by O ligands in S. gilgiana.

This paper reports on the distribution of Cd and essential elements in the stems of rice plants, 'Nipponbare' and 'Milyang 23', measured by synchrotron radiation micro-XRF imaging. X-ray absorption near edge structure (XANES) analysis was applied to estimate the chemical forms of Cd in the roots, stems and leaves, aiming to reveal the mechanisms of Cd transport in rice. The results show that the Cd concentration of 'Nipponbare' was found to be higher than that of 'Milyang 23' at the root, although there was no significant difference between these two cultivars at the shoot. In addition, the distribution of Cd and the essential elements inside the plant were clearly revealed by micro-XRF imaging. It was found that Cd was also localized to the bundle. The Cd K-edge XANES analysis indicated that Cd was bound to sulfur in the root for both rice plants. Furthermore, the content of Cd combining with S (Cd-S) in the stem of 'Nipponbare' became 1.5 times higher after exposing to Cd for a long time, while only a slight change in the stem of 'Milyang 23' was found. In contrast with the stem, the leaf of 'Nipponbare' contained a lower Cd-S content than that of the control after a long-term exposure, while that of 'Milyang 23' became higher. In conclusion, the difference in the chemical form of Cd at the shoots affected the different accumulation behaviors of Cd between 'Nipponbare' and 'Milyang 23'. (author)

The Raya port (eighth to 12th centuries) on the Sinai Peninsula, Egypt, was one of the important port cities for the Red Sea trade. We performed on-site analyses of Islamic glass vessels (used in eighth to 11th centuries) mainly from this site in Egypt using a portable XRF spectrometer. The aim of this paper is to contribute to our understanding of the chemical compositions of early Islamic glass vessels by comparing their archaeological date and typology. In the early Islamic period, glass objects were mainly produced from natron as the soda source. Among the natron glass analyzed in this study, glass vessels with low titanium and iron and high strontium contents, which were probably produced in the Syria–Palestine region, were excavated in the eighth century layer. From the ninth century layer, a large number of samples with high levels of calcium, titanium and iron, probably produced in Egypt, were found. It should be noted that a large number of glass vessels with this chemical composition were found at the Raya site, because this type of glass was rarely reported from other Islamic sites. We finally concluded that this type of glass seems to be produced under a fixed recipe, although some samples contain a colorant or decolorized materials.

To investigate the flow of the metal nutrients iron (Fe), zinc (Zn), manganese (Mn), and copper (Cu) during rice seed germination, we performed microarray analysis to examine the expression of genes involved in metal transport. Many kinds of metal transporter genes were strongly expressed and their expression levels changed during rice seed germination. We found that metal transporter genes such as ZIP family has tendency to decrease in their expressions during seed germination. Furthermore, imaging of the distribution of elements (Fe, Mn, Zn, and Cu) was carried out using Synchrotron-based X-ray microfluorescence at the Super Photon ring-8 GeV (SPring-8) facility. The change in the distribution of each element in the seeds following germination was observed by in vivo monitoring. Iron, Mn, Zn, and Cu accumulated in the endosperm and embryos of rice seeds, and their distribution changed during rice seed germination. The change in the patterns of mineral localization during germination was different among the elements observed.

Electrochemical activities of NaNi0.5Mn0.5O2 and NaCrO2, having the analogous layered structure to LiCoO2, were investigated in 1 mol dm-3 NaClO4 propylene carbonate at room temperature. Almost all sodium ions were extracted from the NaNi0.5Mn0.5O2 and NaCrO2 electrodes by galvanostatic oxidation to 4.5 V accompanied with several phase transitions. Layered NaNi0.5Mn0.5O2 electrode showed a highly reversible capacity of 185 mAh g-1 as positive electrode in Na cell in the potential region between 2.5 and 4.5 V versus Na. A NaCrO2 electrode was hardly electroactive after oxidation up to 4.5 V. When galvanostatic cycling was carried in the limited potential domain between 2 and 3.5 V, both electrodes showed discharge capacities of 100 - 120 mAh g-1 with satisfactory capacity retention. Layered LiCrO2 (R-3m) and NaCrO2 (R-3m) possess the quite similar crystal structures and the same transition metal, nevertheless they were inactive and active in Li and Na cells, respectively.

Layered metastable lithium manganese oxides, Li2/3[Ni1/3−xMn2/3−yMx+y]O2 (x = y = 1/36 for M = Al, Co, and Fe and x = 2/36, y = 0 for M = Mg) were prepared by the ion exchange of Li for Na in P2-Na2/3[Ni1/3−xMn2/3−yMx+y]O2 precursors. The Al and Co doping produced the T#2 structure with the space group Cmca. On the other hand, the Fe and Mg doped samples had the O6 structure with space group R-3m. Electron diffraction revealed the 1:2 type ordering within the Ni1/3−xMn2/3−yMx+yO2 slab. It was found that the stacking sequence and electrochemical performance of the Li cells containing T#2-Li2/3[Ni1/3Mn2/3]O2 were affected by the doping with small amounts of Al, Co, Fe, and Mg. The discharge capacity of the Al doped sample was around 200 mAh g−1 in the voltage range between 2.0 and 4.7 V at the current density of 14.4 mA g−1 along with a good capacity retention. Moreover, for the Al and Co doped and undoped oxides, the irreversible phase transition of the T#2 into the O2 structure was observed during the initial lithium deintercalation.

The Japan Society for Analytical Chemistry has developed some new plastic certified reference materials (CRMs) for the analysis of mercury in polyester disks using XRF analysis. These CRMs (named as JSAC 0621 - 0625) were prepared by casting polyesters including a toluene solution of organometallic compounds as a standard. Concentrations of the five levels of mercury ranged from 0 to 250 mg/kg. Homogeneity tests of prepared disks had shown excellent results. Interlaboratory comparison study for the certification was performed by 15 laboratory participants. The z-scores in robust statistical method was applied for the evaluation of outliers. The certified values were assigned after discarding outliers. The uncertainties of certified values were determined as the confidence levels of 95%.

モエジマシダ（Pteris vittata L.）は，ヒ素を高濃度に蓄積する能力をもつことから，実際にファイトレメディエーションへ応用されつつある植物である．このモエジマシダの根に放射光蛍光X線分析を適用することで，伸長方向に沿ったヒ素の分布と価数を初めて明らかにした．試料の前処理として凍結乾燥を施すことで，X線分析におけるハンドリングを容易にし，測定では縦300 μmと垂直方向に集光する一方で，横2800 μmと水平方向に大きなビームを照射した．以上により，根のうねりや形状の影響を排除して根の伸長方向における元素分布と複数の元素の相関を評価することが可能となった．その結果，根の先端から基部に向かって，カリウムの濃度はほぼ一定であるのに対し，ヒ素の濃度は相対的に高くなることが明らかとなった．またヒ素の価数は，先端では3価の存在が支配的であったが，基部に向かうと次第に5価が支配的になることが分かった．

The origin of the ruby color of Satsuma glass, a famous copper-ruby glass produced in Japan in the mid-19th century, has been examined by electron microprobe analysis (EPMA), X-ray absorption fine structure (XAFS), and optical absorption spectroscopy analyses. CuK XAFS analysis reveals that the major component of copper in the ruby glass consists of Cu(I) ions in the glass structure. This species is distinct from Cu2O (cuprite), which we conclude is not responsible for the ruby color. Optical absorption spectra measured at 300 and 77 K clearly distinguishes the absorptions due to the colloidal particles of metallic copper and Cu2O. It is concluded that the trace amount of copper in the ruby glass, which is below the detection limit of the EPMA and XAFS techniques, exists as metallic copper particles of nanometer size and is responsible for the ruby-red appearance of the Satsuma glass.

Lithium-chromium-manganese oxides, LiMn x Cr 1-x O 2 (0 < x< 0.6), were synthesized as solid solutions by simple calcination of emulsion-dried powder precursor. The product was well crystallized to an α-NaFeO 2 structure (space group: R3m). By combination of Rietveld analysis of X-ray diffraction data and X-ray absorption near edge structure (XANES) techniques, the final product is considered to be [Li 1 ] oct 3a [Mn III x CrIII 1-x ] oct 3b [O 2 ] 6c (0 < x < 0.6). The prepared oxides were electrochemically active, and capacity as cathode materials for lithium-ion battery was improved with increasing Mn substitution amount.

Total reflection X-ray fluorescence analysis (TXRF) has been successfully used to determine trace amounts of Cisplatin platinum in biopsy samples. The minimum detection limit of Pt by TXRF analysis using monochromatic Mo Kα radiation with a LiF (200) crystal was 0.01ppm, and the minimum quantification limit was 0.1ppm for the biological samples. Biopsy tissues and blood serum samples were taken from patients with advanced bladder cancers. Variations of Pt concentration at tumor tissue and in blood serum of the patient with time were clarified for both types of samples. This study indicates that TXRF is a most suitable technique for the analysis of trace platinum in biopsy samples.

Synchrotron radiation-induced X-ray fluorescence (SR-XRF) analysis was applied to examine the distributions and chemical forms of trace titanium in samples of banded iron formations (BIFs) from the Hamersley area of Western Australia. SR-XRF imaging and XANES (X-ray absorption near edge structure) analysis showed that titanium-enriched layers in the BIFs contained two types of titanium compounds: Ti in silicate and titanium oxides. All the compounds were in the tetravalent state. The difference between the two types of compounds may reflect different origins: i.e., the oxide phase may be precipitated from the solutions and the silicate phase may come from clastic input of terrigenous origin. SEM observation revealed peculiar spherical aggregates that contained manganese carbonate, suggesting a possible relation to biological activity.

Spinel lithium manganese oxides LiMn 1.6 M 0.4 O 4 (M=Mn, Co, Cr, Ni) for the cathode materials of the lithium ion secondary batteries were studied by electron energy loss spectroscopy (EELS). The ELNES spectra at Mn L- and O K-edge of the extracted lithium or substituted to Mn 16d site with third cations were successfully obtained. Electrochemically deintercalated Li 1− x Mn 2 O 4 showed a chemical shift of both Mn L- and O K-edges to the higher energy side compared with those of the stoichiometric LiMn 2 O 4 indicating oxidation of Mn and O due to the electrochemical deintercalation of Li. Substitution of M for Mn (M=Co, Cr, Ni) also caused a similar spectral shift of Mn L- and O K-edges. These shifts suggest lowering of the energy levels of the inner atomic orbitals compared with that of LiMn 2 O 4 .

Chemical states and structural changes accompanying the electrochemical Li deintercalation of Li1−x(Mn, M)2O4 (M=Cr, Co, Ni) were studied by the in situ X-ray absorption fine structure (XAFS) technique. The X-ray absorption near-edge structures (XANES) of Mn and M as a function of x showed that the high voltage (∼5 V) in the cathode materials of an Li secondary battery is due to the oxidation of M3+ to M4+ (M=Cr, Co) and M2+ to M4+ (in the case of M=Ni), while the origin of the low voltage (3.9–4.3 V) can be ascribed to the oxidation of Mn3+ to Mn4+. The extended X-ray absorption fine structure (EXAFS) analysis of Li1−x(Mn,Ni)2O4 revealed that Ni2+ is oxidized to Ni4+ via the Ni3+ state with a Jahn–Teller distorted Ni3+–O octahedron.

Synchrotron radiation-induced X–ray fluorescence (SR–XRF) and conventional X-ray fluorescence (XRF) analyses were applied to determine the distributions of iron, manganese, calcium, titanium, and silicon, and chemical forms of iron and trace manganese in three banded iron formation (BIF) samples. The XRF imagings on the weathered and altered BIF from the Cleaverville Formation (3. 3–3. 1 Gyr), Western Australia, showed redistributions of iron, calcium, and manganese with the disappearance of the primary bandings, while, in contrast, titanium preserved its primary depositional distribution. The XRF imagings on the BIF from the Hamersley Group (2. 5 Gyr), Western Australia, showed that manganese and titanium distribute originally at boundary region between the iron-rich mesoband and the silica-rich mesoband. The X-ray Absorption Near Edge Structure (XANES) analysis revealed that the chemical forms of manganese and iron well represent the rhythmic change of the bandings.

Effect of the elevated temperature and that of the lithium deintercalation on the structure of stoichiometric material LiMn 2 O 4 and lithium excess material Li(Mn 1.85 Li 0.15 )O 4 were investigated by in situ XAFS technique. The stoichiometric material showed capacity loss after charge–discharge cycles at 60°C and gave deformed XAFS spectra, while the lithium excess material showed resistance to the high-temperature cycling and gave a similar XAFS spectra to the non-heated material. The XAFS analysis suggests that high-temperature cycles caused structural disorder of LiMn 2 O 4 , but not that of Li(Mn 1.85 Li 0.15 )O 4 . Since the lithium excess material has good structural stability against the cycling at the elevated temperature, this material will be suitable for the cathode material of the commercial batteries.

An electrochemical cell was developed for the in situ transmission X–ray Absorption Fine Structure measurements of the charge/discharge process of the cathode materials of lithium secondary batteries, from which Li can be electrochemically deintercalated or intercalated. The dynamical structural behavior of Mn in Li(Mn 1.93 Li 0.07 )O 4 , and Li(Mn 1.85 Li 0.15 )O 4 as a function of both excess Li content and the Li deintercalation was revealed using the in situ cell. The analysis disclosed the coexistence of two MnO 6 –coordination polyhedra with different Mn–O distances for the Mn 3+ and Mn 4+ ions at the 16d site of the spinel structure. Because the charge–discharge process accompanies the oxidation–reduction of the Mn ions, this size difference causes an unfavorable lattice distortion for the electrode materials which can cause a loss of cell capacity after cyclic use of the cell. A partial substitution of Li for Mn will diminish this effect and will be favorable for the battery material.

The fluorescence XAFS (X–ray absorption fine structure) technique using synchrotron radiation was applied to characterize zinc in the Hg–Zn, Cd–Zn, and Bi–Zn coprecipitates, and to elucidate the reaction mechanism of the coprecipitation of zinc from a strong acidic solution. Hg LII–, Cd K–, and Bi LIII–edge XAFS spectra suggested that the respective host materials of the coprecipitates listed above are metacinnabar (HgS), greenockite (CdS), and bismuthinite (Bi2S3) and that existence of zinc has not affected the local structure of the host metal sulfides in each system. On the other hand, the Zn K–edge XAFS spectra of each coprecipitate indicated that the chemical forms of zinc compounds are controlled by the crystal structure of the host sulfides.The shapes of the Zn K–XAFS spectra of the Hg–Zn and Cd–Zn coprecipitates showed a strong resemblance to those of crystalline standards ZnS, wurtzite and spharelite. It was suggested that the two coprecipitated phases (HgS, ZnS) and (CdS, ZnS) may form a solid solution in the Hg–Zn and Cd–Zn coprecipitates. The local structure around the zinc(II) ion in the Bi–Zn coprecipitate is the same as that around hexaaqua–zinc(II) ions, and adsorption of soluble ions or mechanical occlusion from the mother liquor is regarded as a driving force of coprecipitation in the Bi–Zn system.

Distribution of trace elements such as Cu, Se, and Zn in human kidney was examined by use of nondestructive synchrotron radiation X-ray fluorescence (SR-XRF) imaging technique. All elements measured were more accumulated in the renal cortex than in the medulla. The renal Cu and Zn distributions obtained by SR-XRF imaging were consistent with those obtained by inductively coupled plasma atomic emission spectrometry (ICP-AES). Furthermore, correlation analysis based on the X-ray intensity data of each analytical point showed a positive correlation of the distribution of these elements.

Layered NaNi(0.5)Mn(0.5)O(2) (space group: R ̅3m), having an O3-type (α-NaFeO(2) type) structure according to the Delmas' notation, is prepared by a solid-state method. The electrochemical reactivity of NaNi(0.5)Mn(0.5)O(2) is examined in an aprotic sodium cell at room temperature. The NaNi(0.5)Mn(0.5)O(2) electrodes can deliver ca. 105-125 mAh g(-1) at rates of 240-4.8 mA g(-1) in the voltage range of 2.2-3.8 V and show 75% of the initial reversible capacity after 50 charge/discharge cycling tests. In the voltage range of 2.2-4.5 V, a higher reversible capacity of 185 mAh g(-1) is achieved; however, its reversibility is insufficient because of the significant expansion of interslab space by charging to 4.5 V versus sodium. The reversbility is improved by adding fluoroethylene carbonate into the electrolyte solution. The structural transition mechanism of Na(1-x)Ni(0.5)Mn(0.5)O(2) is also examined by an ex situ X-ray diffraction method combined with X-ray absorption spectroscopy (XAS). The staking sequence of the [Ni(0.5)Mn(0.5)]O(2) slabs changes progressively as sodium ions are extracted from the crystal lattice. It is observed that the original O3 phase transforms into the O'3, P3, P'3, and P3" phases during sodium extraction. XAS measurement proves that NaNi(0.5)Mn(0.5)O(2) consists of divalent nickel and tetravalent manganese ions. As sodium ions are extracted from the oxide to form Na(1-x)Ni(0.5)Mn(0.5)O(2), nickel ions are oxidized to the trivalent state, while the manganese ions are electrochemically inactive as the tetravalent state.

Lithium-excess manganese layered oxides, which are commonly described by the chemical formula zLi(2)MnO(3)-(1-z)LiMeO(2) (Me = Co, Ni, Mn, etc.), are of great importance as positive electrode materials for rechargeable lithium batteries. In this Article, Li(x)Co(0.13)Ni(0.13)Mn(0.54)O(2-δ) samples are prepared from Li(1.2)Ni(0.13)Co(0.13)Mn(0.54)O(2) (or 0.5Li(2)MnO(3)-0.5LiCo(1/3)Ni(1/3)Mn(1/3)O(2)) by an electrochemical oxidation/reduction process in an electrochemical cell to study a reaction mechanism in detail before and after charging across a voltage plateau at 4.5 V vs Li/Li(+). Changes of the bulk and surface structures are examined by synchrotron X-ray diffraction (SXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), and time-of-flight secondary ion mass spectroscopy (SIMS). SXRD data show that simultaneous oxygen and lithium removal at the voltage plateau upon initial charge causes the structural rearrangement, including a cation migration process from metal to lithium layers, which is also supported by XAS. This is consistent with the mechanism proposed in the literature related to the Li-excess manganese layered oxides. Oxygen removal associated with the initial charge on the high voltage plateau causes oxygen molecule generation in the electrochemical cells. The oxygen molecules in the cell are electrochemically reduced in the subsequent discharge below 3.0 V, leading to the extra capacity. Surface analysis confirms the formation of the oxygen containing species, such as lithium carbonate, which accumulates on the electrode surface. The oxygen containing species are electrochemically decomposed upon second charge above 4.0 V. The results suggest that, in addition to the conventional transition metal redox reactions, at least some of the reversible capacity for the Li-excess manganese layered oxides originates from the electrochemical redox reaction of the oxygen molecules at the electrode surface.

The dynamics of the brain distributions of Hg, Zn, Cu and Se in guinea pigs exposed to methylmercury and selenium were examined by X-ray fluorescence imaging utilizing synchrotron radiation. Male Hartley guinea pigs were administered methyl mercury chloride and/or sodium selenite every day for ten days (s.c. 3mg as Hg/kg/day, mole ratio Hg:Se=1:1). Two dimensional distributions of Hg, Zn, Cu and Se in guinea pig brain were observed by nondestructive X-ray fluorescence imaging. Using the

The comprehensive characterization of As(V)-bearing iron minerals from the Gunma iron deposit, which were probably formed by biomineralization, was carried out by utilizing multiple synchrotron radiation (SR)-based analytical techniques at BL37XU at SPring-8. SR microbeam X-ray fluorescence (SR-mu-XRF) imaging showed a high level of arsenic accumulation in the iron ore as dots of ca. 20 microm. Based on SEM observations and SR X-ray powder diffraction (SR-XRD) analysis, it was found that arsenic is selectively accumulated in strengite (FePO4 x 2H2O) with a concentric morphology, which may be produced by a biologically induced process. Furthermore, the X-ray absorption fine structure (XAFS) analysis showed that arsenic in strengite exists in the arsenate (AsO4(3-)) form and is coordinated by four oxygen atoms at 1.68 angstroms. The results suggest that strengite accumulates arsenic by isomorphous substitution of AsO4(3-) for PO4(3-) to form a partial solid-solution of strengite and scorodite (FeAsO4 x 2H2O). The specific correlation between the distribution of As and biominerals indicates that microorganisms seems to play an important role in the mineralization of strengite in combination with an arsenic-accumulating process.

Structure analysis of unilamellar manganese oxide nanosheets obtained via exfoliation of layered manganese oxides was carried out utilizing synchrotron radiation (SR) X-ray in-plane diffraction and polarization-dependent total reflection fluorescence X-ray absorption fine structure (PTRF-XAFS) analyses. A combination of SR excitation and the total reflection of incoming X-rays provides signals strong enough for both analyses even from a monolayer of the MnO(2) nanosheets having a concentration of 0.7 microg cm(-2). In addition, the mean oxidation state of constituent manganese ions in the MnO(2) sheets was estimated on the basis of XANES spectra, and bond valence sum calculations with the bond length obtained from the present EXAFS analyses. The obtained structural data revealed that the two-dimensional lattice of the MnO(2) sheets underwent a slight elongation upon delamination. These changes correspond to approximately 1% expansion of sheet area and 1-2% expansion of thickness, which can be understood by reduction of the mean oxidation number of manganese ions in the sheet through the exfoliation process.

Marine mammals and seabirds tend to exhibit high accumulations of mercury, cadmium, and selenium in their livers and kidneys. In this study, chemical forms of mercury, cadmium, and selenium accumulated in the livers and kidneys of northern fur seal (Callorhinus ursinus), Risso's dolphin (Grampus griseus), and black-footed albatross (Diomedea nigripes) were studied by extended X-ray absorption fine structure (EXAFS) spectroscopy to reveal the detoxification mechanisms of these metals. It was found that mercury and selenium exist in the form of HgSe in the liver of northern fur seal. Mercury levels were found to be higher than those of Se, based on their molar ratio, in black-footed albatross. XAFS analysis disclosed an existence of chalcogenide containing both Hg-Se and the Hg-S bonds, suggesting the existence of a solid solution Hg(Se, S) as granules in black-footed albatross. In contrast, Cd concentrations in the kidney were higher than those in the liver for northern fur seal, black-footed albatross, and Risso's dolphin. It was found that Cd was bound to sulfur, which was probably derived from the metallothionein. The Cd-O bond was observed in the tissues of northern fur seal.

We have directly observed the early process of arsenic transfer in the leaf tissue of hyperaccumulator fern (Pteris vittata L.) within 12 h after the arsenic feeding, by utilizing a synchrotron rad...

The monochromatic X-ray (37 keV) focused to microbeam (3 × 3 μm2) with a Fresnel zone plate allows us for the first time to measure a cellular distribution of cadmium in the cadmium hyperaccumulati...

X-ray fluorescence XAFS technique was successfully applied to the archaeological study to find colorant elements in old glass samples and to characterize the chemical states of iron in the ceramic sherds excavated from an archaeological site in Turkey. The origin of red color of the mosaic glass is found to be due to the colloidal copper particles in the glass. Blue color is attributed to divalent cobalt. Fe K-XANES spectra revealed that the color of the sherds changes from black, gray, brown, to orange with increasing the absorption edge energy. The gray ceramics typical for Phrygia age were produced in a reducing condition. The cream color of the central Anatolian Iron Age could not be related with the oxidation state of iron.

Marine mammals accumulate mercury in their tissues at high concentration and detoxify by forming mercury selenide (HgSe, tiemannite) mainly in the liver. We investigated the possibility of formation of HgSe in various tissues (liver, kidney, lung, spleen, pancreas, muscle and brain) other than the liver of the striped dolphin (Stenella coeruleoalba). We applied a combination method of micro-X-ray fluorescence (μ-XRF) imaging and micro-X-ray diffraction (μ-XRD) using a synchrotron radiation X-ray microbeam to analyze the tissue samples directly with minimal sample preparation. By this method, many accumulation points for Hg and Se on a micron scale were found in thin sections of the spleen and liver tissue and consequently, the XRF spectra and the XRD pattern of the hot spots confirmed the presence of tiemannite, HgSe. On the other hand, the insoluble fractions after enzyme digestion of the nuclear and mitochondrial fractions of all tissues were subjected to X-ray absorption fine structure (XAFS) analysis. XAFS analysis confirmed the presence of HgSe in all the tissues examined (liver, kidney, lung, spleen, pancreas, muscle and brain) of the striped dolphin. The presence of HgSe in all the tissues examined suggests that Se would be involved in the detoxification process of Hg in various tissues other than the liver. This contribution seems to be large especially in the liver and spleen but relatively small in the kidney, pancreas and brain, because the proportion of insoluble fraction containing HgSe was lower in these tissues (25 to 46%). This is the first report on the presence of tiemannite HgSe in various tissues of marine mammals.

In vivo X-ray analysis utilizing synchrotron radiation was performed to investigate the distribution and oxidation state of arsenic in the gametophytes of two hyperaccumulators, Pteris vittata L. and Pteris cretica L., and an arsenic-accumulating fern, Athyrium yokoscense in the several growth stages from germination. The distribution of arsenic in P. vittata changed through the development of the plant tissues as follows. In two-week-old gametophyte, arsenic was mainly present along the rhizoid. In the one-month-old gametophyte with reproductive organs, arsenic was accumulating uniformly in the sheet of cells, except in the reproductive area. After fertilization, arsenic was observed in the aboveground part of the sporophyte structures. P. cretica and A. yokoscense showed different distributions, respectively. P. cretica showed an accumulation of arsenic in the reproductive area, in contrast to P. vittata, before fertilization, while arsenic was observed in the aboveground part of the sporophyte after fertilization. A. yokoscense showed an accumulation of arsenic along the rhizoids before fertilization, while it was present mainly along the roots of the sporophyte after fertilization. Reduced arsenic (As(iii)) was observed in all stages and in all tissues of P. vittata gametophytes. Further, a reduction of arsenic was commonly observed among the three ferns, although arsenic was bounded to sulfur in A. yokoscense. These findings may be related to their own reproductive process or to detoxification mechanism. They provide basic information for the understanding of arsenic hyperaccumulation in these ferns, leading to further application of these gametophyte systems.

Monochromatic high-energy X-rays (37 keV) focused into a microbeam (3.8 × 1.3 μm2) with a Kirkpatrick-Baez mirror allows us for the first time to reveal the striking sub-cellular distribution and the chemical form of cadmium in the cadmium hyperaccumulating plant, Arabidopsis halleri ssp. gemmifera, by detecting the Cd Kα line. Micro X-ray fluorescence analysis (μ-XRF) and micro X-ray absorption near-edge structure analysis (μ-XANES) were used for the nondestructive analysis of the Cd distribution and chemical form of Cd at a cellular level in the plant in order to investigate the Cd accumulation mechanism. It was clearly observed by two-dimensional μ-XRF imaging that Cd was highly accumulated in a part of the trichomes, epidermal hairs existing on the surface of the leaves. The bases of the trichomes contained Cd, Zn and Mn at high concentrations and their distribution patterns were similar to each other. These elements were located near the surface of the trichome in the form of a ring. The μ-XANES analysis revealed that the majority of the Cd exists in the divalent state and bound to the O and/or N ligands. This study has demonstrated the potential of the Cd K-edge μ-XANES spectroscopy, which was applied here for the first time to plant samples.

The catadromous migration of freshwater eels, in which they migrate from freshwater streams to the sea to spawn1, is widely accepted. The proportion of time spent in freshwater and ocean habitats can be determined by studying the ratio of strontium (Sr) and calcium (Ca) in the otoliths (ear-stones) of the eels. Here we use this technique to show that Atlantic and Pacific eels collected in the ocean have spent their entire lifetime there and have never migrated into fresh water. This finding indicates that freshwater eels need not be catadromous, and that populations from the sea contribute primarily to future recruitment.

Nb 2 O 5 exhibits various crystal systems, such as orthorhombic (o), tetragonal (t), and monoclinic (m), among which Nb 2 O 5 synthesized at 900-1000°C is commercially used as a cathode material of the 2-V lithium ion battery. The battery performances depended on the structure of Nb 2 O 5 , and the t-Nb 2 O 5 synthesized at 1000°C exhibited an excellent cycling performance with a large discharge capacity of 190 mAh (g oxide) -1 . The structural variations of Nb 2 O 5 during electrochemical reaction were examined. The in situ synchrotron radiation-X-ray diffraction (XRD) measurement indicated that o- and t-Nb 2 O 5 maintain their original crystal lattices, accompanying a small change in the cell volume even after the Li intercalation. The in situ X-ray absorption fine structure (XAFS) analysis of o- and t-Nb 2 O 5 revealed that the continuous variation from Nb 5+ to Nb 4+ took place during the intercalation process. A significant rearrangement of the Nb-O octahedra accompanied by the change of Nb-O and Nb-Nb interactions occurred in both structures with Li intercalation. XRD and XAFS data suggests that the two-dimensional layer structure of t-Nb 2 O 5 seems to be more flexible regarding the Li intercalation compared with the three-dimensional structure of o-Nb 2 O 5 . This may account for the better cyclic performance of the former material as the electrode material.

The arsenic distribution in the arsenic hyper-accumulating fern (Pteris vittata L.) was investigated using a synchrotron X-ray fluorescence microprobe. Fronds of various ages were subjected to XRF imaging analysis, and it was found that the arsenic distribution in the pinnae of fronds changed according to their stage of growth. The focused microbeam (3.5 × 5.5 μm2) produced by Kirkpatrick–Baez optics was applied to the fern in order to determine the elemental distribution in plant tissue and cell levels. The results indicated that high levels of arsenic accumulate at the base of sporangium with lamina of pinnae. Also, the fern was subjected to X-ray absorption near edge structure (XANES) analysis without any sample treatment to directly elucidate the arsenic oxidation state in fern. It was found that arsenic exists as the As(III) form in pinnae, and as a mixture of As(III) and As(V) in rachis, while As(V) is present in cultivated soil. These findings indicate that the fern uptakes arsenic as As(V) from soil and that the As(V) is then partially reduced to As(III) within the plant, with the arsenic finally accumulating as As(III) in a specific area of the pinna.