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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...

A portable X-ray powder diffractometer (p-XRD) PT-APXRD III has been developed for onsite analysis of paintings and archaeological samples. By using a Cu anode X-ray tube and a silicon drift diode (SDD) detector, diffraction patterns with a high signalnoise (S/N) ratio can be recorded. The X-ray tube can be operated at a maximum voltage of 60 kV, which makes it possible to simultaneously record X-ray fluorescence spectra up to the high-energy region. The total weight of this instrument is 16 kg, which can be carried anywhere and the goniometer unit (5.6 kg) can be placed on a tripod for analysis of mural paintings. We brought the instrument to the Rijksmuseum in the Netherlands to examine its applicability for the analysis of oil paintings. We successfully analyzed two seventeenthcentury oil paintings by Johannes Vermeer and Jan Davidsz de Heem (copy after). Ultramarine blue, leadtin yellow type I, and Naples yellow were identified from the diffraction patterns, demonstrating the high practicality of this instrument. Furthermore, it was found from the SEM-EDX analysis of a paint cross section that the yellow pigment was applied in separate layers rather than being mixed. This diffractometer will be commercially available in the near future and will have many applications in the field of material analysis. (C) 2018 Elsevier B.V. All rights reserved.

This paper reports on how the application of macro X-ray fluorescence (MA-XRF) imaging, in combination with the re-examination of existing paint cross-sections, has led to the discovery of a new pigment in Rembrandt’s palette: artificial orpiment. In the NWO Science4Arts ‘ReVisRembrandt’ project, novel chemical imaging techniques are being developed and applied to the study of Rembrandt’s late paintings in order to help resolve outstanding questions and to gain a better understanding of his late enigmatic painting technique. One of the selected case studies is the Portrait of a Couple as Isaac and Rebecca, known as ‘The Jewish Bride’, dated c. 1665 and on view in the Rijksmuseum. During the re-installation of the Rijksmuseum in 2013, the picture was scanned using the Bruker M6 Jetstream MA-XRF scanner. The resulting elemental distribution maps made it possible to distinguish many features in the painting, such as bone black remains of the original hat (P, Ca maps), and the now discolored smalt-rich background (Co, Ni, As, K maps). The arsenic (As) map also revealed areas of high-intensity in Isaac’s sleeve and Rebecca’s dress where it could be established that it was not related with the pigment smalt that also contains arsenic. This pointed to the presence of a yellow or orange arsenic-containing pigment, such as realgar or orpiment that is not associated with the artist’s palette. Subsequent examination of existing paint cross-sections from these locations taken by Karin Groen in the 1990s identified isolated, almost perfectly round particles of arsenic sulfide. The round shape corresponds with published findings on a purified form of artificial orpiment glass obtained by dry processing, a sublimation reaction. In bright field, the particles characteristically exhibit a dark cross in the middle caused by internal light reflections. The results of additional non-invasive techniques (portable XRD and portable Raman) are discussed, as well as the implications of this finding and how it fits with Rembrandt’s late experimental painting technique.

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)

実験室レベルで高感度な分析が可能な三次元偏光光学系蛍光X線分析装置を用いて，コーヒー豆の微量元素を定量し，統計解析を行った．産地判別に有用な元素を明らかにし，簡易・迅速な産地判別法として確立することを目指した．産地の指標となる6元素（Mn，Fe，Ni，Rb，Sr，Ba）を高感度に分析するために測定条件を最適化した結果，各元素において直線性のよい検量線を作成することができ，各元素の検出限界は，サブppmレベルとなった．コーヒー生豆75試料中の6元素を定量し，主成分分析を行った結果，6産地（ブラジル，コロンビア，ベトナム，インドネシア，タンザニア，グアテマラ）の生豆を特性化することができた．また，同ロットの生豆と焙煎豆の各元素濃度を比較した結果，これらの6元素について大きな差は見られなかったため，今回の産地判別手法における焙煎の影響は小さいことが分かった．本手法では，試料の前処理は10分程度，測定時間は2時間30分であり，自動連続測定が可能であることから，簡易・迅速な実用性の高い分析手法として，コーヒー豆の産地判別への応用が更に期待される．

The analytical performance of a scanning electron microscopy-energy dispersive spectroscopy (SEM–EDS) system equipped with a transition edge sensor (TES) microcalorimeter (µ-cal) in forensic analysis is examined. The TES microcalorimeter shows much better energy resolution than the conventional solid-state detector (SSD). We solved some identification problems caused by peak overlaps when forensic samples were analyzed by a conventional SEM-EDS system based on SSD. The microcalorimeter ED spectrum can reveal the coexistence of Ba and S in a paint layer of an automotive white paint fragment containing TiO2 as pigment and this may indicate the existence of BaSO4. The coexistence of K, Mg, Al, Si and Ti in the surface layer suggests the use of titanium dioxide (TiO2)-coated mica as a pearlescent pigment in paint. GSR particles are successfully discriminated by detecting Ba, Sb, Pb and S. An elemental mapping function of the TES microcalorimeter system was introduced for the first time and revealed the accumulation of Pb- and Sb-rich particles in GSR. These results suggest that the microcalorimeter SEM–EDS system offers analysis with both high-energy resolution and high-spatial resolution at low-excitation voltages. These advantages are fully utilized as powerful analytical tools in forensic laboratories. Copyright © 2009 John Wiley & Sons, Ltd.

Blue-painted pottery was produced in the New Kingdom, Egypt, and decorated with blue, red, and black pigment. In this study, two newly developed portable instruments, a portable X-ray fluorescence spectrometer and a portable X-ray powder diffractometer, were brought to the site on the outcrop at Northwest Saqqara, an archaeological site in Egypt, to verify their performance in on-site analysis of excavated artifacts at the site. Pigments used for the blue-painted pottery and plasters in the New Kingdom were analyzed by these instruments on the basis of both their chemical compositions and crystal-structural information. The blue pigments were identified as two different pigments, Egyptian blue and cobalt blue. The diffraction pattern of the blue pigment of the painted pottery exhibited that of spinel structure. The XRF spectrum of the blue pigment obtained by the same instrument from the same position indicates the presence of Mn, Co, Fe, Ni, and Zn. The possibility of compositional transitions of the cobalt blue pigment with time was revealed on by detailed analysis of the XRF data. The reason for the transitions is considered together with the archaeological background of the New Kingdom, Egypt.

Suspended particulate matter (SPM) collected in the urban area of Tokyo was analyzed using a transition edge sensor (TES) microcalorimeter x-ray detector mounted on a FE-SEM system. This prototype microcalorimeter spectrometer with an energy resolution of 19 eV identified some severe peak overlaps in the spectra measured by the traditional Si(Li) solid state detector, including S Kα with Pb Mα, Zn Lα with Na Kα, and Ti Kα with Ba Lα. In addition, the TES microcalorimeter showed good spatial resolution for the microanalysis of SPM. The focused ion beam(FIB) was successfully applied to fabricate a cross section of a single SPM particle. The chemical compositonal difference between surface and inner parts, and among different surface parts of the SPM was also determined. Through combination of the FIB technique and the TES microcalorimeter, we achieved a better understanding of the SPM. Copyright © 2009 John Wiley & Sons, Ltd.

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.

A newly developed portable x-ray fluorescence spectrometer has been evaluated through the onsite and nondestructive analyses of 109 Roman glass artifacts excavated at a Roman cemetery found in Zadar, Croatia. The spectrometer has been designed for on-site analysis of archaeological glass objects. The instrument consists of an x-ray tube with a Pd target operated at up to 40 kV, silicon drift detector (SDD) with a polymer window, and an enlargeable vacuum sampling chamber. With this system, quantitative analysis of the light elements such as Na and Mg that are important components of glass, as well as heavy trace elements, was successfully carried out. The obtained results evidenced the use of Natron as fluxing agent with alkali contents of 14–22 wt% Na2O, 0.5 wt% MgO and 1.2 wt% Al2O3. In addition, it was found that the differences in the use of Mn and/or Sb as decolorizing agent in colorless bell-shaped flasks collected from 10 different localities along the coast of Croatia comparing with the same type flasks excavated from Zadar. Copyright © 2009 John Wiley & Sons, Ltd.

小麦粉の産地判別を目的として，蛍光X線分析法により小麦粉中の微量元素の高感度定量を試みた．三次元偏光光学系エネルギー分散型蛍光X線分析装置を用い，測定条件を最適化した結果，小麦粉中の17元素（Na，Mg，Al，P，S，Cl，K，Ca，Mn，Fe，Cu，Zn，Br，Rb，Sr，Mo，Cd）において直線性のよい検量線を作成することができた．本法はサブppmレベルの重元素の定量が可能であった．63試料の小麦粉の定量分析を行ったところ，国産と外国産・混合とで微量元素組成に異なった傾向がみられた．更に，産地の指標となると考えられた特定の元素の定量値を用いた多変量解析から，国産の小麦粉をほぼ正確に判別できる判別式を構築することができた．本研究により，迅速・簡便な蛍光X線分析が産地判別に有用であることを示すことができた．今後は，本法がその他の食品へと応用されるだけでなく，多検体の分析を要する食品の品質検査における実用的な分析法として利用されることが期待される．

Potassic-ferropargasite, ideally KCa2(Fe42+Al)Si6Al2O22(OH)2, is a new member of the amphibole group occurring in a schistose calcareous hornfels from Kabutoichiba, Kameyama, Mie Prefecture, central Japan. The amphibole occurs as black subhedral to anhedral crystals, up to about 700 μm long, associated with calcite, biotite, K-feldspar, plagioclase, scapolite, chlorite and titanite. Potassic-ferropargasite is optically biaxial negative with α = 1.680(2), β = 1.690 (calc.), γ = 1.698(2) and 2V = 80-90°. The mineral is monoclinic, space group C2/m, with refined unit-cell parameters a = 9.937(5), b = 18.108(5), c = 5.335(4) A, β = 105.30(3)°, V = 926.0(9) A3, Z = 2. The three strongest lines in the X-ray powder-diffraction pattern [d in A (I) hkl] are 2.72 (100) 151, 8.48 (81) 110 and 2.61 (59) 061. Electron-microprobe gave SiO2 38.08, TiO2 1.92, Al2O3 15.12, Cr2O3 0.44, FeO 19.96, MnO 0.22, MgO 6.22, CaO 11.73, Na2O 1.57, K2O 2.74, F 0.13, Cl not detected, O = F + Cl -0.05, total 98.08 wt%, corresponding to (K0.54Na0.42)Σ0.96(Ca1.95Na0.05)Σ2.00(Fe2+2.59Mg1.44Al0.67Ti0.22Cr0.05Mn0.03)Σ5.00(Si5.91Al2.09)Σ8.00O22(OH1.94F0.06)Σ2.00 on the basis of O = 23, assuming OH + F + Cl = 2. The crystal structure of the clinoamphibole type was refined to an R of 6.5%.

Rare earth carbonate hydroxides, RE(CO3)OH, were hydrothermally synthesized from formic acid and the hydroxide gels of Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, and Y. An orthorhombic phase with a kozoite-type structure was obtained for RE = Nd and Sm. Another orthorhombic modification of the kozoite-type structure was obtained for RE = Eu, Gd, Tb, Dy, Ho, Er, Tm, and Y. The latter phase has a lower symmetry (space group: P212121) in comparison to the true kozoite-type structure (Pnma). A new tetragonal phase (space group: P42/nmc) was found for RE = Tm and Yb. The crystal structures of RE(CO3)OH were refined for Pnma (RE = Nd and Sm), P212121 (RE = Eu, Gd, Tb, Dy, Ho, Er, Tm and Y), and P42/nmc phases (RE = Tm and Yb) using single-crystal X-ray diffraction intensity data. The distinct features of the differences among the three structures are the coordination numbers of the RE3+ ions: 10, 9, and 8 for the Pnma, P212121, and P42/nmc phases, respectively. A systematic comparison of the two orthorhombic structures revealed a dynamic variation in the coordination environment of the RE3+ ions accompanied by variations in their ionic radii. Although the interatomic RE—O distances tend to decrease with the lanthanide contraction, exceptions were observed for two of the RE—O distances. The mutual close proximity of CO3 2– anions caused by the lanthanide contraction led to repulsion between the CO3 2– anions, which decreased the symmetry of the configuration of CO3 2– anions around the central RE3+ ion, and some oxygen atoms of CO3 2– moved away from the first coordination shell of the RE3+ ions due to the elongation of the RE-O distances. The crystal structures of the tetragonal RE(CO3)OH are distinct from those of the orthorhombic phases. They consist of ladders of RE3+ ions 8-coordinated by the CO3 2– and OH– anions arranged in the form of a double cross. The powder XRD patterns of the tetragonal RE(CO3)OH are identical to that of a synthetic material previously reported as Tm6(OH)4(CO3)7.

野菜中の無機元素を簡便で高感度に定量するための蛍光X線分析法の開発を目的とした．その結果，三次元偏光光学系を採用したエネルギー分散型装置を用い，対象元素を高効率に励起できる二次ターゲットを選択し，発生する蛍光X線強度を散乱線で規格化することで野菜中のサブppm（μg g−1）レベルの重元素の分析が可能となった．本法を用いて群馬県産と岐阜県産のホウレンソウの分析を行ったところ，数% レベルの元素（K，Ca等）から数ppm程度の元素（Cd，Ba等）まで幅広い濃度範囲にわたる多元素を同時に定量できた．その結果，産地によりCa，Zn，Br，Rb，Mo，Ba等で含有量に違いが見られ，産地判別に応用できる可能性が示唆された．また，本法では，重元素の高感度分析が可能なことから，野菜中のCd含有量のスクリーニング検査としても有用であることが分かった．

Total reflection X-ray fluorescence spectrometry (TXRF) has been applied for trace elemental analysis of small glass fragments. A small glass sample (a fragment with weight less than 0.5 mg) was decomposed by 100 microg of HF/HNO3 acid; the material was condensed to 10 microl and was dried on a Si wafer. Since the size of the dried residue on the Si wafer was less than 1 cm in diameter, an incident X-ray beam with about 1 cm in width could effectively excite elemental components in such a small glass fragment. The precision of the present technique was checked by analyzing the glass fragments (0.5 mg) from NIST SRM612; the relative standard deviations (RSD) of less than 8.1% were achieved for elemental ratios that were normalized by Sr. Fragments (0.5 mg) obtained from 23 figured sheet glasses were used as samples for estimating the utility of this technique to forensic discrimination. Comparison of five elemental ratios of Ti/Sr, Mn/Sr, Zn/Sr, Rb/Sr, and Pb/Sr calculated from X-ray fluorescence spectra was effective in distinguishing glass fragments that could not be differentiated by their refractive indexes (RI).

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%.

This paper demonstrates that high-energy SR-XRF (synchrotron radiation x-ray fluorescence spectrometry) utilizing 116 keV x-rays is a powerful technique for nondestructive discrimination of small glass fragments. An XRF spectrum of glass fragments of a standard material SRM612 gave well-resolved K-line peaks of 34 elements, including the rare-earth elements. The relative standard deviations (RSD) of the ratios of the intensities of heavy elements normalized by that of Ba were less than 8.2% for the analyses of 10 fragments (

The measurement conditions for the precise analysis of the lead stable isotope ratio by using an ICP-MS equipped with a quadrupole mass spectrometer were studied in order to apply the technique to the forensic identification of bullet samples. The values of the relative standard deviation obtained for the ratio of 208Pb/206Pb, 207Pb/206Pb and 204Pb/206Pb were lower than 0.2% after optimization of the analytical conditions, including the optimum lead concentration of the sample solution to be about 70 ppb and an integration time for 1 m/z of 15 s. This method was applied to an analysis of lead in bullets for rifles and handguns; a stable isotope ratio of lead was found to be suitable for the identification of bullets. This study has demonstrated that the lead isotope ratio measured by using a quadrupole ICP-MS was useful for a practical analysis of bullet samples in forensic science.

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.

Fe K-XANES spectra of a series of pottery sherds excavated from the archaeological site of Kaman-Kalehoyuk, Turkey, were measured to reveal the firing technique of the pottery. The analysis disclosed relationships among the chemical form of the iron, the firing conditions and the colour of the pottery. The pottery referred to as ‘Grey Ware’ found at this site was classified into two groups according to the chemical form of the iron. Also, it was revealed that the Iron Age pottery referred to as ‘Cream Ware’ was produced first under reducing conditions, and then fired under oxidizing conditions.

A portable x-ray fluorescence spectrometer equipped with a silicon drift detector (SDD) and a digital signal processor (DSP) was developed for in-field analysis of archeological samples at an excavation site. This spectrometer allows us to carry out highly sensitive analyses of various elements with atomic numbers down to Na in air by using two monochromatic x-ray sources obtained by doubly bent toroidal monochromators of graphite (0002) (Pd Kα for medium–heavy elements) and PET (200) (Pd Lα for light elements) and white x-rays with a Zr filter excited at 40 kV for heavy elements. The detection limit was 0.31% for Al and 4 ppm for Sr in a standard cement sample. The spectrometer was set in a room of the excavation laboratory at al-Tūr Sinai in the Sinai Peninsula in Egypt in the summer of 2001. The Middle Eastern Culture Center has been conducting an excavation of the sites in al-Tūr al-Kilani and Rāya, which were important port cities of Red Sea trade from early Islamic periods: al-Tūr (A.D.14–20) and Rāya (A.D.8–12). The instrument was operated without any problems and 222 glass objects, 26 pottery sherds, seven pigments and 88 metallic objects were analyzed non-destructively during a 1 month stay. Since this was the first chemical analysis done at the sites, many important archaeological findings were obtained in the present study. Glass objects were successfully classified based on their chemical compositions. Characterization of stained (luster) glasses was conducted. Copyright © 2004 John Wiley & Sons, Ltd.

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.

放射光蛍光X線を用いて, 動物プランクトンの一種であるシオミズツボワムシ (Brachionus plicatilis) 1個体に含まれる微量元素の2次元分析, 定量分析を行った. その結果, 4日齢単性生殖雌の2次元元素分布からは, 胃にFe, Zn, 生殖器にはFe, Zn, Cu, Ca, 頭部にMnが局所的に濃集していることが分かった. これらの元素は, 餌であるクロレラに含まれていることから, 餌を摂取することによりワムシ体内に蓄積されることがICP-MSの定量分析結果からも得られた. 放射光蛍光X線によるMn, Cu, Znの定量分析の結果は, 複数個体を用いて硝酸分解後ICP-MS測定により求めて平均化した値と同じ挙動を示した. 放射光を用いることで, ワムシ1個体の微量元素分析が可能であることが本研究により実証できた.

High-energy (116 keV) synchrotron radiation X-ray fluorescence analysis has for the first time been applied to the quantitative analysis of trace heavy elements of geological samples. Calibration c...

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 .