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We have started to construct a nationwide forensic soil sediment database for Japan, based on the heavy mineral and trace heavy element compositions of stream sediments collected at 3024 points across Japan. The data were measured by high-resolution synchrotron radiation X-ray powder diffraction (SR-XRD) and high-energy SR X-ray fluorescence analysis (XRF) using the SR source of SPring-8, the SR radiation facility in Japan. The automated sampling systems allow the measurement of 130 powder diffraction patterns and 100 XRF spectra per day using sediment samples of just a few milligrams, which enabled us to construct a database of a large number of samples. The concentrations of heavy elements such as rare earth elements, Cs and W up to 500 ppm level in soil sediments can be determined by the calibration curve method by using high-energy SR-XRF utilizing monochromatic X-rays of 116 keV. A heavy element concentration map superimposed on a geographical map of Japan was successfully prepared from these analytical data. The heavy mineral compositions were quantitatively evaluated by using the peak intensity of characteristic XRD peaks of the component minerals measured by a Debye–Scherrer camera having a radius of 286.5 mm, recorded with an imaging plate and monochromatic X-rays (λ = 1.0 A). This study demonstrates that XRF and XRD data collected from the sediments of Shizuoka Prefecture closely reflect the geological and geographical signature of the sediment samples, which can be used for the provenance determination of soil evidence from a crime scene. Copyright © 2013 John Wiley & Sons, Ltd.

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.

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.

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.

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 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.

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.

The crystal structure of Na3Sb7O9Se3·Sb0.319(H2O,OH)3 has been determined using a single crystal prepared by hydrothermal synthesis to a conventional R = 0.043, Rw = 0.039 for 1556 reflections. It is hexagonal with a space group of P63; a = 14.422(4), c = 5.5448(8) A, Z = 2. The structure consists of infinite tunnels formed by the linkages of SbO3 pyramids. SbSe3 pyramids among the tunnels connect the tunnels to form a three-dimensional structure. Na atoms were on the inside wall of the tunnel. It was revealed that statistically occupied Sb(H2O,OH)6-octahedra are located at the center of the tunnel. Two statistical sites for the Sb atom of the SbSe3 pyramids are pointed out.

Forms of iron in leaves of wild-type tomato (Lycopersicon esculentum Mill. cv. Bonner Beste) and of the nicotianamine-free mutant, chloronerva, were analysed by X-ray absorption near-edge structure (XANES). The XANES spectra of the wild-type leaf veins and of the interveinal areas of leaves of both wild-type and chloronerva had a lower edge energy than the spectrum of the chloronerva leaf veins. This decrease may be caused by the presence of ferrous iron. Thus nicotianamine may play an important role in maintaining iron in the ferrous form in the veins of tomato leaves. Copyright © 2000 John Wiley & Sons, Ltd.

A multi-purpose analyzer was developed to carry out x-ray fluorescence (XRF) analysis of micro-samples and total reflection x-ray fluorescence (TXRF) analysis of environmental samples using either conventional x-ray or synchrotron radiation as an excitation source. Cosmic dust samples collected in Antarctica were successfully analyzed using a conventional x-ray source. XRF spectra of 36 cosmic dust samples were measured automatically using a combination of specially designed software and a sample holder, and trace amounts of heavy elements (10 ppm level in the sample) were detected. The potential ability of the XRF analyzer in TXRF mode using synchrotron x-rays from a third-generation light source, SPring-8, was tested using a standard river water and arsenic-containing water as samples. Satisfactory linearity of concentration versus net intensity of As was obtained in the concentration range 100 fg–100 ng with a detection limit of 10 fg. Copyright © 1999 John Wiley & Sons, Ltd.

Single crystals of a recently described metal oxide sulfide mineral sarabauite and three related oxide-sulfides of alkaline earths and antimony were hydrothermally synthesized. (1) CaSb10O10S6: color, carmine red; crystal system, monoclinic; space group, C2/c. (2) Compound in Sr–Sb–O–S system (O S), reddish orange, triclinic P1 or P\bar1. (4) Compound in Ba–Sb–S–O system (O

Die kurzlich neu dargestellte Titelverbindung kristallisiert in der Raumgruppe Pbnm mit Z=8.

Some varieties of zircon which contain yttrium, niobium, and phosphorus in solid solution have been synthesized at temperatures 500–550 °C and under pressures 700–1000 kg/cm2. In zircon containing yttrium, the unit cell constants a and c increase with increase in yttrium content up to 70 mol%. From IR and TGA studies, a valence compensation accompanying the substitution of yttrium is assumed to be effected by a concomitant substitution of OH for O sites, and the variety is represented by a formula (Zr,Y)Si(O,OH)4. On the other hand, the substitution of Nb5+ for Zr4+ is followed by a decrease in the cell constants. Zircon phase did not form from starting materials with more than 20 mol% of niobium content. From the syntheses of zircon containing both yttrium and niobium, the formula (Zr,Y,Nb) Si(O,OH)4 is found to be appropriate for naegite. An attempt was made to synthesize some solid solutions between zircon and xenotime. The unit cell constant c of the products is found to decrease with the substitution...

Three new La–Sb chalcogenides were synthesized by hydrothermal or evacuated silica tube methods. (1) LaSbO2S2: a bright-red needle crystal; crystal system, hexagonal; space group, P63/m; lattice constants, a=14.954(3), c=3.898(2) A, and Z=6. (2) La6Sb8S21: a blackish-red columnar crystal with metallic luster, orthorhombic, P222, a=14.317(2), b=15.239(4), c=8.685(1) A, and Z=2. (3) La3Sb3S10: a bright-red platelike crystal, monoclinic, a=13.209(6), b=14.229(6), c=5.583(1) A, β=94.54(3)°, and Z=2.