Analytical Sciences
Online ISSN : 1348-2246
Print ISSN : 0910-6340
ISSN-L : 0910-6340
Volume 34 , Issue 6
Showing 1-19 articles out of 19 articles from the selected issue
Rapid Communications
Guest Editorial
Reviews
  • Yu-ki TANAKA, Takafumi HIRATA
    Type: Reviews
    2018 Volume 34 Issue 6 Pages 645-655
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Stable isotope composition varies due to different reactivity or mobility among the isotopes. Various pioneering studies revealed that isotope fractionation is common for many elements, and it is now widely recognized that the stable isotope compositions of biometals can be used as new tracers for element metabolism. In this review, we summarize the recently published isotope compositions of iron (Fe), copper (Cu), zinc (Zn), and calcium (Ca) in various biological samples, including tissues from plants, animals, and humans. Discussions were carried out with respect to age, sex, organ, and the presence or absence of particular diseases for animals and humans. For Fe and Cu isotopes, changes in oxidation states generate large isotopic fractionation through the metabolism of those elements. Isotope composition of Zn greatly fractionates among tissues even without changes in oxidation state. Isotopic composition of Ca is a powerful tracer for the metabolism of Ca in bones. The review results suggest that the stable isotope compositions of the biometals can be used as effective markers for diagnostics of various kinds of diseases related to metabolic disorders.

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  • Masaki OHATA, Kohei NISHIGUCHI
    Type: Reviews
    2018 Volume 34 Issue 6 Pages 657-666
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    A novel gas to particle conversion–gas exchange technique coupled with inductively coupled plasma mass spectrometry (GPD-GED-ICP-MS) was recently proposed for the direct analysis of ultra-trace levels of metallic compound gases such as metal carbonyl and semiconductor gases as well as gaseous mercury (Hg) in ambient air. These metallic compound gases should reveal reactivity with respect to ozone and gas to particle conversion could be obtained in a gas to particle conversion device (GPD) through metal oxides by oxidation. The particles converted were separated from non-reactive gases such as nitrogen, oxygen, carbon dioxide in ambient air by a gas exchange device (GED) and the particles in argon, otherwise ICP cannot be maintained, were directly introduced and measured by ICP-MS. Since the technique detects the metallic compound gas directly without any sampling methods, it is expected to be applied to real-time monitoring. This article highlights the research progress and novelty on GPD-GED-ICP-MS for the direct analysis of ultra-trace metallic compound gas. It was also noted that the direct analysis of gaseous Hg at the concentration level of a few ng m−3 in ambient air mentioned in this article was world-first achieved by GPD-GED-ICP-MS. The research progress for multi-element analysis in suspended particulate matter by GED-ICP-MS was also mentioned since the GED was always used for GPD-GED-ICP-MS.

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Original Papers
  • Masaharu TANIMIZU, Kazuya NAGAISHI, Tsuyoshi ISHIKAWA
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 667-674
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    We developed a method for rapid and precise determination of B isotope ratios by MC-ICP-MS through an optimization of washout method, mass-discrimination correction and chemical separation. Resultant reproducibility of δ11B values was ±0.4‰ (2 × SD) when a simple standard-sample bracketing technique was used, and it was improved to be better than ±0.2‰ by a mass discrimination correction with a 7Li/6Li isotopic reference. A mixed solution, which consists of HNO3–HF–mannitol, allowed a rapid washout of B memory in the sample introduction line. The validation of this technique to a wide range of δ11B value and various B signal intensities was confirmed from a series of B reference solutions with δ11B values of –20 to +40‰ and 25 to 125 ng/g B. Analyses of seawater standard (BCR-403) and carbonate standard (JCp-1) with sample sizes of less than 50 ng B gave δ11B values consistent with those determined by TIMS as Cs2BO2+. The simple and high-precision technique developed here is applicable to various types of commercially supplied multiple collector ICP mass spectrometers without any modification of the sample introduction system from their original instrumental setting.

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  • Michihiro AIMOTO, Shun-ichi HAYASHI, Kazuko YAMAMOTO, Masaki OHATA, Yu ...
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 675-679
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    A novel microwave-induced helium plasma optical emission spectrometry (He-MIP-OES) combined with a thermal hydrolysis sample introduction system was newly established for the determination of fluorine (F) compounds in slags. The MIP maintained through an Okamoto cavity was adopted, which was quite stable and provided a higher detection capability of F by helium plasma. The basic analytical performance of He-MIP-OES combined with an ultrasonic nebulizer for F analysis was also examined, and expected results could be obtained. The thermal hydrolysis behavior of CaF2, Ca4(Si2O7)(F,OH)2 and Ca5(PO4)3F, as known F chemical structures in slag, was also examined by thermal hydrolysis He-MIP-OES; F compounds in actual slag could be successfully identified and determined by this developed system.

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  • Yanbei ZHU, Kazumi NAKANO, Yasuyuki SHIKAMORI
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 681-685
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    A determination of rubidium (Rb) was carried out by isotope dilution (ID) using an inductively coupled plasma tandem quadrupole mass spectrometer (ICP-QMS/QMS) with an octupole reaction-cell (ORC). Spectral interference of 87Sr with the measurement of 87Rb was effectively removed by using fluoromethane (CH3F) as the reaction cell gas at the optimum flow rate. In comparison to the measurement obtained with a mathematical correction, good precision for the analysis of the Rb isotope could be obtained independent of the concentration of Sr without any chemical separation in advance. The usefulness of the present approach was confirmed by an analysis of Rb in multiple certified reference materials (CRMs) for food and environmental analysis, for which the results agreed with their certified values in the range of expanded uncertainty.

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  • Tomohiro NARUKAWA, Takahiro IWAI, Koichi CHIBA
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 687-691
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    The inorganic arsenic (i-As) in grape products, in particular juice, wine and raisins, collected from the Japanese market was investigated. The concentrations of total As in nine grape concentrated juices ranged from 3 to 20 ng g−1, and more than 80% of the As was inorganic according to the results of speciation by HPLC-ICP-MS. Among them, four samples contained more than 10 ng g−1 of i-As, although 10 ng g−1 of i-As is the limit for apple juice recommended by the U.S. Food and Drug Administration. Moreover, more than 10 ng g−1 of i-As was found in some of the wine and raisin samples, with the total As concentrations ranging from 17 to 37 ng g−1. When fresh grapes were analyzed, As was mainly concentrated in the pericarp and a small amount was found in the fruit, although no As was observed in the branches and the juice. When grapes, including the pericarp, are processed, the As concentration in the products may increase during production processes such as drying, concentration, and ripening.

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  • Koyo IDO, Hideyuki OBAYASHI, Yanbei ZHU, Takafumi HIRATA, Akiko HOKURA ...
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 693-699
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    A method was established for the quantitative analysis of the elements (Cu, Ag, Pb, and Sn) in solder samples by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), with Sn-based matrix matched standard solutions for defining the calibration curves. It was found that chloride-ion presented in commercially available Sn standard solution resulted in a precipitation of AgCl and caused the deterioration of the linearity of the calibration curve for Ag. Therefore, a laboratory-made chloride-free Sn solution was used to prepare Sn matrix matched standard solutions so as to ensure the stability of the elements including Ag. For the quantitative analysis of solder samples by LA-ICP-MS, the operating conditions of the LA instruments were set to obtain a fluence of over 12 J cm−2. This is mainly because of larger LA-induced elemental fractionations using a fluence of <10 J cm−2. The results for Ag, Cu, Pb, and Sn in a certified reference material (NMIJ CRM 8203-a) were close to, or in agreement with, the certified values, indicating that the present method was valid for the quantitative analysis of the elements in solder samples. In comparison to the certified values, relatively larger uncertainties were obtained for the analytical results by LA-ICP-MS, which could be attributed to the dependence on the homogeneity of the sample because the sample aliquots used for analysis were much smaller than those required for the traditional analytical procedures (i.e., sample quantity ratio of ca. 1:13000). Further improvement of the uncertainty might be obtained by using a larger sample quantity for the analysis by LA-ICP-MS so as to improve the representativeness of the sample.

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  • Yanbei ZHU, Kazumi NAKANO, Zhongyuan WANG, Yasuyuki SHIKAMORI, Koichi ...
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 701-710
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    The standard addition method (SAM) based on gravimetric sample preparation was investigated as an approach for the removal or cancelling of matrix effects in measurements by inductively coupled plasma mass spectrometry (ICP-MS). Deduction of the equations and experimental confirmation of the method are both given in the present work. After measuring both spiked and non-spiked samples by ICP-MS, the concentration of an element could be calculated based on the signal intensity ratio to an internal standard. A practical example was provided for the measurement of Fe in a certified reference material (CRM), i.e. NMIJ CRM 7512-a (milk powder). The validity of the method had been confirmed by the results of international comparisons with various kinds of matrix, including bioethanol, human serum, biodiesel fuel, drinking water, infant formula milk power, and seafood. The suggested method had been applied to measurements of multiple elements in three CRMs, including tap water, milk powder, and tea leave powder, respectively.

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  • Ka-Him CHUN, Hua ZHANG, Wing-Tat CHAN
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 711-717
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Double-viewing-position single-particle inductively coupled plasma–atomic emission spectrometry (DVP-SP-ICP-AES) measures emission intensity at two ICP vertical positions simultaneously using a single photomultiplier tube. A particle travelling up the ICP gives two consecutive temporal emission peaks. The Yb II 328.937-nm emission intensity of the two peaks for single Yb2O3 particles of diameter of 200 – 2000 nm are plotted against each other in a correlation plot. The correlation is poor when the gas temperature at the lower observation position is approximately the boiling point of the particles. Poor particle vaporization at the center of the central channel occurs because the gas temperature is 400 K lower than the temperature at the rim. The correlation is improved by shifting the observation positions up or using helium–argon mixed carrier gas to increase the gas temperature. Gas temperature is an important parameter for precise single particle-ICP measurements. DVP-SP-ICP-AES can be used to identify poor particle vaporization without the need of temperature measurement.

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  • Michihisa UEMOTO, Masanori MAKINO, Yuji OTA, Hiromi SAKAGUCHI, Yukari ...
    Type: Original Papers
    2018 Volume 34 Issue 6 Pages 719-724
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Minor and trace metals in aluminum and aluminum alloys have been determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) as an interlaboratory testing toward standardization. The trueness of the measured data was successfully investigated to improve the analytical protocols, using certified reference materials of aluminum. Their precision could also be evaluated, feasible to estimate the uncertainties separately. The accuracy (trueness and precision) of the data were finally in good agreement with the certified values and assigned uncertainties. Repeated measurements of aluminum solutions with different concentrations of the analytes revealed the relative standard deviations of the measurements with concentrations, thus enabling their limits of quantitation. They differed separately and also showed slightly higher values with an aluminum matrix than those without one. In addition, the upper limit of the detectable concentration of silicon with simple acid digestion was estimated to be 0.03 % in the mass fraction.

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Notes
  • Tomoki YABUTANI, Shingo KISHIBE, Miki KAMIMURA, Kosuke NOZOE, Yohei YA ...
    Type: Notes
    2018 Volume 34 Issue 6 Pages 725-728
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Herein, we determined the contents of Cu(I), Cu(II), and hydrophobic Cu in natural water using on-site sample treatment, solid-phase extraction (SPE), and inductively coupled plasma mass spectrometry (ICP-MS) analysis. To prevent Cu species changes in the sampling, filtering and preconditioning steps were performed in a closed system using plastic syringes and a disposable membrane filter. Bathocuproin disulfonate (BCS) and ethylenediaminetetraacetic acid (EDTA) were selected as a Cu(I)-selective complexing agent and a Cu(II) masking agent, respectively, whereas ascorbic acid (AA) was used to reduce Cu(II) to Cu(I). Pre-conditioned samples were passed through a hydrophobic SPE column, and the retained Cu species were eluted with ethanol. Subsequently, the eluate was concentrated, and the residue was re-dissolved in 2 M HNO3 and subjected to ICP-MS analysis. No artificial changes of Cu(I) and Cu(II) species were observed at any time, with the analytical detection limit of total Cu and the blank value equaling 0.0008 and 0.0025 μg kg−1, respectively. The developed method was applied to real estuarine, riverine, and seawater samples collected in Tokushima prefecture, Japan.

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  • Masaaki KASAMATSU, Takao IGAWA, Shinichi SUZUKI, Yasuhiro SUZUKI
    Type: Notes
    2018 Volume 34 Issue 6 Pages 729-733
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Since fragments of concrete can be evidence of crime, a determination of whether or not they come from the same origin is required. The authors focused on nitric acid-soluble components in the fragments of concrete. As a result of qualitative analysis with ICP-MS, it was confirmed that elements such as Cu, Zn, Rb, Sr, Zr, Ba, La, Ce, Nd, and Pb were contained in the fragments. After the nitric acid-soluble components in the fragments of concrete were separated by dissolving them in nitric acid, the concentrations of these elements in the dissolved solution were quantitatively determined by ICP-MS. The concentration ratios of nine elements compared to La were used as indicators. By comparing these indicators, it was possible to discriminate between the fragments of concrete.

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  • Junko SHIRATAKI, Kazuyuki FUJISAKI, Kouichi SAKAGUCHI, Nobuyuki SATO
    Type: Notes
    2018 Volume 34 Issue 6 Pages 735-738
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    ICP-QMS/QMS was applied to whole blood samples to determine the quantity of trace As. It was found that Fe also causes polyatomic interference with As in conventional ICP-QMS, in addition to Ca and Cl, and ICP-QMS/QMS can remove these interferences in mass-shift mode using O2 as reaction gas. The ICP-QMS/QMS technique allows the determination of As at sub-ng mL−1 levels.

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  • Daisuke SAKATE, Yoshiki IWAZAKI, Yoshiaki KON, Takaomi YOKOYAMA, Masak ...
    Type: Notes
    2018 Volume 34 Issue 6 Pages 739-742
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    The mass transfer of additive elements during the sintering of barium titanate (BaTiO3) ceramic was examined by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) in the present study. An analytical sample consisting of two pellets of BaTiO3 with different concentrations of additive elements of manganese (Mn) and holmium (Ho) as well as silicon (Si) as a sintering reagent was prepared and measured by LA-ICP-MS with small laser irradiated diameter of 10 μm to evaluate the distributions and concentrations of additive elements in order to examine their mass transfers. As results, enrichments of Mn and Si as an additive element and a sintering reagent, respectively, were observed on the adhesive surface between two BaTiO3 pellets, even though Ho did not show a similar phenomenon. The mass transfers of additive elements of Mn and Ho were also examined, and Mn seemed to show a larger mass transfer than that of Ho during the sintering process for BaTiO3 ceramics. The results obtained in this study shows the effectives of LA-ICP-MS for the future improvement of MLCCs.

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  • Kentaro YAMADA, Michihisa UEMOTO
    Type: Notes
    2018 Volume 34 Issue 6 Pages 743-746
    Published: June 10, 2018
    Released: June 10, 2018
    JOURNALS FREE ACCESS

    Relative sensitivity factors on glow discharge mass spectrometry were evaluated for unalloyed and alloyed metals of aluminum and magnesium using a glow discharge mass spectrometer operated with fast flow Grimm-type source. All the elements measured could be classified into two groups, i.e. a group of elements could be determined with repeatability equal to or less than 15% relative standard deviation, while another group could be determined with RSDs of greater than 15%. The latter is mainly due to the instability of discharge condition and elemental segregation onto certified reference materials.

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