Vol. 52 No. 11
November, 2003
Kaoru Ariyama1, Hiroshi Horita1 and Akemi Yasui1
1 National Food Research Institute, 2-1-12, Kannondai, Tsukuba-shi, Ibaraki 305-8642(Received 24 April 2003, Accepted 20 August 2003)
A method to quantify 22 inorganic elements in order to determination of the geographic origin of Welsh onion (Allium fistulosum L.) was established. A sodium extraction method with 1% HCl and an acid digestion method with HNO3/HClO4 and HNO3/HClO4/HF were studied and compared by using certified reference materials of Spinach Leaves and Apple Leaves. As a result, we applied a Na extraction method with 1% HCl and a HNO3/HClO4/HF digestion method to an inorganic elements measurement of Welsh onion. After analyzing different parts (lower, middle and upper, as well as outer and center) of Welsh onion, we decided to analyze a 10 cm part located in the lower part of Welsh onion and 22 elements. We determined Na by flame atomic absorption spectroscopy; Mg, P, K, Ca, Mn, Fe, Cu, Zn, Sr and Ba by ICP-AES; and Al, Co, Ni, Rb, Mo, Cd, Cs, La, Ce, Tl and Pb by ICP-MS in sample solutions. A principal component analysis using 22 elements for 47 Japanese and 15 Chinese samples showed a different tendency, and suggested that Chinese Welsh onions could be distinguished from Japanese ones.
Keywords : Welsh onion; geographic origin; inorganic elements measurement; principal component analysis; acid digestion.
Masae Inoue1, Atushi Murase1 and Motoyasu Sugiura1
1 Toyota Central R&D Labs. Inc., 41-1, Nagakute, Nagakute-cho, Aichi 480-1192(Received 9 July 2003, Accepted 3 September 2003)
Molecular ions include information about end groups, functional groups and molecular weight. A method for the directly detecting these of high mass area of more than 1000 from poly(dimethylsiloxane) (PDMS) on a solid surface was investigated. It was also found that a TOF-SIMS analysis of silver-deposited surfaces (silver deposition/TOF-SIMS) is useful for this purpose. Two methods for silver deposition, the diode sputtering method and the vacuum evaporation coating method, were tried. The former required the sample to be cooled so as to prevent damage of the sample surface due to thermal oxidation; the latter caused no damage to sample surfaces at room temperature. Using silver deposition/TOF-SIMS analysis, silver-cationized quasi-molecular ions were clearly detected from PDMS on solid surfaces, and their images were observed without the interference of deposited silver. By applying to the analysis of paint defects etc, it was confirmed that this technique is useful to analyze practical industrial materials. Silver-cationized ions were detected not only from PDMS, but also from other organic materials, such as lubricant additives and oils on solid surfaces. Therefore, silver deposition/TOF-SIMS was proved to be useful for the analysis of thin substances on solid surfaces.
Keywords : TOF-SIMS; silver deposition; silver cationization; molecular weight evaluation; poly(dimethylsiloxane).
Takashi Miyawaki1, Ayato Kawashima1 and Katsuhisa Honda1
1 Environmental Science for Industry, Faculty of Agriculture, Ehime University, 3-5-7, Tarumi, Matsuyama-shi, Ehime 790-8566(Received 11 July 2003, Accepted 6 September 2003)
Supercritical fluid extraction (SFE) with CO2 was applied to an analysis of Polychlorinated dibenzo-p-dioxins/Polychlorinated dibenzofurans (PCDD/DFs) in paddy soil. At a constant pressure of 30 MPa and a temperature of 70°C, elevating the moisture content in soil from 1.6% to 9.8%, resulted in enhancing the extraction efficiency of PCDD/DFs. In particular, the tendency was remarkable for highly chlorinated congeners of PCDD/DFs. A similar increase in the extraction efficiency was also found in Soxhlet extraction. These results indicate that moisture content in soil affected the extraction efficiency of PCDD/DFs with SFE and Soxhlet extraction. This was considered to be due to changing the adsorption form of PCDD/DFs in soil and/or playing a role as a modifier on the SFE, contributing to the extraction of PCDD/DFs from the soil.
Keywords : polychlorinated dibenzo-p-dioxins; polychlorinated dibenzofurans; supercritical fluid extraction; Soxhlet extraction; moisture.
Sachiko Wakasugi1, Miho Tanaka1 and Masaru Maeda1
1 Tokyo University of Fisheries, 4-5-7, Konan, Minato-ku, Tokyo 108-8477(Received 8 May 2003, Accepted 15 September 2003)
In order to estimate influences on the environment of the Miyake Island by sulfur compounds emitted by volcanic activity in 2000, volcanic ash of Mt. Oyama was washed with Mill-Q water. The contents and chemical forms of the sulfur, mainly originating in sulfur dioxide adsorbed on the ash, in the washed water were determined by ion chromatography and the turbidimetry using the precipitation of barium sulfate. Ion chromatography showed that the washed water contained only sulfate and chloride anions. The concentration of the sulfate ion dissolved in the washed water maintained the same value after hydrogen peroxide was added to it. By turbidimetry, sulfate ion was identified in the water. These results suggest that only the sulfate ion existed in the washed water. Most of the sulfate ion was extracted to the water immediately when the volcanic ash and the water were contacted. The pH values of the water also decreased immediately upon contact. Then, the concentrations of sulfate ion and proton, together, were slightly increased according to the contact time. By washing volcanic ashes with Milli-Q water, more than 23% of the total sulfur in the volcanic ash was quickly extracted out as the sulfate ion. This result suggested a possibility that the volcanic ash may result in serious problems involving the reconstruction of daily lives on the Miyake Island, e.g. to get the city water.
Keywords : sulfate ion; ion chromatography; turbidimetry; volcanic ashes; Miyake island.
Takahide Nishiyama1, Zilin Chen1,2, Tatsuro Nakagama1, Katsumi Uchiyama1 and Toshiyuki Hobo1
1 Department of Applied Chemistry, Graduate School of Engineering, Tokyo Metropolitan University, 1-1 Minamiohsawa, Hachioji-shi, Tokyo 192-0397(Received 8 May 2003, Accepted 19 September 2003)
An L-lysinamide-modified monolithic column has been prepared by a sol-gel process and chemical modifications, and used for the enantioseparation of dansyl amino acids by both modes of capillary electrochromatography (CEC) and micro-high performance liquid chromatography (µ-HPLC). The electroosmotic flow (EOF), separation conditions and enantioselectivity have been investigated. The chiral selector of L-lysinamide loaded with Cu(II) ion generates a strong EOF, probably due to the nature of lysinamide containing two amino groups in a molecule. Besides, the separation behaviors in CEC and µ-HPLC have been compared.
Keywords : chiral separation; capillary electrochromatography; monolithic column; dansyl amino acids; lysinamide.
Takashi Yarita1, Atsuko Nakama1, Masahiko Numata1, Yoshie Aoyagi1, Misako Yamazaki1 and Akiko Takatsu1
1 National Metrology Institute of Japan (NMIJ), National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba Central 3-10, 1-1-1, Umezono, Tsukuba-shi, Ibaraki 305-8563(Received 6 June 2003, Accepted 26 August 2003)
A rapid and accurate method for the determination of polychlorinated biphenyls (PCBs) in sediments was developed using pressurized fluid extraction (PFE) and isotope-dilution gas chromatography/mass spectrometry (ID-GC/MS). Four PCB congeners used as the target compounds could be quantified using an equation that has been used for describing the IDMS method. The PFE behavior of PCBs from a sediment sample was evaluated in terms of the extraction solvent, pressure and temperature, and the PFE conditions were established so as to provide a higher extraction efficiency, as follows: extraction solvent, hexane/acetone (1:1, v/v); extraction pressure, 15 MPa; extraction temperature, 150°C; static time, 30 min. Under these conditions, the recoveries of 13C12-labelled PCB congeners spiked onto the sediment sample were in the range of 79.5~86.8%, and no significant degradation of target PCB congeners was observed. The present method was then applied to an analysis of a certified reference material, 536 (PCBs in freshwater harbor sediment), supplied by the Community Bureau of Reference, and compared with those using Soxhlet extraction; the present method was suitable for the rapid and accurate determination of PCB congeners.
Keywords : polychlorinated biphenyls; sediment; isotope-dilution mass spectrometry; pressurized fluid extraction; gas chromatography/mass spectrometry.
Noboru Hiraki1, Akinori Isozaki2 and Hisomu Nagashima3
1 Tokyo Kaseigakuin high school, 22, Sanbanchou Chiyoda-ku, Tokyo, 102-8341(Received 24 July 2003, Accepted 3 September 2003)
A method for the determination of several inorganic anions containing thiocyanate has been developed for ion-pair chromatography (IP-HPLC) with a new C30 column, coupled with a UV detector at 220 nm. A phosphate buffer (pH 6.0) containing 2 mM tetrabutylammonium (TBA-Cl) in 15 (v/v)% acetonitrile was used as an optimal mobile phase for the separation of five anions (NO2-, NO3-, I-, S2O32- and SCN-). The five anions were efficiently separated within 15 minutes. The determination range of thiocyanate ion was to 40 mg/ml from 2.0 µg/ml, and the calibration curve were linear with excellent correlation coefficients of more than 0.999. The relative standard deviation at 20 µg/ml was under 0.2% based on 10 repeated measurements, and the limit of detection was 10 ng/ml(S/N=3). The method was applied to the determination of thiocyanate ion in human saliva and rat blood.
Keywords : C30-column; ion-pair chromatography with UV detection thiocyanate ion; human saliva and rat blood.
Hitoshi Yamaguchi1, Shinji Itoh1, Shin'ichi Hasegawa1, Kunikazu Ide1 and Takeshi Kobayashi1
1 Materials Analysis Station, National Institute for Materials Science, 1-2-1, Sengen, Tsukuba-shi, Ibaraki 305-0047(Received 24 July 2003, Accepted 3 September 2003)
We examined matrix masking methods for analyzing copper metal by ICP-OES using ion-exchange separation. In the ion-exchange separation of copper, it is vital to separate only those elements that are targeted. Therefore, the matrix was masked with ethylenediamine tetra-acetic acid (EDTA) to prevent it from being adsorbed by resin. After the copper metal was decomposed by heating with nitric acid and combined with EDTA, impurities were removed using a cation-exchange resin. The impurities attracted by resin adsorption were dissolved with nitric acid, and those detected were measured by ICP-OES. This method enabled the separation of matrix Cu by over 99.9%, and recovered more than 98% of aluminum, calcium and magnesium. The determined values of beryllium and manganese impurities, which are the components of a MBH CRM CB2 Cu-based alloy, were in good agreement with the certified values.
Keywords : ion exchange separation; elemental analysis; copper matrix; matrix masking reagent; ICP-OES.
Takeshi Saito1, Toshihide Ihara1, Hiroshi Sato1, Harald Jancke2 and Shinichi Kinugasa1
1 National Metrology Institute of Japan, AIST, Tsukuba Central 5, 1-1-1, Higashi Tsukuba-shi, Ibaraki 305-8565(Received 14 April 2003, Accepted 14 September 2003)
Quantitative nuclear magnetic resonance (NMR) has attracted much attention because quantitation with NMR is in principle traceable to the SI units. However, only few studies have been reported for accurate and precise NMR measurements. In this paper, a quantitation of aqueous ethanol, which was one of the intercomparison studies organized by Comité Consultatif pour la Quantité de Matiére, is described. Our result was within 0.2% of the reference value set by the pilot laboratory. An internal standard material used in this study was 3-Trimethylsilyl-2,2,3,3-tetradeutero propionic acid, Na salt (TSP). Peak integrations obtained with methyl signals showed much less scattering than those obtained with methylene signals of ethanol. The large scattering of methylene peak integrations in repeated experiments suggested that the baseline of the methylene resonance peak was disturbed by a strong water signal. The repeatability of NMR signal integration was less than 0.4%. From an analysis of the variance, the repeatability of the NMR area integration was as precise as mass measurements of sample preparations. Additionally, the data indicated the that combination of TSP and ethanol may not be sufficient for this study. An intercomparison study indicated that the accuracy of quantitative NMR is as good as that of quantitation performed with gas chromatography.
Keywords : nuclear magnetic resonance (NMR); quantitative NMR; ethanol; uncertainty; CCQM intercomparison.
Hiroshi Nakamura1, Masako Ueji1, Mariko Murayama1, Yoshitsugu Odanaka1, Toshihiro Nagayama1, Yasusuke Matsumoto1, Minoru Ishii1, Takahiro Fujikawa1, Masahiro Hanai1, Akira Tsuruta1, Kazutoshi Kakita1, Akihiro Ono1 and Mamoru Sakata1
1 The Japan Society for Analytical Chemistry, 1-26-2, Nishi-gotanda, Shinagawa-ku, Tokyo 141-0031(Received 24 June 2003, Accepted 23 August 2003)
The Japan Society for Analytical Chemistry has developed two new certified reference materials (CRMs) for the analysis of residual amounts of simazine and dieldrin in field soils. A study team has been organized to prepare 2 kinds of field soils by blending loan soil that contains simazine and former farmland soil that contains dieldrin. An interlaboratory comparison test, in which 22 laboraotries participated, was carried out. In a statistical analysis of all data, z-scores in robust method were applied to reject outliers, followed by the usual statistical procedure. The presented CRMs are expected to be useful for quality assurance and quality control in the analysis of residual pesticide in soils.
Keywords : field soil; residual pesticide; simazine; dieldrin; certified reference material.
Yuetsu Danzaki1 and Kazuaki Wagatsuma1
1 Institute for Materials Research, Tohoku University, 2-1-1, Katahira, Aoba-ku, Sendai-shi, Miyagi 980-8577(Received 7 April 2003, Accepted 14 September 2003)
It is relatively difficult to dissolve metallic Ru and Ru alloys by using acids; therefore, proper dissolution methods should be investigated for each Ru alloy. In general, the dissolution procedure should be selected depending on the elemental composition of the alloys. In addition, it should be noted that Ru oxide is easily volatilized by heating due to the low boiling point, possibly causing a serious loss of Ru. The following dissolution methods are recommended to obtain completely dissolved solutions as well as to prevent from the volatilization of Ru. Alloys containing Ru of less than 36% could be dissolved in proper acid mixtures. Al-Ru-Cu alloy samples and Ni-Al-Ru alloy samples could be dissolved by heating in HNO3:HCl:H2O=1:3:4 and HNO3:HCl:H2O=1:1:2, respectively. Ce-Sn-Ru alloy samples were dissolved in a mixed acid of HNO3:HCl:H2O=1:3:4, tartaric acid, and H2O2 at room temperature. Ru alloy samples that cannot be dissolved in any mixed acid need to be fused with a mixture of NaOH and Na2O2. The melts of Ru-Mn-Si alloy samples were dissolved with water, followed by the addition of HCl (1+1). Then residual MnO2 was dissolved by dropping H2O2, and white Zr oxide was filtered off. The melts of Mo-Ru-B alloy samples were dissolved in HNO3:HCl:H2O=1:3:4 and white Zr oxide was then dissolved by heating. The melts of Ce-Ru-Ge alloy samples were dissolved with water, and subsequently a mixed acid of H2SO4 (1+1), HNO3
Keywords : Ru alloys; dissolution method; alkaline fusion; ICP-OES.
Toshihide Ihara1, Kazuhiro Shikakume2, Satoko Otsuka1, Hiroko Ueno2, Kazuko Yoshimura1,3, Yoko Ohte1, Yasusuke Matsumoto2 and Akira Nomura1
1 National Metrology Institute of Japan, AIST, Tsukuba Central 3, 1-1-1, Umezono, Tsukuba-shi, Ibaraki 305-8563(Received 16 April 2003, Accepted 14 September 2003)
Keywords : CCQM inter-comparison; mutual recognition arrangement for calibration and measurement certificates; determination of ethanol in aqueous matrix; gas chromatography-flame ionization detection; uncertainty evaluation of chemical measurement.
Seiji Muratsu
Forensic Science Laboratory, Hyogo Prefectural Police Headquarters, 5-4-1, Shimoyamate-dori, Chuo-ku, Kobe-shi, Hyogo 650-8510
(Awarded by Himeji Institute of Technology dated March 26, 2003)
Synchrotron radiation was applied to analyze various forensic samples, mainly drugs of abuse. In the first study, an impurity profiling analysis of heroin and 3,4-methylenedioxymethamphetamine (MDMA) samples was presented by using total reflection X-ray fluorescence spectroscopy (TXRF) in our laboratory. After recognizing the utility of this technique, synchrotron radiation total reflection X-ray fluorescence spectroscopy was applied to analyze various trace elements in small amounts of drugs of abuse. By using the synchrotron radiation experimental system, pg amounts of each trace element in 10 mg of various drugs could be easily detected, which was not the case for a standard TXRF experimental system, or for other elemental analysis techniques. In the second study, high energy X-ray fluorescence spectroscopy was applied to analyze various heavy elements in small amounts of drugs of abuse. In the third study, a new imaging of forensic samples was performed by phase-contrast X-ray imaging method using synchrotron radiation. In the forth study, elemental mappings using an X-ray microbeam derived from synchrotron radiation were applied to analyze a meteorite. As a result, those techniques were shown to be very useful discrimination methods applicable to forensic samples, mainly drugs of abuse. The utilization of synchrotron radiation will open new application fields for forensic science.
(Received September, 5, 2003)
Keywords : synchrotron radiation; X-ray fluorescence analysis; total reflection; drugs of abuse; impurity profiling; phase-contrast X-ray imaging; forensic science.
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